EP2459369A1 - Solar mirror film composite having particularly high weathering and uv stability - Google Patents
Solar mirror film composite having particularly high weathering and uv stabilityInfo
- Publication number
- EP2459369A1 EP2459369A1 EP10721769A EP10721769A EP2459369A1 EP 2459369 A1 EP2459369 A1 EP 2459369A1 EP 10721769 A EP10721769 A EP 10721769A EP 10721769 A EP10721769 A EP 10721769A EP 2459369 A1 EP2459369 A1 EP 2459369A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- weight
- layer
- film composite
- solar
- 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- Withdrawn
Links
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004609 Impact Modifier Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical group CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- RTNVDKBRTXEWQE-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-butan-2-yl-4-tert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O RTNVDKBRTXEWQE-UHFFFAOYSA-N 0.000 description 1
- WOUPGSLKKQVWQN-UHFFFAOYSA-N 2-[4-hydroxy-3-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-1-yl]butanedioic acid Chemical compound OCCC1C(N(C(CC1O)(C)C)C(CC(=O)O)C(=O)O)(C)C WOUPGSLKKQVWQN-UHFFFAOYSA-N 0.000 description 1
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 1
- ISDGWTZFJKFKMO-UHFFFAOYSA-N 2-phenyl-1,3-dioxane-4,6-dione Chemical compound O1C(=O)CC(=O)OC1C1=CC=CC=C1 ISDGWTZFJKFKMO-UHFFFAOYSA-N 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- XVKLGCDWSRXKNR-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CCCCCOC(=O)C=C XVKLGCDWSRXKNR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- IUKQLMGVFMDQDP-UHFFFAOYSA-N azane;piperidine Chemical compound N.C1CCNCC1 IUKQLMGVFMDQDP-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- GOJOVSYIGHASEI-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) butanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCC(=O)OC1CC(C)(C)NC(C)(C)C1 GOJOVSYIGHASEI-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical class C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
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- 239000013500 performance material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
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- 238000006748 scratching Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical class OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- 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
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- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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- 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
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
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- 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
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- 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
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2804—Next to metal
Definitions
- the invention relates to a film composite and its application as a mirror film in solar reflectors under the background of the most sustainable possible guarantee of the required reflection of solar radiation (total solar reflection).
- the invention relates to the use of cover films based on polymethyl (meth) acrylate (PMMA) in the film composite, with a particularly high UV stability and high weathering stability. Furthermore, the invention relates to a UV and weather protection package for said solar mirror film, as they are used in
- the invention further relates to a surface treatment. Scratch resistance, antisoil and
- cover film is synonymous with a surface coating layer
- the wavelength spectrum of solar radiation relevant for "solar thermal energy” ranges from 300 nm to 2500 nm.
- the range below 400 nm, in particular below 375 nm, should be filtered out in order to extend the service life of the solar mirror film, so that the "effective wavelength range" of 375 nm or 400 nm to 2500 nm remains.
- the reflectance of the flexible mirror film laminates in this application is determined by the quality and durability.
- Such a laminate is made by vacuum evaporation of a flexible polymer film (carrier film) with a thin
- Silver layer produced. Due to the particularly high reflectivity in the relevant wavelength range compared to other metals, silver is the preferred metal for this application.
- Silver layer to protect against external influences it is additionally coated with a protective layer.
- a protective layer which is usually a cover film for surface treatment, is the protection against mechanical abrasion, weathering and degradation by UV radiation.
- Such a protective system for aluminum mirrors is described in US 4,307,150.
- carrier film a PET laminate is used, which is vapor-deposited with aluminum and protected by gluing a (meth) acrylate film against corrosion and weathering. An explicit UV protection is not considered.
- 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, small holes or insufficient tightness will be sufficient at the edge of the laminate to cause unwanted oxidation.
- both silver and aluminum have an absorption gap in the spectral range of the ultraviolet light (300-400 nm), in particular in the range around a wavelength of 320 nm, which is an important part of the sunlight. 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, in particular for mostly used polyester films or laminates or the adhesive used for the production of laminates, especially in the case of prolonged exposure, as is the case in the field of solar mirrors. 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, even a reduced one
- UV absorbers alone do not contribute to the corrosion protection of
- the vaporized layer contains no lubricant to ensure the smoothest possible surface.
- the inner (meth) acrylate layer contains between 0.5 and 2.5% by weight glycol dimercaptoacetate, which acts as a dispersant, coupling reagent, adhesion promoter and inhibitor.
- the outer (meth) acrylate layer contains a UV absorption reagent, which is active in radiation with a wavelength between 300 nm and 400 nm. The two-layer structure further precludes corrosion of the silver by the UV absorption reagent.
- the uncoated side of the polyester laminate is with a PSA
- Poly (meth) acrylate coating can then be used for the described degradation of the
- Polyester laminate come.
- US 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 surface, but steamed on the side facing away from the light with silver.
- a poly (meth) acrylate protective film is attached, which is equipped with UV absorption reagents. The doctrine that a long-lasting UV protection equipment is needed is not considered in WO 2007/076282.
- 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.
- PSA pressure-sensitive adhesive
- poly (meth) acrylate film for UV protection is it is a Korad ® film from SPARTECH PEP.
- This film has the disadvantage that "benzotriazoles” are used as UV absorbers, which have only a comparatively “short” intrinsic stability under UV radiation influence and thus - in said application - no effective UV protection for the adhesive layer and the associated polyester support film represent.
- the Korad films analogous or similar poly (meth) acrylate films have for use as surface protection films of plastic molded parts for various reasons
- UV absorbers In the film laminates for solar mirrors which were previously available on the market, exclusively UV absorbers of the benzotriazole type were introduced for stabilization against UV rays in the cover film. These UV absorbers are sold, for example, under the trademark Tinuvin 234 by Ciba Specialty Chemicals Inc. These UV absorbers are known to last for a period of 5 to 10 years Significantly lose effectiveness, which degrades the surface coating layer. This results in a significant decrease in the solar reflection of the solar mirror film composite.
- the object was to provide a novel solar mirror film composite for solar reflectors with improved or at least equivalent optical properties and improved weathering resistance, especially with regard to a long-term use, compared with the prior art.
- Long-term use is understood to mean in particular an application over a period of more than 10 years, in particular more than 15 years, particularly preferably more than 20 years.
- the object was that the film composite for
- the more stable film composite should be as color-neutral and moisture-stable as possible.
- the film composite should be scratch-resistant and have dirt-repellent properties.
- This film composite consists of at least the following layers: a cover film, a carrier film, a metal layer and a pressure-sensitive adhesive layer.
- a cover film is a PMMA-based film
- the carrier film is a polyester film
- the metal layer is a silver layer.
- an adhesive layer is additionally applied underneath the cover film and a migration barrier layer and / or a primer below the metal layer.
- This film composite is preferably in listed order from the later outside to the PSA layer which is bonded to a carrier material, comprising at least the following layers: a cover film, a carrier film, a metal layer and a pressure-sensitive adhesive layer.
- a cover film preferably a cover film, a carrier film, a metal layer and a pressure-sensitive adhesive layer.
- an adhesive layer is additionally applied between the cover film and the carrier film, and a migration barrier layer and / or a primer is applied between the metal layer and the pressure-sensitive adhesive.
- the novel composite film is characterized by a very high stability, in particular UV stability, even under continuous irradiation.
- the cover sheet contains at least one triazine as UV absorber and a UV stabilizer.
- UV absorbers consisting of at least one triazine and at least one benzthazole.
- the UV stabilizer is a HALS compound or a mixture of different HALS compounds.
- Thazine-based UV absorbers have a particularly high intrinsic resistance under the influence of UV radiation.
- Stability is understood at the same time as the inherent stability of the cover film against UV and weathering effects and the stability of the UV protection effect, for example, from obtaining the solar reflection.
- the cover film may preferably contain between 0.1% by weight and 10% by weight, preferably between 0.2% by weight and 6% by weight and particularly preferably between 0.5% by weight and 4% by weight of the benzotriazole type UV absorbers,
- UV stabilizers preferably UV stabilizers of the HALS type.
- the cover sheet containing the mixture of UV stabilizers and UV absorbers, of poly (meth) acrylate and polyvinylidene fluoride in a weight ratio between 1 to 0.01 and 1 to 1, preferably between 1 to 0.1 and 1 to 0 , 5 be composed.
- the cover sheet comprises two layers. One layer is a layer of poly (meth) acrylate and the other is a layer of polyvinylidene fluoride (PVDF).
- PVDF polyvinylidene fluoride
- the PVDF layer is preferably the layer located on the surface of the film composite.
- the cover film has a thickness in the range from 10 ⁇ m to 200 ⁇ m, preferably in the range from 40 ⁇ m to 120 ⁇ m, particularly preferably in the range from 50 ⁇ m to 90 ⁇ m.
- the cover sheet used according to the invention is optionally scratch-resistant, preferably by a coating to increase the scratch resistance.
- the surface of the cover sheet can also be equipped with an anti-siding coating.
- the inventive novel film composite has the following properties, in combination as an advantage over the prior art, especially with regard to optical properties, on:
- the transparent portion of the film composite according to the invention is particularly neutral in color and does not cloud when exposed to moisture.
- the film composite exhibits excellent weathering resistance and, if optionally equipped with a PVDF surface and / or a scratch-resistant finish, very good resistance to chemicals, for example against all commercially available cleaning agents. These aspects also contribute to maintaining solar reflection over a long period of time.
- the surface has dirt-repellent properties.
- the surface is optionally abrasion-resistant and / or scratch-resistant.
- the film composite according to the invention finds particular application as a mirror film in sun reflectors.
- Pressure-sensitive adhesive layer causes.
- the film composite according to the invention is distinguished by its markedly improved UV stability compared with the prior art and the associated longer service life.
- 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.
- the long-lived solar reflector equipped with the film composite according to the invention has a maximum decrease of 8%, preferably a maximum decrease of 5% and more preferably a maximum decrease of 3%, with respect to the solar reflection within 10 years.
- cover sheets for the UV protection of the mirror film composites constructed according to the invention which are ideally used, correspond to the UV protection films disclosed in WO 2007/073952 (Evonik Röhm) or in DE 10 2007 029 263 A1.
- these films may have the components briefly outlined below. A more complete description can be found in WO 2007/073952.
- cover films used according to the invention are PMMA-based films.
- the films are not limited to pure methacrylate compositions
- the PMMA may contain in the films comonomers, which are not methacrylates.
- the films may be composed of blends of various plastics which need not contain all methacrylates.
- the films may additionally have a polybutyl acrylate elastomer content for Schlähma modification.
- the cover sheet may 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 general, these mixtures contain at least 40% by weight,
- Polymethylmethacrylaten further (meth) acrylates containing, with
- Methyl methacrylate are copolymerizable.
- 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 which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates.
- These include, inter alia, 1-alkenes, such as hexene-1, acrylonitrile;
- Vinyl esters such as 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.
- cover films used in the invention also have large
- the components used such as the UV stabilizers and UV absorbers, enable the economical operation of an extrusion line. For example, outgassing does not occur during film extrusion. Thus, complex and quality-related cleaning processes can be saved.
- the PMMA-based film used in the invention can be any PMMA-based film used in the invention.
- Impact modifier included. A more detailed description of these impact modifiers can also be found in WO 2007/073952.
- PVDF polyvinylidene fluoride
- cover film instead of pure methacrylate films, PMMA / PVDF films can also be used as the cover film.
- PVDF polyvinylidene fluoride
- PVDF has high chemical resistance and low surface energy.
- PVDF is water-repellent and shows almost no fouling, even with long-term use, comparable to antibiocidal materials.
- Very thin PVDF layers with a layer thickness between 1 .mu.m and 10 .mu.m, preferably between 2 .mu.m and 5 .mu.m, can also be realized with a high degree of transparency.
- a detailed description of the production of PMMA / PVDF films can be found in DE 10 2007 029 263 A1.
- the PMMA / PVDF films can be obtained in one layer (production by means of a chill-roll process) or in multiple layers (production by lamination of two films or coextrusion of the corresponding melt layers), both variants being able to realize all the advantages mentioned in the product.
- the UV stabilizers and / or UV absorbers can be contained in one or both films.
- PVDF polymers used in the context of the invention are polyvinylidene fluorides, which are generally transparent, partially crystalline, thermoplastic fluoroplastics.
- Polyvinylidene fluoride is vinylidene fluoride, which is reacted (polymerized) in highly pure water under controlled pressure and temperature conditions by means of a special catalyst to polyvinylidene fluoride.
