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    • 专利摘要:
    The invention relates to a polymer sheet and its use as part of a solar panel and a glass element. The plate contains several co-extruded polymer layers, with at least two or more layers of the polymer plate containing a luminescent downshifting mixture to at least partially absorb radiation of a certain wavelength and re-emit radiation at a wavelength longer than the wavelength of the absorbed radiation , and wherein a luminescent downshifting mixture in a first polymeric layer can absorb more radiation at a lower wavelength than the luminescent downshifting mixture present in the next layer.
    公开号:BE1021330B1
    申请号:E2013/0348
    申请日:2013-05-16
    公开日:2015-10-30
    发明作者:Johan Willy Declerck；Koen Hasaers；Kristof Proost
    申请人:Novopolymers N.V.；
    IPC主号:
    专利说明:

    Polymer film
    The invention relates to a polymer film with a luminescence downshifting (Luminescence Downshifting; in the following LDS) component. Such components have the property that they can absorb radiation of a certain wavelength at least partially and can radiate again with a wavelength longer than the wavelength of the absorbed radiation. The invention further relates to the different applications of the co-extruded polymer film for glass elements and for photovoltaic cells and solar panels.
    Such a polymer film is known from WO-A-2008/110567. This publication describes a polymer encapsulation film that is used to protect a photovoltaic cell and the polymer encapsulation film of which contains an LDS component. This publication does not make working examples public.
    The specification makes a long list of LDS components, including many organic components.
    Many organic components have more favorable properties with regard to their efficiency to absorb radiation of a certain wavelength and to radiate it with a higher wavelength. A problem with the use of such components is their stability. When a film containing such an organic component is used in combination with a photovoltaic cell in a solar cell, it is preferred that they remain stable over the lifetime of the solar cell.
    The object of the present invention is to provide a polymer film with an LDS component, wherein the LDS component retains the downshifting capacity for a longer period of time.
    This object is achieved by the following polymer film. Polymer films containing a plurality of co-extruded polymer layers, wherein at least one of these layers contains an LDS component to at least partially absorb radiation of a certain wavelength and radiate radiation with a wavelength longer than the absorbed wavelength.
    Applicants discovered that by using separate polymer layers, the stability of the LDS component as present in at least one layer can be improved.
    The polymer film can have a first polymer layer that contains a UV stabilizer additive and another polymer layer that contains the LDS component. In this way, the LDS component can be protected against UV radiation and UV-induced degradation, which usually affects the stability of the LDS components and the polymers in the polymer layers. This can result in a reduction of UV stabilizers, whereby not only the stability of the LDS components can be increased, but also the costs and the total amount of absorbed sunlight. Moreover, the use of different LDS components on different layers allows a finer alignment with the environment of the LDS components, which can react with other LDS components, in particular in the excited state, but also with chemicals in the layers, such as peroxides. Furthermore, the use of co-extruded polymer layers makes it possible to precisely determine the properties of each layer, e.g. the copolymers, while benefiting from high adhesion due to additional polymer layers and moisture-repellent properties. Preferably, two or more layers of polymer film contain an LDS component. This allows a layer containing an LDS component that is less stable when exposed to radiation of a certain wavelength to be used in combination with a layer containing an LDS component that by means of a Stoke shift convert harmful radiation into less harmful radiation. The above configuration results in a more stable polymer film.
    The invention further enables UV-sensitive polymers, such as, for example, ethylene vinyl acetate (EVA), to be used without or with considerably fewer UV stabilizers. Previously, UV stabilizers were required to protect the polymer encapsulation film containing EVA. The use of these stabilizers reduced the efficiency of a solar panel because the UV radiation is converted into heat by these UV stabilizers. By using an LDS component that can absorb radiation in a UV wavelength range and can radiate it again with a higher wavelength range, the UV light is converted into radiation that is less harmful to the polymer and that can be effectively used to generate electricity to be generated through the photovoltaic effect.
    Unless otherwise stated, all percentages, fractions, fractions, etc., are by weight. When a quantity, concentration or other value or parameter is given as a range, preference range or list of highest preferred values and lowest preferred values, this should be understood as all ranges formed by all pairs of upper limits or preferred values and lower limits or preferred values, also if ranges are not listed separately. When a range of numerical values is quoted below, this also includes the end points, and all integers and fractions within the range, unless stated otherwise. It is not intended that the scope of the invention be limited to the specific values mentioned in the definition of a range.
    When the term "about" is used to describe a value or an endpoint of a range, it also includes the specific value or endpoint that is referred to.
    The terms "include", "including," contain "," characterized by "," has ", or any variation thereof, used herein are to be understood as a non-exclusive inclusion, for example, a process, method, article, or equipment that contains a list of elements is not necessarily limited to these elements, but may also contain other elements that are not explicitly mentioned or inherent to such processes, methods, articles, or equipment. Furthermore, "or unless expressly stated otherwise means an inclusive "or and not an exclusive" or. The transitional phrase "essentially consists of" limits the scope of a claim to the specified materials or steps and those that do not directly materially affect the elemental and novel properties of the claimed invention.
    Where applicants have defined an invention or a part thereof with an open concept such as "includes", it should be understood that unless otherwise stated this can also be read as "consists essentially of".
    The indefinite article "a" is used to describe elements and components of the invention. This is only for convenience and to give a general impression of the invention. This description always relates to one or at least one and the singular also includes the plural unless it is evident that it is intended otherwise.
    In describing certain polymers, applicants sometimes refer to the polymers via the monomers used to produce them or the amount of monomers to produce the polymers. Although such a description does not necessarily use the specific nomenclature to describe the final polymer, or does not use product-to-process terminology, all such references to monomers and quantities mean that the polymer contains these monomers (ie, copolymerized units of these monomers ) or that amount of monomers, and the corresponding polymers and compositions thereof.
    In describing and / or claiming this invention, the term "copolymer" is used for polymers formed by copolymerization of two or more monomers. Such copolymers include dipolymers, terpolymers or higher order polymers.
    The melt flow index (MFI), hereinafter referred to as MFI, is a measure of the flow of a molten thermoplastic polymer. It is defined as the polymer mass, in grams, flowing through a capillary of a specific diameter and length in ten minutes under pressure caused by prescribed alternative gravimetric weights for alternative prescribed temperatures, and is determined according to ASTM D1238.
    It should be noted that when a polymer is formulated with a crosslinker mechanism that starts above a certain temperature, e.g. EVA copolymers and peroxides, the rheology values used herein refer to materials that are not, or are only partially, crosslinkers. When cross-linking is complete, i.e., in the lamination process of a photovoltaic module, the polymers that have been crosslinked are no longer considered a thermoplastic material. Therefore, the described properties concern the polymers for the lamination process, including the cross-linked polymers.
    The term melting point as used herein refers to the transition from a crystalline or semi-crystalline phase to a solid amorphous phase, also known as the crystalline melting temperature. The melting point of a polymer can advantageously be determined by DSC. In the case of a block copolymer, the term "melting point" hereinafter refers to the temperature at which the higher melting block component exceeds its glass transition temperature, thereby melting and flowing the polymer. The "extrusion temperature" means the temperature at which a polymer is heated during extrusion, by means of a heated extruder or a heated die.
    When reference is made to the melting temperature of a particular layer, this temperature, due to the fact that the layers consist essentially of polymer materials with only additives or optional other polymers, is largely determined by the melting temperature of the polymer material present in the layer. Accordingly, the melting temperature is to be considered as the temperature of the polymeric material present in the layer. The additives and / or optional polymers can be present in an amount of up to 25% by weight, based on the total weight of the main polymer in a layer, provided that the inclusion of such additives and / or optional polymers does not negatively influence the melt flow index.
    The term "first polymer layer" refers to a layer of the polymer film located in the direction of the glowing light. The layer may be in direct contact with the glass or the front film, or it may be an intermediate layer. In this context, the next layer means the adjacent layer in the direction of the glowing light. The layers can connect directly to each other, or can be separated by further intermediate layers.