- Vinylidene fluoride is, for example, from the base materials
- PVDF Chlorodifluoroethane accessible.
- 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 stabilizer package (sunscreen)
- UV stabilizer package A particular constituent of the UV protective films used according to the invention is the UV stabilizer package, which will be described in more detail below.
- UV absorbers are well known and are described in detail, for example, in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th edition, 2001, pp. 141 et seq.
- 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,
- UV stabilizers / radical scavengers The best known representative of UV stabilizers / radical scavengers is the group of hindered amines (Hindered Amine Light Stabilizer;
- the stabilizer package used in the films used according to the invention consists of the following components:
- Component A a benzotriazole type UV absorber
- Component B a triazine-type UV absorber
- Component C a UV stabilizer, preferably a HALS compound
- the components A and B can be used as a single substance or in mixtures. At least one UV absorber component must be included in the film. Component C is mandatory in the film used in the invention.
- Component A UV absorber of the benzotriazole type
- benzotriazole-type UV absorber there can be used, for example, 2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2- [2-hydroxy-3,5-di (alpha, alpha-dimethyl-benzyl) -phenyl] - benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -benzotriazole, 2- (2-hydroxy-3, 5-butyl-5-methylphenyl) -5-chlorobenzthazole, 2- (2-hydroxy -3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) -benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) - benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) -benzotriazole; and 2- (2-hydroxy-5-methyl
- the benzotriazole-type UV absorbers are used in amounts between 0.1% and 10% by weight, preferably in amounts between 0.2% and 6% by weight and most preferably in amounts between 0.5% and 4% by weight, based on the weight of the monomers used to make the polymethyl methacrylates. It is also possible to use mixtures of different benzotriazole UV absorbers.
- Component B UV absorber of the triazine type
- triazines such as 2- (4,6-diphenyl-1, 3,5-thazin-2-yl) -5-hexyloxy-phenol, can be used as UV stabilizers.
- the triazines are used in amounts between 0.0% by weight and 5% by weight.
- Polymethyl methacrylates are used. It is also possible to use mixtures of different triazines.
- Component C UV stabilizers
- radical scavengers / UV stabilizers are sterically hindered amines, which are known by the name HALS (JHindered Amine Light Stabilizer). They can be used for the inhibition of aging processes in paints and plastics, in particular in polyolefin plastics (Kunstscher, 74 (1984) 10, pp. 620 to 623; Paint + Varnish, 96 Volume, 9/1990, pp. 689 to 693 ). The stabilizing effect of the HALS compounds is due to the tetramethylpiperidine group contained therein.
- Compound class can be both unsubstituted on piperidine nitrogen as well be substituted with alkyl or acyl groups.
- the sterically hindered amines do not absorb in the UV range. They catch formed radicals, which the UV absorbers can not do.
- stabilizing HALS compounds which can also be used as mixtures are: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1, 3-8-triazaspiro (4,5) -decane-2,5-dione, bis (2,2,6,6-tetramethyl-4-piperidyl) -succinate, poly (N ⁇ -hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine-succinic acid ester) or bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate.
- the HALS compounds are used in amounts between 0.0% by weight and 5% by weight, preferably in amounts of between 0.1% by weight and 3% by weight and very particularly preferably in amounts of between 0.2% by weight % and 2% by weight, based on the weight of the monomers used to prepare the
- Polymethyl methacrylates are used. It is also possible to use mixtures of different HALS compounds.
- HALS compounds which can be used are, furthermore, the HALS compounds already described, disulfites, for example sodium disulfite, and also sterically hindered phenols and phosphites.
- the adhesive layer is the adhesive layer
- the optional adhesive layer is used depending on the manufacturing process for connecting the cover and the carrier film. It is only present if adhesion between the two films is not directly possible.
- the choice of suitable adhesive results from the composition of the two films - for example, PMMA and PET - and the optical properties.
- the adhesive layer must also be highly transparent. Suitable, for example, special
- scratch-resistant coating is understood in the context of this invention as collective term for coatings which are applied to reduce surface scratching and / or to improve the abrasion resistance.
- Foil composites in solar reflectors is particularly high
- scratch-resistant coating in the broadest sense is that this layer does not adversely affect the optical properties of the film composite.
- 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. These paint formulations are e.g. about rollcoating, knifecoating or
- PVD physical vapor deposition
- CVD chemical vapor deposition
- the carrier foil is the carrier foil
- the film must be highly transparent, flexible,
- films with such a property profile have especially polyester films, especially coextruded, biaxially oriented polyethylene terephthalate (PET) films. These are optional with
- Adhesives for better adhesion of the metal for better adhesion of the metal, bruisenvergütungst, the adhesive layer equipped.
- PMMA foils, PVDF / PMMA two-layer foils or films of PVDF / PMMA blends can also be used as carrier foils.
- the metal layer is preferably applied to the back of the carrier film and is preferably made of silver or aluminum, more preferably of silver.
- the metal layer can optionally be coated with a second metal layer, for example made of copper or a nickel-chromium alloy. This serves as a protection of the metal mirror layer and on the other hand for better adhesion of the
- cover films used according to the invention can also be used for surface treatment or for improving the weathering protection of multi-layered films
- Aluminum band-based layer systems such as those sold by the company Alanod solar under the name MIRO-SUN ® can be used. Special embodiment
- a metal layer system in the form of a metal strip preferably based on aluminum, such as MIRO-SUN ® , which also serves as a carrier film, is used.
- the carrier film and the metal layer are thus identical and no further polymer-based carrier film is required.
- the pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer
- the pressure-sensitive adhesive layer is used for bonding the film composite, for example, to a carrier material, such as a curved aluminum plate.
- a carrier material such as a curved aluminum plate.
- PSA pressure-sensitive adhesive
- Adhesive layer a low permeability to atmospheric oxygen
- the pressure-sensitive adhesive layer is glued on a siliconized paper for transport and storage. Before gluing on the carrier this can be easily removed.
- Water vapor or even mirgationsseriee constituents of the pressure-sensitive adhesive prevent.
- This may be, for example, an epoxy resin layer.
- the film composite - from outside to inside - can also be constructed in the following layer sequence:
- the single-layer or multi-layer cover film used according to the invention can be produced in any desired thickness, depending on the intended use. Decisive in any case is the high transparency of the cover film, coupled with an extraordinary weathering stability as well as the extreme weathering protection for the substrate.
- the preparation of the single or multilayer cover sheet is carried out by methods known per se, such as extrusion through a
- the film composite is produced, for example, by lamination and / or by (co) extrusion coating and / or by lamination.
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Abstract
The invention relates to a film composite and the use thereof as a mirror film in solar reflectors in view of the sustainable guarantee of the required reflection of solar radiation (total solar reflection). In particular, the invention relates to the use of cover films on the basis of polymethyl methacrylate (PMMA) in the film composite, having an especially high UV stability, and a high weathering stability. The invention further relates to a UV and weather protection package for said solar mirror film, as utilized in solar reflectors, for improving the optical life span, weathering stability, and for avoiding delamination. The invention further relates to a surface finish with regard to scratch resistance, anti-soil and chemical stability of the solar mirror film.
Description
Solarspiegelfolienverbund mit besonders hoher Witterungs- und UV- Beständigkeit Solar mirror film compound with particularly high weathering and UV resistance
Gebiet der Erfindung Field of the invention
Die Erfindung betrifft einen Folienverbund und dessen Anwendung als Spiegelfolie in Solarreflektoren unter dem Hintergrund der möglichst nachhaltigen Gewährleistung der geforderten Reflektion solarer Strahlung (total solar reflection). The invention relates to a film composite and its application as a mirror film in solar reflectors under the background of the most sustainable possible guarantee of the required reflection of solar radiation (total solar reflection).
Insbesondere betrifft die Erfindung die Anwendung von Deckfolien basierend auf Polymethyl(meth)acrylat (PMMA) im Folienverbund, mit einer besonders hohen UV- Stabilität und einer hohen Witterungsstabilität. Ferner betrifft die Erfindung ein UV- und Witterungsschutzpaket für besagte Solarspiegelfolie, wie sie Verwendung in In particular, the invention relates to the use of cover films based on polymethyl (meth) acrylate (PMMA) in the film composite, with a particularly high UV stability and high weathering stability. Furthermore, the invention relates to a UV and weather protection package for said solar mirror film, as they are used in
Solarreflektoren finden, zur Verbesserung der optischen Lebensdauer, Find solar reflectors, to improve the optical life,
Witterungsbeständigkeit und Verhinderung einer Delaminierung. Die Erfindung betrifft ferner eine Oberflächenvergütung betreffend. Kratzfestigkeit, Antisoil und Weathering resistance and prevention of delamination. The invention further relates to a surface treatment. Scratch resistance, antisoil and
Chemikalienbeständigkeit der Solarspiegelfolie. Chemical resistance of the solar mirror foil.
Der Begriff Deckfolie ist synonym zu einer Oberflächenvergütungsschicht, The term cover film is synonymous with a surface coating layer,
Oberflächenvergütungsfolie oder allgemein einer Oberflächenvergütung zu verstehen. Surface coating or generally a surface finish to understand.
Stand der Technik State of the art
Flexible Spiegelfolien-Laminate in Solarreflektoren nach dem Stand der Technik weisen Nachteile in Bezug auf eine ausreichende Witterungsbeständigkeit und Abbau durch ultraviolette (UV-)Strahlung. Insbesondere für Außenanwendungen bestehen jedoch hohe Anforderungen an solche Folien bezüglich Beständigkeit und Resistenz gegenüber UV-Strahlung und sonstigen Witterungseinflüssen. Diese Ansprüche
bestehen insbesondere in Hinblick auf Formbeständigkeit, den Reflexionsgrad im sichtbaren bzw. im näheren Infrarot-Spektrum und das äußere Erscheinungsbild. Flexible mirror film laminates in prior art solar reflectors have disadvantages in terms of sufficient weatherability and degradation by ultraviolet (UV) radiation. In particular, for outdoor applications, however, there are high demands on such films in terms of resistance and resistance to UV radiation and other weather conditions. These claims exist in particular with regard to dimensional stability, the reflectance in the visible or in the near infrared spectrum and the external appearance.
Das für„Solarthermie" relevante Wellenlängenspektrum der solaren Strahlung reicht von 300 nm bis 2500 nm. The wavelength spectrum of solar radiation relevant for "solar thermal energy" ranges from 300 nm to 2500 nm.
Der Bereich unter 400 nm, insbesondere unter 375 nm sollte zur Verlängerung der Lebensdauer der Solarspiegelfolie jedoch ausgefiltert werden, so dass der„Wirksame Wellenlängenbereich" von 375 nm bzw. von 400 nm bis 2500 nm bestehen bleibt. However, the range below 400 nm, in particular below 375 nm, should be filtered out in order to extend the service life of the solar mirror film, so that the "effective wavelength range" of 375 nm or 400 nm to 2500 nm remains.
Der Reflexionsgrad der flexiblen Spiegelfolien-Laminate in dieser Anwendung wird bestimmt durch die Qualität und die Beständigkeit. Ein solches Laminat wird durch Vakuumbedampfen einer flexiblen Polymerfolie (Trägerfolie) mit einer dünnen The reflectance of the flexible mirror film laminates in this application is determined by the quality and durability. Such a laminate is made by vacuum evaporation of a flexible polymer film (carrier film) with a thin
Silberschicht hergestellt. Begründet durch den gegenüber anderen Metallen besonders hohen Reflexionsgrad im relevanten Wellenlängenbereich ist Silber das für diese Anwendung bevorzugte Metall. Um die polymere Trägerfolie und optional die Silver layer produced. Due to the particularly high reflectivity in the relevant wavelength range compared to other metals, silver is the preferred metal for this application. To the polymeric carrier film and optionally the
Silberschicht gegenüber äußeren Einflüssen zu schützen, wird sie zusätzlich mit einer Schutzschicht überzogen. Zweck dieser Schutzschicht, bei der es sich in der Regel um eine Deckfolie zur Oberflächenvergütung handelt, ist der Schutz vor mechanischem Abrieb, Witterungseinflüssen und Abbau durch UV-Strahlung. Silver layer to protect against external influences, it is additionally coated with a protective layer. The purpose of this protective layer, which is usually a cover film for surface treatment, is the protection against mechanical abrasion, weathering and degradation by UV radiation.
In US 4,307,150 wird ein solches Schutzsystem für Aluminiumspiegel beschrieben. Als Trägerfolie wird ein PET-Laminat verwendet, das mit Aluminium bedampft wird und durch Aufkleben einer (Meth)acrylat-Folie gegen Korrosion und Witterungseinflüsse geschützt wird. Ein expliziter UV-Schutz ist nicht berücksichtigt. Such a protective system for aluminum mirrors is described in US 4,307,150. As carrier film, a PET laminate is used, which is vapor-deposited with aluminum and protected by gluing a (meth) acrylate film against corrosion and weathering. An explicit UV protection is not considered.
Eine Silberbedampfung ist gegenüber einer Aluminiumschicht aufgrund des höheren Reflektionsgrades deutlich besser zur Konstruktion solcher Spiegel geeignet. Die Verwendung von Silber wird in US 4,645,714 beschrieben. Silber hat im Prinzip jedoch zwei Nachteile. Zum einen sind insbesondere dünne Silberschichten besonders Korrosionsempfindlich. Aus diesem Grund müssen Schutzschichten bzw. -laminate besonders dicht sein. Andernfalls reichen kleine Löcher oder unzureichende Dichtigkeit am Rand des Laminats, um eine ungewünschte Oxidation hervorzurufen. Zum anderen haben sowohl Silber als auch Aluminium eine Absorptionslücke im Spektralbereich des
ultravioletten Lichts (300 - 400 nm), insbesondere im Bereich um eine Wellenlänge von 320 nm, der ein wichtiger Bestandteil des Sonnenlichts ist. Die Durchlässigkeit ist insbesondere bei sehr dünnen Schichten gegeben. Diese kurzwellige Strahlung ist vor allem bei einer längeren Exposition, wie sie im Anwendungsfeld von Solarspiegeln gegeben ist, schädlich für die Trägerfolie sowie die Silber-Metallspiegelschicht, insbesondere für zumeist verwendete Polyesterfolien oder -laminate bzw. die zur Laminatherstellung verwendeten Kleber. Es kann zur Blasenbildung und damit zur Verformung und zur Reduzierung des Reflektionsgrades kommen. 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, small holes or insufficient tightness will be sufficient at the edge of the laminate to cause unwanted oxidation. On the other hand, both silver and aluminum have an absorption gap in the spectral range of the ultraviolet light (300-400 nm), in particular in the range around a wavelength of 320 nm, which is an important part of the sunlight. 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, in particular for mostly used polyester films or laminates or the adhesive used for the production of laminates, especially in the case of prolonged exposure, as is the case in the field of solar mirrors. It can lead to blistering and thus to deformation and to reduce the degree of reflection.
Inhibitoren zur Korrosionsvermeidung und UV-Absorptionsreagenzien können zum besseren Schutz in die oben aufgeführte Schutzfolie eingebracht werden. Die zumeist verwendeten Inhibitoren haben jedoch den Nachteil, selbst nur eine verminderte Anticorrosion inhibitors and UV absorption reagents can be incorporated into the protective film listed above for better protection. However, the most commonly used inhibitors have the disadvantage, even a reduced one
Witterungs- oder sogar UV-Stabilität aufzuweisen und nach einiger Zeit zu Weathering or even UV stability and after some time to
Verfärbungen zu führen. Letztere reduzieren jedoch die Reflektion in anderen Cause discoloration. The latter, however, reduce the reflection in others
Spektralbereichen und damit den Wirkungsgrad der Solaranlage. Spectral ranges and thus the efficiency of the solar system.
UV-Absorber dagegen alleine tragen nicht zum Korrosionsschutz der UV absorbers alone do not contribute to the corrosion protection of
Silberbeschichtung bei, sondern verhindern nur eine witterungsbedingte Alterung das Polyesterlaminats. Um einen optimierten Schutz zu erhalten werden demnach beide Komponenten - Inhibitor und UV-Absorber - voneinander getrennt. Silver coating, but prevent weather-related aging of the polyester laminate. In order to obtain optimized protection, both components - inhibitor and UV absorber - are separated from each other.
IN US 4,645,714 werden dazu zwei getrennte (Meth)acrylat basierte Beschichtungen aufgetragen. Die äußere enthält den UV-Absorber, die innere den Inhibitor. Durch diesen Aufbau wird die innere durch die äußere Schicht geschützt und es treten in deutlich verringertem Maße Verfärbungen auf. Die Inhibitor-Schicht wird dabei direkt auf der Silberbedampfung aufgetragen. Die zweite, den UV-Absorber enthaltende Schicht wiederum über diese erste Schicht. Als Polyesterlaminat wird eine zweischichtige, durch Coextrusion hergestellte PET-Folie verwendet, wobei die eine Schicht ein In US Pat. No. 4,645,714, two separate (meth) acrylate-based coatings are applied for this purpose. The outer contains the UV absorber, the inner contains the inhibitor. By this construction, the inner is protected by the outer layer and it occur to a much reduced extent discoloration. The inhibitor layer is applied directly to the silver vaporization. The second layer containing the UV absorber again via this first layer. As a polyester laminate, a two-layer, produced by coextrusion PET film is used, wherein the one layer
Gleitmittel zur Verbesserung der Flexibilität enthält und die andere, mit Silber Lubricant to improve flexibility and the other, with silver
bedampfte Schicht, kein Gleitmittel enthält, um eine möglichst glatte Oberfläche zu gewährleisten. Die innere (Meth)acrylatschicht enthält zwischen 0,5 und 2,5 Gew% Glykol-dimercaptoacetat, das als Dispergator, Kupplungsreagenz, Haftvermittler und Inhibitor wirkt.
Die äußere (Meth)acrylatschicht enthält ein UV-Absorptionsreagenz, welches bei Strahlung mit einer Wellenlänge zwischen 300 nm und 400 nm aktiv ist. Durch den Zweischichtaufbau wird weiterhin eine Korrosion des Silbers durch das UV- Absorptionsreagenz ausgeschlossen. vaporized layer, contains no lubricant to ensure the smoothest possible surface. The inner (meth) acrylate layer contains between 0.5 and 2.5% by weight glycol dimercaptoacetate, which acts as a dispersant, coupling reagent, adhesion promoter and inhibitor. The outer (meth) acrylate layer contains a UV absorption reagent, which is active in radiation with a wavelength between 300 nm and 400 nm. The two-layer structure further precludes corrosion of the silver by the UV absorption reagent.
Die nicht beschichtete Seite des Polyesterlaminats wiederum ist mit einem PSA The uncoated side of the polyester laminate, in turn, is with a PSA
(pressure sensitive adhesive bzw. Haftklebstoff) auf Basis eines Isooctylacrylat- Acrylamid-Copolymers beschichtet. Diese Beschichtung kann z.B. mit einer (Pressure sensitive adhesive or adhesive) based on a isooctyl acrylate-acrylamide copolymer coated. This coating can e.g. with a
siliconbeschichteten Polyesterfolie vor dem Verwendung des Spiegellaminats geschützt werden. silicone-coated polyester film to be protected before using the mirror laminate.
Die in US 4,645,714 und US 4,307,150 beschrieben (Meth)acrylatbeschichtungen haben beide jedoch den Nachteil, dass sie bei einer Außenanwendung eine However, the (meth) acrylate coatings described in US Pat. Nos. 4,645,714 and 4,307,150 both have the disadvantage of being used in an outdoor application
verminderte Witterungsstabilität aufweisen und somit für Solaranwendungen im have reduced weathering stability and thus for solar applications in the
Außenbereich grundsätzlich nur schlecht geeignet sind. Diese Beschichtungen wässern nur sehr schlecht ab, sind nicht abriebsbeständig und haben nur eine sehr begrenzte Beständigkeit gegenüber Luftfeuchtigkeit. Nach Erosion der Outdoor are basically poorly suited. These coatings are very poor at watering, abrasion resistant, and have very limited resistance to atmospheric moisture. After erosion of the
Poly(meth)acrylatbeschichtung kann es dann zur beschriebenen Abbau des Poly (meth) acrylate coating can then be used for the described degradation of the
Polyesterlaminats kommen. Um dieses Problem zu umgehen, wird in US 5,118,540 eine abriebsfeste und feuchtigkeitsbeständige Folie auf Basis von Fluorkohlenstoff- Polymeren 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. Polyester laminate come. To circumvent this problem, US 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.
Allerdings werden als UV-Absorptionsreagenzien ausschließlich Benzthazole However, as UV absorption reagents only Benzthazole
eingesetzt, welche nur eine vergleichsweise„kurze" Eigenbeständigkeit unter UV- Strahlungseinfluss aufweisen und somit - in der besagten Anwendung - keinen wirkungsvollen UV-Schutz für die Klebschicht selber und die verbundene used, which have only a comparatively "short" intrinsic resistance under UV radiation influence and thus - in the said application - no effective UV protection for the adhesive layer itself and the associated
Metalloberfläche bzw. Polyesterträgerfolie darstellen. Represent metal surface or polyester carrier film.
In WO 2007/076282 wird dagegen eine alternative Struktur zum besseren Schutz der Silberbeschichtung aufgeführt. Die PET-Trägerfolie wird nicht mehr auf der Oberfläche,
sondern auf der dem Licht abgewandten Seite mit Silber bedampft. Auf der anderen Seite der PET-Folie wird eine Poly(meth)acrylat Schutzfolie aufgeklebt, die mit UV- Absorptionsreagenzien ausgestattet ist. Die Lehre, dass eine langlebige UV- Schutzausrüstung benötigt wird, ist in WO 2007/076282 nicht berücksichtigt. In contrast, WO 2007/076282 mentions an alternative structure for better protection of the silver coating. The PET carrier film is no longer on the surface, but steamed on the side facing away from the light with silver. On the other side of the PET film, a poly (meth) acrylate protective film is attached, which is equipped with UV absorption reagents. The doctrine that a long-lasting UV protection equipment is needed is not considered in WO 2007/076282.
Die Rückseite der Silberbedampfung kann entweder direkt mit einem Haftkleber (PSA) versehen werden oder zur Verbesserung der Korrosionsbeständigkeit auf der Rückseite und zur besseren Haftung des PSA mit einer zusätzlichen Kupferschicht bedampft werden. 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.
Bei der verwendeten Poly(meth)acrylatfolie zum UV-Schutz handelt es sich um eine Korad® Folie der Firma SPARTECH PEP. Diese Folie hat den Nachteil, dass als UV- Absorber„Benztriazole" eingesetzt werden, welche nur eine vergleichsweise„kurze" Eigenbeständigkeit unter UV-Strahlungseinfluss aufweisen und somit - in der besagten Anwendung - keinen wirkungsvollen UV-Schutz für die Klebschicht und die verbundene Polyesterträgerfolie darstellen. When used poly (meth) acrylate film for UV protection is it is a Korad ® film from SPARTECH PEP. This film has the disadvantage that "benzotriazoles" are used as UV absorbers, which have only a comparatively "short" intrinsic stability under UV radiation influence and thus - in said application - no effective UV protection for the adhesive layer and the associated polyester support film represent.
Den Korad Folien analoge oder ähnliche Poly(meth)acrylat-Folien haben sich für den Einsatz als Oberflächenschutzfolien von Kunststoff-Formteilen für diverse The Korad films analogous or similar poly (meth) acrylate films have for use as surface protection films of plastic molded parts for various
Aussenanwendungen wie z.B. im Nutzfahrzeugbereich am Markt etabliert. Die Outdoor applications such as established in the commercial vehicle sector on the market. The
Performance dieses Typs Deckfolie reicht jedoch nicht aus, die geforderte However, performance of this type cover sheet is not enough, the required
Langzeitwitterungsbeständigkeit in der Anwendung Spiegelfolie für Solarreflektoren unter Erhaltung eines hohen solaren Reflektionsgrades zu ermöglichen. Long-term weathering resistance in the application to enable mirror film for solar reflectors while maintaining a high solar reflectance.
Eine Lehre betreffend der Darstellung einer Deckfolie mit langlebiger UV- Schutzfunktion, wie sie den Langlebigkeitsanforderungen bzw. A teaching regarding the presentation of a cover sheet with a long-lasting UV protection function, as they meet the longevity requirements or
Gewährleistungsanforderungen für Solarreflektoren entspricht, ist nicht Stand der Technik. Warranty requirements for solar reflectors is not state of the art.
In den bisher am Markt erhältlichen Folienlaminaten für Solarspiegel wurden zur Stabilisierung gegen UV-Strahlen in der Deckfolie ausschließlich UV-Absorber des Benztriazol-Typs eingebracht. Diese UV-Absorber werden beispielsweise unter der Marke Tinuvin 234 von Ciba Specialty Chemicals Inc. vertrieben. Von diesen UV- Absorbern ist bekannt, dass sie über einen Zeitraum von 5 bis 10 Jahren ihre
Wirksamkeit signifikant einbüßen, wodurch die Oberflächenvergütungsschicht degradiert. Hieraus resultiert eine deutliche Abnahme der solaren Reflektion des Solarspiegelfolienverbunds. In the film laminates for solar mirrors which were previously available on the market, exclusively UV absorbers of the benzotriazole type were introduced for stabilization against UV rays in the cover film. These UV absorbers are sold, for example, under the trademark Tinuvin 234 by Ciba Specialty Chemicals Inc. These UV absorbers are known to last for a period of 5 to 10 years Significantly lose effectiveness, which degrades the surface coating layer. This results in a significant decrease in the solar reflection of the solar mirror film composite.
Es gibt eine steigende Nachfrage nach Solarspiegelfolien, die die bestehenden Anforderungen an die Langlebigkeit bzw. den Performanceerhalt der etablierten Solarspiegelfolien deutlich übertreffen.
There is an increasing demand for solar mirror foils, which clearly exceed the existing requirements for the longevity or the performance of the established solar mirror foils.
Aufgabe task
Es bestand die Aufgabe, einen neuartigen Solarspiegel-Folienverbund für Solarreflektoren mit gegenüber dem Stand der Technik verbesserten oder zumindest gleichwertigen optischen Eigenschaften und einer verbesserten Witterungsbeständigkeit, insbesondere in Hinblick auf eine Langzeitanwendung, zur Verfügung zu stellen. The object was to provide a novel solar mirror film composite for solar reflectors with improved or at least equivalent optical properties and improved weathering resistance, especially with regard to a long-term use, compared with the prior art.
Unter Langzeitanwendung wird hier insbesondere eine Anwendung über einen Zeitraum von mehr als 10 Jahre, insbesondere mehr als 15 Jahren, besonders bevorzugt mehr als 20 Jahren verstanden. Long-term use is understood to mean in particular an application over a period of more than 10 years, in particular more than 15 years, particularly preferably more than 20 years.
Es bestand insbesondere die Aufgabe, dass der Folienverbund für In particular, the object was that the film composite for
Solarreflektoren unter besonders starker Sonnenbestrahlung, wie sie z.B. in der Sahara oder im Südwesten der USA vorkommt, für lange Zeit stabil bleibt. Dies gilt insbesondere betreffend der Eigenbeständigkeit und Filtereffizienz der der Deckfolie dieser Verbundfolien gegenüber dem UV-Wellenlängenspektrum zwischen 300 nm und 400 nm. Solar reflectors under particularly strong sunlight, as they are e.g. occurs in the Sahara or the Southwest of the US, remains stable for a long time. This applies in particular with regard to the inherent stability and filter efficiency of the cover film of these composite films with respect to the UV wavelength spectrum between 300 nm and 400 nm.
Es bestand darüber hinaus die Aufgabe, einen Folienverbund für There was also the task of a film composite for
Solarreflektoren zur Verfügung zu stellen, die einfach und kosteneffizient herzustellen und weiterzuverarbeiten sind. To provide solar reflectors that are simple and cost-effective to manufacture and process.
Darüber hinaus soll der stabilere Folienverbund möglichst farbneutral und feuchtigkeitsstabil sein. In addition, the more stable film composite should be as color-neutral and moisture-stable as possible.
Darüber hinaus soll der Folienverbund kratzfest sein und Schmutz abweisende Eigenschaften aufweisen.
Lösung In addition, the film composite should be scratch-resistant and have dirt-repellent properties. 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, einen bis zur Metallschicht transparenten Folienverbund mit verbesserter Witterungsstabilität und einer über einen langen Zeitraum stabilen guten solaren Reflektion bereitzustellen, die zudem noch über eine Reihe weiterer Vorteile verfügt. Against the background of the state of the art and the technical solutions described therein for long-term applications, it is possible in the present invention to provide a film composite transparent to the metal layer with improved weatherability and over a long period of time, which is not easily foreseeable by the person skilled in the art provide stable, good solar reflection, which also has a number of other advantages.
Gelöst wird die Aufgabe durch Bereitstellung eines neuartigen Folienverbunds, der in Solarreflektoren angewendet werden kann. Dieser Folienverbund besteht aus mindestens folgenden Schichten: eine Deckfolie, eine Trägerfolie, eine Metallschicht und eine Haftklebstoffschicht. Insbesondere handelt es sich um einen Folienverbund, in dem es sich bei der Deckfolie um eine PMMA-basierte Folie, bei der Trägerfolie um eine Polyesterfolie und bei der Metallschicht um eine Silberschicht handelt. Optional ist unterhalb der Deckfolie zusätzlich eine Klebschicht und unterhalb der Metallschicht eine Migrationssperrschicht und/ oder ein Primer aufgebracht. The problem is solved by providing a novel film composite that can be used in solar reflectors. This film composite consists of at least the following layers: a cover film, a carrier film, a metal layer and a pressure-sensitive adhesive layer. In particular, it is a film composite in which the cover film is a PMMA-based film, the carrier film is a polyester film and the metal layer is a silver layer. Optionally, an adhesive layer is additionally applied underneath the cover film and a migration barrier layer and / or a primer below the metal layer.
Dieser Folienverbund besteht bevorzugt in aufgeführter Reihenfolge von der späteren Außenseite zur PSA-Schicht, die mit einem Trägermaterial verbunden wird, aus mindestens folgenden Schichten: eine Deckfolie, eine Trägerfolie, eine Metallschicht und eine Haftklebstoffschicht. Optional ist zwischen Deckfolie und Trägerfolie zusätzlich eine Klebschicht und zwischen Metallschicht und Haftkleber eine Migrationssperrschicht und/ oder ein Primer aufgebracht.
Ein weiteres wichtiges Merkmal der vorliegenden Erfindung ist, dass sich der neuartige Folienverbund durch eine sehr hohe Stabilität, insbesondere UV- Stabilität, auch unter Dauerbestrahlung, auszeichnet. Dazu enthält die Deckfolie mindestens ein Triazin als UV-Absorber und einen UV-Stabilisator. This film composite is preferably in listed order from the later outside to the PSA layer which is bonded to a carrier material, comprising at least the following layers: a cover film, a carrier film, a metal layer and a pressure-sensitive adhesive layer. Optionally, an adhesive layer is additionally applied between the cover film and the carrier film, and a migration barrier layer and / or a primer is applied between the metal layer and the pressure-sensitive adhesive. Another important feature of the present invention is that the novel composite film is characterized by a very high stability, in particular UV stability, even under continuous irradiation. For this purpose, the cover sheet contains at least one triazine as UV absorber and a UV stabilizer.
Insbesondere handelt es sich um ein Gemisch aus UV-Absorbern, bestehend aus mindestens einem Triazin und mindestens einem Benzthazol. Bei dem UV- Stabilitsator handelt es sich um eine HALS-Verbindung oder eine Mischung verschiedener HALS-Verbindung. Thazin-basierende UV-Absorber weisen eine besonders hohe Eigenbeständigkeit unter UV-Strahlungseinfluss aus. In particular, it is a mixture of UV absorbers, consisting of at least one triazine and at least one benzthazole. The UV stabilizer is a HALS compound or a mixture of different HALS compounds. Thazine-based UV absorbers have a particularly high intrinsic resistance under the influence of UV radiation.
Unter Stabilität wird gleichzeitig die Eigenstabilität der Deckfolie gegen UV- und Witterungseinflüsse und die Stabilität der UV-Schutzwirkung, abzulesen beispielsweise aus dem Erhalt der solaren Reflektion, verstanden. Stability is understood at the same time as the inherent stability of the cover film against UV and weathering effects and the stability of the UV protection effect, for example, from obtaining the solar reflection.
Bevorzugt kann die Deckkfolie zwischen 0,1 Gew% und 10 Gew%, bevorzugt zwischen 0,2 Gew% und 6 Gew% und besonders bevorzugt zwischen 0,5 Gew% und 4 Gew% der UV-Absorber vom Benztriazol-Typ, The cover film may preferably contain between 0.1% by weight and 10% by weight, preferably between 0.2% by weight and 6% by weight and particularly preferably between 0.5% by weight and 4% by weight of the benzotriazole type UV absorbers,
zwischen 0,1 Gew% und 5 Gew%, bevorzugt zwischen 0,2 Gew% und 3 Gew% und besonders bevorzugt zwischen 0,5 Gew% und 3 Gew% der UV-Absorber vom Triazin-Typ und between 0.1% by weight and 5% by weight, preferably between 0.2% by weight and 3% by weight and more preferably between 0.5% by weight and 3% by weight of the triazine-type UV absorbers and
zwischen 0,1 Gew% und 5 Gew%, bevorzugt zwischen 0,5 Gew% und 3 Gew% und besonders bevorzugt zwischen 0,2 Gew% und 2 Gew% der UV- Stabilisatoren, bevorzugt UV-Stabilisatoren vom HALS-Typ enthalten. 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 of the HALS type.
Die erfindungsgemäß eingesetzte Mischung aus UV-Absorbern und UV- Stabilisatoren zeigt über ein breites Wellenlängenspektrum (300 nm - 400 nm) einen stabilen, langlebigen UV-Schutz.
Optional kann die Deckfolie, die Mischung aus UV-Stabilisatoren und UV- Absorbern enthaltend, aus Poly(meth)acrylat und Polyvinylidenfluorid in einem Gewichtsverhältnis zwischen 1 zu 0,01 und 1 zu 1 , bevorzugt zwischen 1 zu 0,1 und 1 zu 0,5 zusammensetzt sein. Bevorzugt umfasst die Deckfolie zwei Lagen. Dabei handelt es sich bei einer Lage um eine Lage aus Poly(meth)acrylat und bei der anderen um eine Lage aus Polyvinylidenfluorid (PVDF). Bevorzugt ist die PVDF-Lage die an der Oberfläche des Folienverbundes befindliche Schicht. The mixture of UV absorbers and UV stabilizers used according to the invention exhibits stable, long-lasting UV protection over a broad wavelength spectrum (300 nm-400 nm). Optionally, the cover sheet, containing the mixture of UV stabilizers and UV absorbers, of poly (meth) acrylate and polyvinylidene fluoride in a weight ratio between 1 to 0.01 and 1 to 1, preferably between 1 to 0.1 and 1 to 0 , 5 be composed. Preferably, the cover sheet comprises two layers. One layer is a layer of poly (meth) acrylate and the other is a layer of polyvinylidene fluoride (PVDF). The PVDF layer is preferably the layer located on the surface of the film composite.
Unabhängig von der Zusammensetzung weist die Deckfolie eine Dicke im Bereich von 10 μm bis 200 μm, vorzugsweise im Bereich von 40 μm bis 120 μm, besonders bevorzugt im Bereich von 50 μm bis 90 μm auf. Regardless of the composition, the cover film has a thickness in the range from 10 μm to 200 μm, preferably in the range from 40 μm to 120 μm, particularly preferably in the range from 50 μm to 90 μm.
Die erfindungsgemäß verwendete Deckfolie ist optional kratzfest ausgestattet, bevorzugt durch eine Beschichtung zur Erhöhung der Kratzfestigkeit. Die Oberfläche der Deckfolie kann darüber hinaus mit einer Antisoiling- Beschichtung ausgestattet sein. The cover sheet used according to the invention is optionally scratch-resistant, preferably by a coating to increase the scratch resistance. The surface of the cover sheet can also be equipped with an anti-siding coating.
Darüber hinaus weist der erfindungsgemäße, neuartige Folienverbund folgende Eigenschaften, in Kombination als Vorteil gegenüber dem Stand der Technik, besonders in Hinblick auf optische Eigenschaften, auf: Der transparente Anteil des erfindungsgemäßen Folieverbundes ist besonders farbneutral und trübt sich bei Feuchtigkeitseinfluß nicht ein. Der Folienverbund zeigt zudem eine ausgezeichnete Witterungsbeständigkeit und bei optionaler Ausstattung mit einer PVDF-Oberfläche und/oder einer Kratzfestausrüstung eine sehr gute Chemikalienbeständigkeit, beispielsweise gegen sämtliche handelsübliche Reinigungsmittel. Auch diese Aspekte tragen zum Erhalt der solaren Reflektion über einen langen Zeitraum bei.
Um die Reinigung zu erleichtern, weist die Oberfläche schmutzabweisende Eigenschaften auf. Zusätzlich ist die Oberfläche optional abriebsfest und/oder kratzfest. In addition, the inventive novel film composite has the following properties, in combination as an advantage over the prior art, especially with regard to optical properties, on: The transparent portion of the film composite according to the invention is particularly neutral in color and does not cloud when exposed to moisture. In addition, the film composite exhibits excellent weathering resistance and, if optionally equipped with a PVDF surface and / or a scratch-resistant finish, very good resistance to chemicals, for example against all commercially available cleaning agents. These aspects also contribute to maintaining solar reflection over a long period of time. To facilitate cleaning, the surface has dirt-repellent properties. In addition, the surface is optionally abrasion-resistant and / or scratch-resistant.
Der erfindungsgemäße Folienverbund findet insbesondere Anwendung als Spiegelfolie in Sonnenreflektoren. Das Aufbringen der Spiegelfolie auf einem Trägerblech, zum Beispiel einem Aluminiumblech, erfolgt mittels The film composite according to the invention finds particular application as a mirror film in sun reflectors. The application of the mirror film on a support plate, for example an aluminum sheet, by means of
Folienlamination und die Haftung zum Trägerblech wird durch die Folienlamination and the adhesion to the carrier sheet is by the
Haftklebstoffschicht bewirkt. Pressure-sensitive adhesive layer causes.
Insbesondere zeichnet sich der erfindungsgemäße Folienverbund durch seine gegenüber dem Stand der Technik deutlich verbesserten UV-Stabilität und die damit einhergehende längere Lebensdauer aus. Das erfindungsgemäße Material kann so auch über einen sehr langen Zeitraum von mindestens 10 Jahren, bevorzugt sogar mindestens 15 Jahren, besonders bevorzugt mindestens 20 Jahren an Orten mit besonders vielen Sonnenstunden und besonders intensiver Sonnenstrahlung, wie z.B. im Südwesten der USA oder der Sahara in Sonnenreflektoren eingesetzt werden. In particular, the film composite according to the invention is distinguished by its markedly improved UV stability compared with the prior art and the associated longer service life. 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 southwestern United States or the Sahara in solar reflectors.
Der mit dem erfindungsgemäßen Folienverbund ausgestattete, langlebige Sonnenreflektor weißt bezüglich der solaren Reflektion innerhalb von 10 Jahren eine maximale Abnahme von 8%, bevorzugt eine maximal Abnahme von 5% und besonders bevorzugt eine maximal Abnahme von 3% auf.
The long-lived solar reflector equipped with the film composite according to the invention has a maximum decrease of 8%, preferably a maximum decrease of 5% and more preferably a maximum decrease of 3%, with respect to the solar reflection within 10 years.
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Die idealerweise verwendeten Deckfolien zum UV-Schutz der erfindungsgemäß aufgebauten Spiegelfolienverbünde entsprechen den in WO 2007/073952 (Fa. Evonik Röhm) oder den in DE 10 2007 029 263 A1 offenbarten UV- Schutzfolien. Beispielhaft können diese Folien die im Weiteren kurz skizzierten Bestandteile aufweisen. Eine umfassendere Beschreibung findet sich in WO 2007/073952. The cover sheets for the UV protection of the mirror film composites constructed according to the invention, which are ideally used, correspond to the UV protection films disclosed in WO 2007/073952 (Evonik Röhm) or in DE 10 2007 029 263 A1. By way of example, these films may have the components briefly outlined below. A more complete description can be found in WO 2007/073952.
Bei den erfindungsgemäß verwendeten Deckfolien handelt es sich um PMMA- basierte Folien. Mit der Formulierung PMMA-basierte Folien sind die Folien jedoch weder auf reine Methacrylatzusammensetzungen noch einen The cover films used according to the invention are PMMA-based films. However, with the formulation of PMMA based films, the films are not limited to pure methacrylate compositions
einschichtigen Aufbau eingeschränkt. Vielmehr kann das PMMA in den Folien Comonomere, bei denen es sich nicht um Methacrylate handelt, enthalten. Auch können die Folien aus Blends verschiedener Kunststoffe, die nicht alle Methacrylate enthalten müssen, zusammengesetzt sein. Die Folien können zusätzlich einen Polybutylacrylat-Elastomeranteil zur Schlazähmodifizierung aufweisen. Darüber hinaus kann die Deckfolie aus mehr als zwei Schichten zusammengesetzt sein. Von diesen Schichten müssen nicht alle zwingend Methacrylate enthalten. single-layered structure limited. Rather, the PMMA may contain in the films comonomers, which are not methacrylates. Also, the films may be composed of blends of various plastics which need not contain all methacrylates. The films may additionally have a polybutyl acrylate elastomer content for Schlähma modification. In addition, the cover sheet may be composed of more than two layers. Not all of these layers necessarily contain methacrylates.
Herstellung der PMMA-Ku nststoffe Production of PMMA plastics
Polymethylmethacrylat-Kunststoffe werden im Allgemeinen durch radikalische Polymerisation von Mischungen erhalten, die Methylmethacrylat enthalten. Im Allgemeinen enthalten diese Mischungen mindestens 40 Gew.-%, Polymethyl methacrylate plastics are generally obtained by free radical polymerization of mixtures containing methyl methacrylate. In general, these mixtures contain at least 40% by weight,
vorzugsweise mindestens 60 Gew.-% und besonders bevorzugt mindestens 80 Gew.-%, bezogen auf das Gewicht der Monomere, Methylmethacrylat.
Daneben können diese Mischungen zur Herstellung von preferably at least 60% by weight and more preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate. In addition, these mixtures for the production of
Polymethylmethacrylaten weitere (Meth)acrylate enthalten, die mit Polymethylmethacrylaten further (meth) acrylates containing, with
Methyl methacrylat copolymehsierbar sind. Der Ausdruck (Meth)acrylate umfasst Methacrylate und Acrylate sowie Mischungen aus beiden. Diese Monomere sind weithin bekannt. Methyl methacrylate are copolymerizable. The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
Neben den zuvor dargelegten (Meth)acrylaten können die zu polymerisierenden Zusammensetzungen auch weitere ungesättigte Monomere aufweisen, die mit Methylmethacrylat und den zuvor genannten (Meth)acrylaten copolymehsierbar sind. Hierzu gehören unter anderem 1 -Alkene, wie Hexen-1 , Acrylnitril; In addition to the (meth) acrylates set out above, the compositions to be polymerized may also contain other unsaturated monomers which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates. These include, inter alia, 1-alkenes, such as hexene-1, acrylonitrile;
Vinylester, wie beispielsweise Vinylacetat; Styrol oder α-Methylstyrol. Vinyl esters such as vinyl acetate; Styrene or α-methylstyrene.
Im allgemeinen werden diese Comonomere in einer Menge von 0 Gew.-% bis 60 Gew.-%, vorzugsweise 0 Gew.-% bis 40 Gew.-% und besonders bevorzugt 0 Gew.-% bis 20 Gew.-%, bezogen auf das Gewicht der Monomeren, eingesetzt, wobei die Verbindungen einzeln oder als Mischung verwendet werden können. In general, 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.
Ferner haben die erfindungsgemäß verwendeten Deckfolien auch große Furthermore, the cover films used in the invention also have large
Vorteile in der Herstellung. Die zum Einsatz kommenden Komponenten wie z.B. die UV-Stabilisatoren und die UV-Absorber ermöglichen den wirtschaftlichen Betrieb einer Extrusionsanlage. So findet beispielsweise eine Ausgasung während der Folienextrusion nicht statt. Somit können aufwendige und qualitätsabträgliche Reinigungsprozesse eingespart werden.
Schlagzähmodifizierter Poly(meth)acrylat-Kunststoff Advantages in the production. The components used, such as the UV stabilizers and UV absorbers, enable the economical operation of an extrusion line. For example, outgassing does not occur during film extrusion. Thus, complex and quality-related cleaning processes can be saved. Impact-modified poly (meth) acrylate plastic
Die erfindungsgemäß verwendete PMMA-basierte Folie kann The PMMA-based film used in the invention can
Schlagzähmodifizierungsmittel enthalten. Eine genauere Beschreibung dieser Schlagzähmodifizierungsmittel findet sich auch in WO 2007/073952. Impact modifier included. A more detailed description of these impact modifiers can also be found in WO 2007/073952.
PMMA/PVDF-Folien PMMA / PVDF films
In einer besonderen Ausführungsform der Erfindung können anstelle von reinen Methacrylatfolien auch PMMA/PVDF-Folien als Deckfolie verwendet werden. PVDF (Polyvinylidenfluorid) als Bestandteil eines Polymerblends oder als Laminat hat einige Vorteile: PVDF weist eine hohe Chemikalienbeständigkeit und eine niedrige Oberflächenenergie auf. Somit ist PVDF wasserabweisend und zeigt auch bei Langzeitanwendung nahezu keinen Bewuchs, vergleichbar mit antibiozidalen Materialien. In a particular embodiment of the invention, instead of pure methacrylate films, PMMA / PVDF films can also be used as the cover film. PVDF (polyvinylidene fluoride) as a component of a polymer blend or as a laminate has several advantages: PVDF has high chemical resistance and low surface energy. Thus, PVDF is water-repellent and shows almost no fouling, even with long-term use, comparable to antibiocidal materials.
Sehr dünne PVDF-Schichten mit einer Schichtdicke zwischen 1 μm und 10 μm, bevorzugt zwischen 2 μm und 5 μm lassen sich zudem auch mit einer hohen Transparenz realisieren. Eine genaue Beschreibung der Herstellung von PMMA/PVDF-Folien findet sich in DE 10 2007 029 263 A1. Very thin PVDF layers with a layer thickness between 1 .mu.m and 10 .mu.m, preferably between 2 .mu.m and 5 .mu.m, can also be realized with a high degree of transparency. A detailed description of the production of PMMA / PVDF films can be found in DE 10 2007 029 263 A1.
Die PMMA/PVDF-Folien können einlagig (Herstellung mittels Chill-Roll- Verfahren) oder mehrlagig (Herstellung mittels Lamination zweier Folien oder Coextrusion der entsprechenden Schmelzeschichten) erhalten werden, wobei nach beiden Varianten alle beim Produkt genannten Vorteile realisierbar sind. Die UV-Stabilisatoren und/oder UV-Absorber können dabei in einer oder beiden Folien enthalten sein. The PMMA / PVDF films can be obtained in one layer (production by means of a chill-roll process) or in multiple layers (production by lamination of two films or coextrusion of the corresponding melt layers), both variants being able to realize all the advantages mentioned in the product. The UV stabilizers and / or UV absorbers can be contained in one or both films.
Sowohl in ein- als auch in mehrlagigen Folien liegt das Verhältnis von Both in single and multilayer films the ratio of
Poly(meth)acrylat zu Polyvinylidenfluorid in einem Bereich von 1 : 0,01 bis 0,3 :
1 (bezogen auf Gewicht). Noch mehr bevorzugt sind solche Modifikationen, bei denen die Folie eine Mischung von Poly(meth)acrylat und Polyvinylidenfluorid im Verhältnis von 1 : 0,1 bis 0,4 : 1 umfasst. Poly (meth) acrylate to polyvinylidene fluoride in a range of 1: 0.01 to 0.3: 1 (by weight). Even more preferred are those modifications in which the film comprises a mixture of poly (meth) acrylate and polyvinylidene fluoride in the ratio of 1: 0.1 to 0.4: 1.
Bei den im Rahmen der Erfindung zum Einsatz kommenden PVDF Polymeren handelt es sich um Polyvinylidenfluoride, das sind in der Regel transparente, teilkristalline, thermoplastische Fluorkunststoffe. Grundbaustein für das 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
Polyvinylidenfluorid ist Vinylidenfluorid, welches in hochreinem Wasser unter kontrollierten Druck- und Temperaturbedingungen mittels eines speziellen Katalysators zu Polyvinylidenfluorid umgesetzt (polymerisiert) wird. Das Polyvinylidene fluoride is vinylidene fluoride, which is reacted (polymerized) in highly pure water under controlled pressure and temperature conditions by means of a special catalyst to polyvinylidene fluoride. The
Vinylidenfluorid wiederum ist beispielsweise aus den Grundmaterialien Vinylidene fluoride is, for example, from the base materials
Fluorwasserstoff und Methylchloroform, über die Zwischenstufe Hydrogen fluoride and methylchloroform, via the intermediate
Chlordifluorethan zugänglich. Im Rahmen der Erfindung sind prinzipiell alle am Markt befindlichen Typen von PVDF mit sehr gutem Erfolg einsetzbar. Hierzu gehören unter anderem Kynar® - Typen des Herstellers Arkema, Dyneon® - Typen des Herstellers Dyneon sowie Solef® - Typen des Herstellers Solvay. Chlorodifluoroethane accessible. In principle, 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.
Das Stabilisatorpaket (Lichtschutzmittel) The stabilizer package (sunscreen)
Ein besonderer Bestandteil der erfindungsgemäß verwendeten UV-Schutzfolien ist das UV-Stabilisatorpaket, das im Folgenden näher beschrieben werden soll. A particular constituent of the UV protective films used according to the invention is the UV stabilizer package, which will be described in more detail below.
Lichtschutzmittel sind hinlänglich bekannt und werden beispielsweise in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5. Ausgabe, 2001 , S. 141 ff ausführlich beschrieben. Unter Lichtschutzmitteln sollen UV-Absorber, UV- Stabilisatoren und Radikalfänger verstanden werden. So können UV-Absorber beispielsweise aus der Gruppe der substituierten Benzophenone, Light stabilizers are well known and are described in detail, for example, in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th edition, 2001, pp. 141 et seq. Sunscreens are to be understood as UV absorbers, UV stabilizers and free-radical scavengers. For example, UV absorbers can be selected from the group of substituted benzophenones,
Salicylsäureester, Zimtsäureester, Oxalanilide, Benzoxazinone, Salicylic acid esters, cinnamic acid esters, oxalanilides, benzoxazinones,
Hydroxyphenylbenztriazole, Thazine oder Benzyliden-Malonat ausgewählt werden.
Den bekanntesten Vertreter der UV-Stabilisatoren / Radikalfänger stellt die Gruppe der sterisch gehinderten Amine (Hindered Amine Light Stabilizer; Hydroxyphenylbenztriazole, thazines or benzylidene malonate can be selected. The best known representative of UV stabilizers / radical scavengers is the group of hindered amines (Hindered Amine Light Stabilizer;
HALS) dar. NECK).
Das in den erfindungsgemäß verwendeten Folien eingesetzte Stabilisatorpaket besteht aus folgenden Komponenten: The stabilizer package used in the films used according to the invention consists of the following components:
• Komponente A: einem UV-Absorber vom Benztriazol-Typ, Component A: a benzotriazole type UV absorber,
• Komponente B: einem UV-Absorber vom Triazin-Typ Component B: a triazine-type UV absorber
• Komponente C: einem UV-Stabilisator, bevorzugt einer HALS- Verbindung Component C: a UV stabilizer, preferably a HALS compound
Die Komponenten A und B können als Einzelsubstanz oder in Mischungen eingesetzt werden. Mindestens eine UV-Absorberkomponentne muss in der Folie enthalten sein. Die Komponente C ist zwingend in der erfindungsgemäß verwendeten Folie enthalten. The components A and B can be used as a single substance or in mixtures. At least one UV absorber component must be included in the film. Component C is mandatory in the film used in the invention.
Komponente A: UV-Absorber vom Benztriazol-Typ Component A: UV absorber of the benzotriazole type
Als UV-Absorber vom Benztriazol-Typ können beispielsweise 2-(2-Hydroxy-5- methylphenyl)-benztriazol, 2-[2-Hydroxy-3,5-di-(alpha,alpha-dimethyl-benzyl)- phenyl]-benztriazol, 2-(2-Hydroxy-3,5-di-t-butylphenyl)-benztriazol, 2-(2- Hydroxy-3-5-butyl-5-methylphenyl)-5-chlorbenzthazol, 2-(2-Hydroxy-3,5-di-t- butylphenyl)-5-chlorbenztriazol, 2-(2-Hydroxy-3,5-di-t-amylphenyl)-benztriazol, 2-(2-Hydroxy-5-t-butylphenyl)-benztriazol, 2-(2-Hydroxy-3-sek-butyl-5-t- butylphenyl)-benztriazol und 2-(2-Hydroxy-5-t-octylphenyl)-benztriazol, Phenol, 2,2*-methylenbis[6-(2H-benztriazol-2-yl)-4-(1 ,1 ,3,3,-tetramethylbutyl)] verwendet werden.
Die UV-Absorber vom Benztriazol-Typ werden in Mengen zwischen 0,1 Gew.-% und 10 Gew.-% eingesetzt, bevorzugt in Mengen zwischen 0,2 Gew.-% und 6 Gew.-% und ganz besonders bevorzugt in Mengen zwischen 0,5 Gew.-% und 4 Gew.-%, bezogen auf das Gewicht der Monomeren, die zur Herstellung der Polymethylmethacrylate eingesetzt werden. Es können auch Mischungen unterschiedlicher UV-Absorber vom Benztriazol-Typ eingesetzt werden. As the benzotriazole-type UV absorber, there can be used, for example, 2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2- [2-hydroxy-3,5-di (alpha, alpha-dimethyl-benzyl) -phenyl] - benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -benzotriazole, 2- (2-hydroxy-3, 5-butyl-5-methylphenyl) -5-chlorobenzthazole, 2- (2-hydroxy -3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) -benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) - benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) -benzotriazole; and 2- (2-hydroxy-5-t-octylphenyl) -benzotriazole, phenol, 2,2 * -methylenebis [6 - (2H-benztriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl)]. The benzotriazole-type UV absorbers are used in amounts between 0.1% and 10% by weight, preferably in amounts between 0.2% and 6% by weight and most preferably in amounts between 0.5% and 4% by weight, based on the weight of the monomers used to make the polymethyl methacrylates. It is also possible to use mixtures of different benzotriazole UV absorbers.
Komponente B: UV-Absorber vom Triazin-Typ Component B: UV absorber of the triazine type
Ferner können in der Mischung auch Triazine, wie beispielsweise das 2-(4,6- Diphenyl-1 ,3,5-thazin-2-yl)-5-hexyloxy-phenol, als UV-Stabilisatoren eingesetzt werden. Furthermore, in the mixture, triazines, such as 2- (4,6-diphenyl-1, 3,5-thazin-2-yl) -5-hexyloxy-phenol, can be used as UV stabilizers.
Die Triazine werden in Mengen zwischen 0,0 Gew.-% und 5 Gew.-% The triazines are used in amounts between 0.0% by weight and 5% by weight.
eingesetzt, bevorzugt in Mengen zwischen 0,2 Gew.-% und 3 Gew.-% und ganz besonders bevorzugt in Mengen zwischen 0,5 Gew.-% und 2 Gew.-%, bezogen auf das Gewicht der Monomeren, die zur Herstellung der used, preferably in amounts between 0.2 wt .-% and 3 wt .-% and most preferably in amounts between 0.5 wt .-% and 2 wt .-%, based on the weight of the monomers used for the preparation of the
Polymethylmethacrylate eingesetzt werden. Es können auch Mischungen unterschiedlicher Triazine eingesetzt werden. Polymethyl methacrylates are used. It is also possible to use mixtures of different triazines.
Komponente C: UV-Stabilisatoren Component C: UV stabilizers
Als Beispiel für Radikalfänger/UV-Stabilisatoren seien hier sterisch gehinderte Amine, die unter dem Namen HALS (JHindered Amine Light Stabilizer) bekannt sind genannt. Sie können für die Inhibierung von Alterungsvorgängen in Lacken und Kunststoffen, vor allem in Polyolefinkunststoffen, eingesetzt werden (Kunststoffe, 74 (1984) 10, S. 620 bis 623; Farbe + Lack, 96 Jahrgang, 9/1990, S. 689 bis 693). Für die Stabilisierungswirkung der HALS-Verbindungen ist die darin enthaltene Tetramethylpiperidingruppe verantwortlich. Diese Examples of radical scavengers / UV stabilizers are sterically hindered amines, which are known by the name HALS (JHindered Amine Light Stabilizer). They can be used for the inhibition of aging processes in paints and plastics, in particular in polyolefin plastics (Kunststoffe, 74 (1984) 10, pp. 620 to 623; Paint + Varnish, 96 Volume, 9/1990, pp. 689 to 693 ). The stabilizing effect of the HALS compounds is due to the tetramethylpiperidine group contained therein. These
Verbindungsklasse kann am Piperidinstickstoff sowohl unsubstituiert als auch
mit Alkyl- oder Acylgruppen substituiert sein. Die sterisch gehinderten Amine absorbieren im UV-Bereich nicht. Sie fangen gebildete Radikale ab, was die UV-Absorber wiederum nicht können. Beispiele für stabilisierend wirkende HALS-Verbindungen, die auch als Gemische eingesetzt werden können sind: Bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacat, 8-Acetyl-3-dodecyl-7,7,9,9- tetramethyl-1 ,3-8-triazaspiro(4,5)-decan-2,5-dion, Bis-(2,2,6,6-tetramethyl-4- piperidyl)-succinat, Poly-(N-ß-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy- piperidin-bernsteinsäureester) oder Bis-(N-methyl-2,2,6,6-tetramethyl-4- piperidyl)-sebacat. Compound class can be both unsubstituted on piperidine nitrogen as well be substituted with alkyl or acyl groups. The sterically hindered amines do not absorb in the UV range. They catch formed radicals, which the UV absorbers can not do. Examples of stabilizing HALS compounds which can also be used as mixtures are: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1, 3-8-triazaspiro (4,5) -decane-2,5-dione, bis (2,2,6,6-tetramethyl-4-piperidyl) -succinate, poly (N β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine-succinic acid ester) or bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate.
Die HALS-Verbindungen werden in Mengen zwischen 0,0 Gew.-% und 5 Gew. % eingesetzt, bevorzugt in Mengen zwischen 0,1 Gew.-% und 3 Gew.-% und ganz besonders bevorzugt in Mengen zwischen 0,2 Gew.-% und 2 Gew.-%, bezogen auf das Gewicht der Monomeren, die zur Herstellung der The HALS compounds are used in amounts between 0.0% by weight and 5% by weight, preferably in amounts of between 0.1% by weight and 3% by weight and very particularly preferably in amounts of between 0.2% by weight % and 2% by weight, based on the weight of the monomers used to prepare the
Polymethylmethacrylate eingesetzt werden. Es können auch Mischungen unterschiedlicher HALS-Verbindungen eingesetzt werden. Polymethyl methacrylates are used. It is also possible to use mixtures of different HALS compounds.
Als weitere Costabilisatoren können ferner die bereits beschriebenen HALS- Verbindungen, Disulfite, wie beispielsweise Natriumdisulfit verwendet werden, ferner sterisch gehinderte Phenole und Phosphite. Further costabilizers which can be used are, furthermore, the HALS compounds already described, disulfites, for example sodium disulfite, and also sterically hindered phenols and phosphites.
Die Klebschicht The adhesive layer
Die optionale Klebschicht dient je nach Herstellungsverfahren zur Verbindung der Deck- und der Trägerfolie. Sie liegt nur vor, wenn eine Haftung zwischen den beiden Folien nicht direkt möglich ist. Die Wahl des geeigneten Klebers ergibt sich aus der Zusammensetzung der beiden Folien - beispielsweise PMMA und PET - und den optischen Eigenschaften. Auch die Klebschicht muss hoch transparent sein. Geeignet können beispielsweise spezielle The optional adhesive layer is used depending on the manufacturing process for connecting the cover and the carrier film. It is only present if adhesion between the two films is not directly possible. The choice of suitable adhesive results from the composition of the two films - for example, PMMA and PET - and the optical properties. The adhesive layer must also be highly transparent. Suitable, for example, special
Acrylatkleber sein.
Die Kratzfestbeschichtung Be acrylate adhesive. The scratch-resistant coating
Der Begriff Kratzfestbeschichtung wird im Zusammenhang mit dieser Erfindung als Sammelbegriff für Beschichtungen verstanden, die zur Verminderung einer Oberflächenverkratzung und/oder zur Verbesserung der Abriebsbeständigkeit aufgebracht werden. Für die erfindungsgemäße Verwendung der The term scratch-resistant coating is understood in the context of this invention as collective term for coatings which are applied to reduce surface scratching and / or to improve the abrasion resistance. For the inventive use of
Folienverbünde in Solarreflektoren ist insbesondere eine hohe Foil composites in solar reflectors is particularly high
Abriebsbeständigkeit von großer Bedeutung. Abrasion resistance of great importance.
Eine weitere wichtige Eigenschaft der Kratzfestbeschichtung im weitesten Sinne ist, dass diese Schicht die optischen Eigenschaften des Folienverbundes nicht negativ verändert. Another important feature of the scratch-resistant coating in the broadest sense is that this layer does not adversely affect the optical properties of the film composite.
Als Kratzfestbeschichtung können Polysiloxane, wie CRYSTALCOAT™ MP-100 der Firma SDC Techologies Inc., AS 400 - SHP 401 oder UVHC3000K, beide von der Firma Momentive Performance Materials, verwendet werden. Diese Lackformulierungen werden z.B. über Rollcoating, Knifecoating oder As a scratch-resistant coating, polysiloxanes, such as CRYSTALCOAT ™ MP-100 from SDC Techologies Inc., AS 400 - SHP 401 or UVHC3000K, both from Momentive Performance Materials, can be used. These paint formulations are e.g. about rollcoating, knifecoating or
Flowcoating auf die Oberfläche des Folienverbundes oder der Deckfolie appliziert. Flowcoating applied to the surface of the film composite or the cover sheet.
Als Beispiele weiterer in Frage kommenden Beschichtungstechnologien seien PVD- (physical vapor deposition; physikalische Gasphasenabscheidung) sowie CVD-Plasma (chemical vapor deposition; chemische Gasphasenabscheidung) erwähnt. Examples of other suitable coating technologies include PVD (physical vapor deposition) and CVD (chemical vapor deposition) plasma.
Die Trägerfolie The carrier foil
Die Wahl der Trägerfolie wird durch folgende, zwingend erforderlichen The choice of carrier film is by the following, mandatory
Eigenschaften bestimmt: Die Folie muss hochtransparent, flexibel, Properties determined: The film must be highly transparent, flexible,
wärmeformbeständig und mit einer dünnen Metallschicht bedampfbar sein. Die Metallschicht sollte dazu über einen langen Zeitraum keinen Haftungsverlust aufweisen. Als Folien mit einem solchen Eigenschaftsprofil haben sich
insbesondere Polyesterfolien, ganz besonders coextrudierte, biaxial orientierte Polyethylenterephthalatfolien (PET) erwiesen. Diese sind optional mit heat-resistant and be metallized with a thin metal layer. The metal layer should have no loss of adhesion over a long period of time. As films with such a property profile have especially polyester films, especially coextruded, biaxially oriented polyethylene terephthalate (PET) films. These are optional with
Haftvermittlern zur besseren Anhaftung der Metall-, Oberflächenvergütungsbzw, der Klebschicht ausgestattet. Adhesives for better adhesion of the metal, Oberflächenvergütungsbzw, the adhesive layer equipped.
Alternativ können auch PMMA-FoI ien, PVDF/PMMA-Zweischichtfolien oder Folien aus PVDF/PMMA-Blends als Trägerfolien verwendet werden. Alternatively, PMMA foils, PVDF / PMMA two-layer foils or films of PVDF / PMMA blends can also be used as carrier foils.
Die Metallschicht The metal layer
Die Metallschicht wird bevorzugt auf der Rückseite der Trägerfolie aufgetragen und besteht bevorzugt aus Silber oder Aluminium, besonders bevorzugt aus Silber. Auf der der Trägerfolie abgewandten Seite, kann die Metallschicht optional mit einer zweiten Metallschicht, beispielsweise aus Kupfer oder einer Nickel-Chrom-Legierung, überzogen werden. Diese dient zum einen als Schutz der Metallspiegelschicht und zum anderen zur besseren Haftung der The metal layer is preferably applied to the back of the carrier film and is preferably made of silver or aluminum, more preferably of silver. On the side facing away from the carrier film, the metal layer can optionally be coated with a second metal layer, for example made of copper or a nickel-chromium alloy. This serves as a protection of the metal mirror layer and on the other hand for better adhesion of the
Haftklebeschicht. Pressure-sensitive adhesive layer.
Alternativ zu Silber findet Aluminium als Metall für die Spiegelschichten Alternative to silver is aluminum as metal for the mirror layers
Verwendung. Bevorzugt wird hierbei die vergleichsweise„niedrige" Reflektion des Aluminiumspiegels im relevanten Wellenlängenbereich durch die Use. In this case, the comparatively "low" reflection of the aluminum mirror in the relevant wavelength range by the
Applikation sogenannter„Enhancement Stack"-Schichten (mittels„Physical Vapor Deposition") angehoben. Application of so-called "enhancement stack" layers raised (by means of "Physical Vapor Deposition").
Alternativ zu der Verwendung in dem beschriebenen Folienverbund können die erfindungsgemäß verwendeten Deckfolien auch zur Oberflächenvergütung bzw. zur Verbesserung des Witterungsschutzes von mehrschichtigen As an alternative to the use in the film composite described, the cover films used according to the invention can also be used for surface treatment or for improving the weathering protection of multi-layered films
Aluminiumband-basierenden Schichtsystemen, wie sie z.B. von der Firma Alanod solar unter dem Namen MIRO-SUN® vertrieben werden, verwendet werden.
Besondere Ausführungsform Aluminum band-based layer systems, such as those sold by the company Alanod solar under the name MIRO-SUN ® can be used. Special embodiment
In einer besonderen Ausführungsform wird ein Metall-Schichtsystem in Form eines Metallbandes, bevorzugt auf Aluminiumbasis, wie z.B. MIRO-SUN®, das gleichzeitig als Trägerfolie dient, eingesetzt. In dieser Ausführungsform sind die Trägerfolie und die Metallschicht somit identisch und es wird keine weitere Trägerfolie auf Polymerbasis benötigt. In a particular embodiment, a metal layer system in the form of a metal strip, preferably based on aluminum, such as MIRO-SUN ® , which also serves as a carrier film, is used. In this embodiment, the carrier film and the metal layer are thus identical and no further polymer-based carrier film is required.
Die Haftklebeschicht The pressure-sensitive adhesive layer
Die Haftklebeschicht dient zum Verkleben des Folienverbundes beispielsweise auf ein Trägermaterial, wie zum Beispiel eine gewölbte Aluminiumplatte. Die Auswahl des Haftklebers (PSA) wird durch die Haftung gegenüber diesem Trägermaterial und der Rückseite der Metallbeschichtung bestimmt. Zum Schutz der Metallbeschichtung wäre es ferner von Vorteil, wenn die The pressure-sensitive adhesive layer is used for bonding the film composite, for example, to a carrier material, such as a curved aluminum plate. The choice of pressure-sensitive adhesive (PSA) is determined by the adhesion to this substrate and the back of the metal coating. To protect the metal coating, it would also be advantageous if the
Haftklebeschicht eine nur geringe Durchlässigkeit für Luftsauerstoff und Adhesive layer a low permeability to atmospheric oxygen and
Wasserdampf aufweist. Has water vapor.
Die Haftklebeschicht wird zum Transport und Lagerung auf ein silikonisiertes Papier geklebt. Vor dem Verkleben auf dem Trägermaterial kann dieses einfach wieder entfernt werden. The pressure-sensitive adhesive layer is glued on a siliconized paper for transport and storage. Before gluing on the carrier this can be easily removed.
Migrationssperrschicht und Primer Migration barrier layer and primer
Als Migrationssperre kommen Materialien zum Einsatz, die eine Migration der für die Metallschicht schädlichen Bestandteile, wie z.B. Luftsauerstoff, As migration barrier materials are used, which are a migration of harmful for the metal layer components such. Atmospheric oxygen,
Wasserdampf oder auch mirgationsfähige Bestandteile des Haftklebers, verhindern. Dies kann zum Beispiel eine Epoxisharzschicht sein. Water vapor or even mirgationsfähige constituents of the pressure-sensitive adhesive, prevent. This may be, for example, an epoxy resin layer.
Die Wahl und die Notwendigkeit eines Primers ergibt sich aus den Haftungsbzw. Oberflächeneigenschaften der Metallschicht und des eingesetzten The choice and necessity of a primer results from the Haftungsbzw. Surface properties of the metal layer and the used
Haftkleber.
Alternativer Folienverbundaufbau Pressure sensitive adhesive. Alternative film composite construction
Alternativ zu der bereits dargelegten Schichtfolge der erfindungsgemäßen Folienverbund-Systeme, bestehend - von außen nach innen - aus einer optionalen Kratzfestbeschichtung, einer optionalen Antischmutzbeschichtung, einer Deckfolie, einer optionalen Klebschicht, einer Trägerfolie, der Alternatively to the above-described layer sequence of the film composite systems according to the invention, consisting - from outside to inside - of an optional scratch-resistant coating, an optional antifouling coating, a cover sheet, an optional adhesive layer, a carrier film, the
Metallschicht, einer optionalen Primer und/oder Migrationssperrschicht und einem Haftkleber, kann der Folienverbund - von außen nach innen - auch in folgender Schichtabfolge aufgebaut sein: Metal layer, an optional primer and / or migration barrier layer and a pressure-sensitive adhesive, the film composite - from outside to inside - can also be constructed in the following layer sequence:
- Kratzfestbeschichtung und/oder Antischmutzbeschichtung (optional) - Scratch-resistant coating and / or anti-soiling coating (optional)
- Deckfolie - cover sheet
- Klebschicht (optional) - adhesive layer (optional)
- Metallschicht - metal layer
- Primer und/oder Migrationssperre - primer and / or migration barrier
- Trägerfolie - Carrier film
- Haftkleber - Pressure-sensitive adhesive
Herstellung des Folienverbunds Production of the film composite
Die erfindungsgemäß verwendete ein- oder mehrlagige Deckfolie kann je nach Anwendungszweck in jeder beliebigen Dicke hergestellt werden. Entscheidend ist dabei in jedem Falle die hohe Transparenz der Deckfolie, gepaart mit einer außerordentlichen Witterungsstabilität sowie dem extremen Bewitterungsschutz für das Substrat.
Die Herstellung der ein- oder mehrschichtigen Deckfolie erfolgt durch an sich bekannte Methoden, wie beispielsweise der Extrusion durch eine The single-layer or multi-layer cover film used according to the invention can be produced in any desired thickness, depending on the intended use. Decisive in any case is the high transparency of the cover film, coupled with an extraordinary weathering stability as well as the extreme weathering protection for the substrate. The preparation of the single or multilayer cover sheet is carried out by methods known per se, such as extrusion through a
Breitschlitzdüse wie bei der Flachfolienextrusion, der Blasfolienextrusion oder durch Lösungsgießen. Slot die as in flat film extrusion, blown film extrusion or solution casting.
Der Folienverbund wird beispielsweise durch, Kaschierung und/oder durch (Co)Extrusionsbeschichtung und/oder durch Lamination hergestellt werden.
The film composite is produced, for example, by lamination and / or by (co) extrusion coating and / or by lamination.
Claims
1. Folienverbund zur Anwendung in Solarreflektoren dadurch 1. Film composite for use in solar reflectors thereby
gekennzeichnet, dass sich der Folienverbund mindestens aus characterized in that the film composite at least
einer Deckfolie, a cover sheet,
einer Trägerfolie, a carrier film,
einer Metallschicht, a metal layer,
und einem Haftklebstoff zusammensetzt, und dass and a pressure-sensitive adhesive, and that
die Deckfolie mindestens ein Triazin als UV-Absorber und einen UV- Stabilisator enthält. the cover sheet contains at least one triazine as UV absorber and a UV stabilizer.
2. Folienverbund zur Anwendung in Solarreflektoren dadurch 2. Film composite for use in solar reflectors thereby
gekennzeichnet, dass sich der Folienverbund in aufgeführter Reihenfolge mindestens aus characterized in that the film composite in the listed order at least
einer Deckfolie, a cover sheet,
einer Trägerfolie, a carrier film,
einer Metallschicht, a metal layer,
und einem Haftklebstoff zusammensetzt, und dass and a pressure-sensitive adhesive, and that
die Deckfolie mindestens ein Triazin als UV-Absorber und einen UV- Stabilisator enthält. the cover sheet contains at least one triazine as UV absorber and a UV stabilizer.
3. Folienverbund zur Anwendung in Solarreflektoren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei der Deckfolie um eine PMMA-basierte Folie, bei der Trägerfolie um eine Polyesterfolie, PMMA- FoNe, eine PVDF/PMMA-Zweischichtfolie oder eine Folie bestehend aus einem PVDF/PMMA-Blend und bei der Metallschicht um eine Silberoder Aluminiumschicht, bevorzugt um eine Silberschicht handelt. 3. film composite for use in solar reflectors according to claim 1 or 2, characterized in that it consists of the cover sheet to a PMMA-based film in the carrier film to a polyester film, PMMA FoNe, a PVDF / PMMA two-layer film or a film of a PVDF / PMMA blend and the metal layer is a silver or aluminum layer, preferably a silver layer.
4. Folienverbund zur Anwendung in Solarreflektoren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei der Trägerfolie und der Metallschicht um ein und dieselbe Schicht auf Metallbasis, bevorzugt auf Aluminiumbasis, handelt. 4. film composite for use in solar reflectors according to claim 1 or 2, characterized in that it is in the support film and the metal layer to one and the same layer based on metal, preferably based on aluminum.
5. Folienverbund zur Anwendung in Solarreflektoren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass zwischen der 5. film composite for use in solar reflectors according to one of claims 1 to 3, characterized in that between the
Deckfolie und der Trägerfolie bzw. zwischen der Deckfolie und der Metallspiegelschicht zusätzlich eine Klebschicht aufgebracht ist. Cover film and the carrier film or between the cover sheet and the metal mirror layer in addition an adhesive layer is applied.
6. Folienverbund gemäß einem der Ansprüche 1 bis 5, dadurch 6. film composite according to one of claims 1 to 5, characterized
gekennzeichnet, dass die Deckfolie ein Gemisch aus UV-Absorbern, bestehend aus mindestens einem Triazin und mindestens einem in that the cover film comprises a mixture of UV absorbers consisting of at least one triazine and at least one
Benztriazol,.und mindestens einen UV-Stabil itsator, bei dem es sich um eine HALS-Verbindung oder eine Mischung verschiedener HALS- Verbindungen handelt, enthält Benzotriazole, and at least one UV stabilizer, which is a HALS compound or a mixture of different HALS compounds
7. Folienverbund gemäß einem der Ansprüche 1 bis 6, dadurch 7. film composite according to one of claims 1 to 6, characterized
gekennzeichnet, dass die Mischung aus UV-Stabilisatoren und UV- Absorbern aus folgenden Mengen zusammengesetzt ist: in that the mixture of UV stabilizers and UV absorbers is composed of the following amounts:
zwischen 0,1 Gew% und 10 Gew%, bevorzugt zwischen 0,5 Gew% und between 0.1% by weight and 10% by weight, preferably between 0.5% by weight and
4 Gew% der UV-Absorber vom Benztriazol-Typ, 4% by weight of the benzotriazole-type UV absorbers,
zwischen 0,1 Gew% und 5 Gew%, bevorzugt zwischen 0,5 Gew% und 3 between 0.1% by weight and 5% by weight, preferably between 0.5% by weight and 3
Gew% der UV-Absorber vom Triazin-Typ und % By weight of the triazine-type UV absorbers and
zwischen 0,1 Gew% und 5 Gew%, bevorzugt zwischen 0,2 Gew% und 2 between 0.1% by weight and 5% by weight, preferably between 0.2% by weight and 2
Gew% der UV-Stabilisatoren vom HALS-Typ. % By weight of UV stabilizers of the HALS type.
8. Folienverbund gemäß einem der Ansprüche 1 bis 7, dadurch 8. film composite according to one of claims 1 to 7, characterized
gekennzeichnet, dass sich die Deckfolie aus Poly(meth)acrylat und Polyvinylidenfluorid in einem Gewichtsverhältnis zwischen 1 zu 0,01 und 0,3 zu 1 , bevorzugt zwischen 1 zu 0,1 und 0,4 zu 1 zusammensetzt und UV-Stabilisatoren und UV-Absorber enthält. in that the cover sheet of poly (meth) acrylate and polyvinylidene fluoride is composed in a weight ratio of between 1: 0.01 and 0.3: 1, preferably between 1: 0.1 and 0.4: 1, and UV stabilizers and UV Absorber contains.
9. Folienverbund gemäß Anspruch 8, dadurch gekennzeichnet, dass die Deckfolie zwei Lagen umfasst, von denen es sich bei einer um eine Lage bestehend aus Poly(meth)acrylat und bei der anderen um eine Lage bestehend aus Polyvinylidenfluorid handelt. 9. film composite according to claim 8, characterized in that the cover sheet comprises two layers, one of which is a poly (meth) acrylate in one layer and in the other by a layer consisting of polyvinylidene fluoride.
10. Folienverbund gemäß einem der Ansprüche 1 bis 9, dadurch 10. film composite according to one of claims 1 to 9, characterized
gekennzeichnet, dass die Deckfolie kratzfest ausgestattet ist, bevorzugt durch eine Beschichtung zur Erhöhung der Kratzfestigkeit. characterized in that the cover sheet is provided scratch-resistant, preferably by a coating to increase the scratch resistance.
11. Folienverbund gemäß einem der Ansprüche 1 bis 10, dadurch 11. film composite according to one of claims 1 to 10, characterized
gekennzeichnet, dass die Oberfläche der Deckfolie mit einer Antisoiling- Beschichtung ausgestattet ist. in that the surface of the cover foil is provided with an antisoiling coating.
12. Verwendung eines Folienverbundes gemäß einem der vorhergehenden Ansprüche als Spiegelfolie in Sonnenreflektoren. 12. Use of a film composite according to one of the preceding claims as a mirror film in Sonnenreflektoren.
13. Verwendung gemäß Anspruch 12, dadurch gekennzeichnet, dass das Aufbringen der Spiegelfolie auf einem Trägerblech mittels 13. Use according to claim 12, characterized in that the application of the mirror film by means of a carrier sheet
Folienlamination erfolgt und die Haftung zum Trägerblech durch die Haftklebschicht bewirkt wird. Film lamination takes place and the adhesion to the support plate is effected by the pressure-sensitive adhesive layer.
14. Langlebiger Sonnenreflektor, enthaltend einen Folienverbund gemäß einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass die solare Reflektion innerhalb von 10 Jahren um maximal 8%, bevorzugt um maximal 5% und besonders bevorzugt um maximal 3% abnimmt. 14. Long-life solar reflector, comprising a film composite according to one of claims 1 to 11, characterized in that the 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009028168A DE102009028168A1 (en) | 2009-07-31 | 2009-07-31 | Solar mirror film compound with particularly high weathering and UV resistance |
| PCT/EP2010/056680 WO2011012342A1 (en) | 2009-07-31 | 2010-05-17 | Solar mirror film composite having particularly high weathering and uv stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2459369A1 true EP2459369A1 (en) | 2012-06-06 |
Family
ID=42600338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10721769A Withdrawn EP2459369A1 (en) | 2009-07-31 | 2010-05-17 | Solar mirror film composite having particularly high weathering and uv stability |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20120107609A1 (en) |
| EP (1) | EP2459369A1 (en) |
| JP (1) | JP2013501251A (en) |
| KR (1) | KR20120052947A (en) |
| CN (1) | CN102470635A (en) |
| AR (1) | AR079592A1 (en) |
| AU (1) | AU2010278246A1 (en) |
| BR (1) | BR112012002277A2 (en) |
| CL (1) | CL2012000256A1 (en) |
| DE (1) | DE102009028168A1 (en) |
| IL (1) | IL217144A0 (en) |
| MA (1) | MA33498B1 (en) |
| MX (1) | MX2012001148A (en) |
| SG (1) | SG178192A1 (en) |
| TN (1) | TN2011000670A1 (en) |
| WO (1) | WO2011012342A1 (en) |
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| JP5920211B2 (en) * | 2010-03-27 | 2016-05-18 | コニカミノルタ株式会社 | Film mirror for solar power generation, method for manufacturing film mirror for solar power generation, and reflector for solar power generation |
| US20130088774A1 (en) * | 2010-06-23 | 2013-04-11 | Konica Minolta Advanced Layers, Inc. | Film mirror for solar heat generation and process for production thereof, and reflection device for solar heat generation |
| JP5747547B2 (en) * | 2011-02-18 | 2015-07-15 | コニカミノルタ株式会社 | Reflector for film mirror and solar power generation |
| DE102011077878A1 (en) * | 2011-06-21 | 2012-12-27 | Evonik Röhm Gmbh | 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 |
| DE102011113160A1 (en) | 2011-09-14 | 2013-03-14 | Evonik Röhm Gmbh | Polymeric outdoor materials with self-healing surface properties after scratching or abrasion damage |
| JP6702720B2 (en) | 2012-05-03 | 2020-06-03 | スリーエム イノベイティブ プロパティズ カンパニー | Durable solar mirror film |
| KR101489996B1 (en) * | 2012-09-12 | 2015-02-12 | (주)엘지하우시스 | Acryl based multi layer having high weatherability and method for prepareing the same |
| US20170204297A1 (en) * | 2014-07-14 | 2017-07-20 | Denka Company Limited | Polyvinylidene fluoride resin adhesive film |
| US10345495B2 (en) * | 2014-12-30 | 2019-07-09 | 3M Innovative Properties Company | Stain resistant retroreflective articles |
| CN105437569B (en) * | 2015-12-10 | 2018-03-16 | 上海复合材料科技有限公司 | A kind of forming method of composite reflector |
| IT201800003093A1 (en) * | 2018-02-27 | 2019-08-27 | Coveme S P A | Stratiform structure reflecting by solar radiation and method of realization |
| ES1235931Y (en) * | 2019-08-09 | 2020-01-09 | Povedano Gonzalez Vicens | Protective coating for exteriors. |
| CN111154209B (en) * | 2020-01-23 | 2022-04-05 | 上海锦湖日丽塑料有限公司 | Wear-resistant scratch-resistant hydrophobic transparent PMMA composition and preparation method thereof |
| NL2029984B1 (en) * | 2021-12-01 | 2023-05-31 | Jiaxing Gaozheng New Material Tech Co Ltd | Pvdf membrane and preparation device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US6989924B1 (en) * | 1998-08-06 | 2006-01-24 | Midwest Research Institute | Durable corrosion and ultraviolet-resistant silver mirror |
| US7612937B2 (en) | 2001-02-09 | 2009-11-03 | Alliance For Sustainable Energy, Llc | Advanced ultraviolet-resistant silver mirrors for use in solar reflectors |
| DE102005062687A1 (en) * | 2005-12-23 | 2007-07-05 | Röhm Gmbh | Plastic film comprising a transparent plastic and a mixture of UV stabilisers and UV absorbers, used for producing high-quality, permanently non-weathering coatings on substrate materials or on PVC film |
| DE102007029263A1 (en) | 2007-06-22 | 2008-12-24 | Evonik Röhm Gmbh | PMMA / PVDF film with particularly high weather resistance and high UV protection |
-
2009
- 2009-07-31 DE DE102009028168A patent/DE102009028168A1/en not_active Withdrawn
-
2010
- 2010-05-17 EP EP10721769A patent/EP2459369A1/en not_active Withdrawn
- 2010-05-17 KR KR1020127002504A patent/KR20120052947A/en not_active Withdrawn
- 2010-05-17 MX MX2012001148A patent/MX2012001148A/en unknown
- 2010-05-17 US US13/382,577 patent/US20120107609A1/en not_active Abandoned
- 2010-05-17 AU AU2010278246A patent/AU2010278246A1/en not_active Abandoned
- 2010-05-17 MA MA34573A patent/MA33498B1/en unknown
- 2010-05-17 BR BR112012002277A patent/BR112012002277A2/en not_active Application Discontinuation
- 2010-05-17 SG SG2012006813A patent/SG178192A1/en unknown
- 2010-05-17 WO PCT/EP2010/056680 patent/WO2011012342A1/en not_active Ceased
- 2010-05-17 CN CN201080033974XA patent/CN102470635A/en active Pending
- 2010-05-17 JP JP2012522046A patent/JP2013501251A/en not_active Withdrawn
- 2010-07-30 AR ARP100102781A patent/AR079592A1/en unknown
-
2011
- 2011-12-22 IL IL217144A patent/IL217144A0/en unknown
- 2011-12-27 TN TNP2011000670A patent/TN2011000670A1/en unknown
-
2012
- 2012-01-31 CL CL2012000256A patent/CL2012000256A1/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2011012342A1 * |
Also Published As
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| KR20120052947A (en) | 2012-05-24 |
| DE102009028168A1 (en) | 2011-02-10 |
| SG178192A1 (en) | 2012-03-29 |
| AU2010278246A1 (en) | 2012-02-02 |
| MA33498B1 (en) | 2012-08-01 |
| JP2013501251A (en) | 2013-01-10 |
| BR112012002277A2 (en) | 2016-06-14 |
| US20120107609A1 (en) | 2012-05-03 |
| AR079592A1 (en) | 2012-02-08 |
| IL217144A0 (en) | 2012-02-29 |
| MX2012001148A (en) | 2012-02-17 |
| TN2011000670A1 (en) | 2013-05-24 |
| CN102470635A (en) | 2012-05-23 |
| WO2011012342A1 (en) | 2011-02-03 |
| CL2012000256A1 (en) | 2012-09-14 |
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