    An LDS component is preferably present in a first polymer layer, which LDS component has the property that it can absorb more radiation of a lower wavelength than the LDS component in a subsequent layer. This layer will therefore contain LDS file (s) that absorb radiation of a lower wavelength than the LDS file (s) in the remaining polymer layer (s). This is advantageous because many organic components are particularly sensitive to radiation with a shorter wavelength. By filtering this shorter wavelength radiation and delivering longer wavelength radiation, a more stable polymer film is obtained. Preference is given to a first polymer layer, i.e. barrier layer, with the property that it can at least partially absorb UV radiation, suitably between 10 and 400 nm, and can radiate with a higher wavelength. The LDS component / components that absorb this UV wavelength can be combined with traditional UV stabilizers. Preferably, the use of such conventional stabilizers is limited because they convert the absorbed UV radiation into thermal energy instead of emitting it at higher wavelengths. A more efficient polymer film is thus obtained when such UV stabilizers are omitted or used in a low concentration. The LDS component then takes over the protective function of the UV stabilizer.
    The LDS component can be an organic or inorganic LDS component that is capable of partially absorbing radiation with a certain wavelength and re-radiating it with a wavelength higher than the wavelength of the absorbed radiation. Such components are known and are described, for example, in Efthymios Klampaftis, David Ross, Keith R. Mclntosh, Bryce S. Richards, Enhancing the performance of a solar cell via luminescent down-shifting or incident spectrum, a review, Solar Energy Materials & Solar Cells 93 (2009) 1182-1194. Preferably, at least a number of the LDS components are organic components, because the advantages of the invention apply primarily to this group of components.
    A suitable organic LDS component is, for example, laser pigment. The following components, some of which are also used as laser pigments, can be used as an LDS component: Rodamine, for example 5-carboxy tetramethylrodamine, Rodamine 6G, Rodamine B, Rubrene, aluminum tris - ([delta] hydroxyquinoline (Alq3), N, N'-diphenyl-N, N'-bis- (3-methylphenyl) -1,1'-biphenyl-4-4'-diamine (TPD), bis- (8-hydroxyquinoline) chlorogallium (Gaq 2 Cl); a perylene carboxylic acid or a derivative thereof, a naphthalene carboxylic acid or a derivative thereof, a violanthrone or an iso-violanthrone or a derivative thereof Examples of organic LDS components are quinine, fluorescine, sulforhodamine, 5-Bis (5-tert- butyl 2-enzoxazolyl) thiophene, Nile Blue.
    Other examples of suitable organic LDS components are coumarin pigments, for example 7-Diethylaminocoumarin-3-carboxylic acid hydrazide (DCCH), 7-Diethylaminocoumarin-3-carboxylic acid succinimidyl ester, 7-Methoxycoumarin-3-carboxylic acid succinimidyl ester, 7-Hydroxycoumarin-3 carboxylic acid succinimidyl ester, 7-Diethylamino-3 - (((((2-iodoacetamido) ethyl) amino) carbonyl) coumarin (IDCC), 7-Diethylamino-3 - (((((2-maleimidyl) ethyl) amino) carbonyl) coumarin (MDCC), 7-Dimethylamino-4-methyl-coumarin-3-isothiocyanate (DACITC), N- (7-Dimethylamino-4-methyl-coumarin-3-yl) maleimide (DACM), N- (7-Dimethylamino-4-methyl-coumarin- 3-yl) iodoacetamide (DACIA), 7-Diethylamino-3- (4'-maleimidylphenyl) -4-methyl coumarin (CPM), 7-Diethylamino-3 - ((4 '- (iodoacetyl) amino) phenyl) -4- methyl coumarin (DCIA), 7-Dimethylaminocoumarin-4-acetic acid (DMACA) and 7-Dimethylaminocoumarin-4-acetic acid succinimidyl ester (DMACASE).
    Other examples of suitable organic LDS components are perylene pigments, for example N, β'-Bis (2,6-diisopropylphenyl) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-Bis (2,6-dimethylphenyl) ) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-Bis (7-tridecyl) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-Bis (2,6-diisopropylphenyl) ) -1,6,7,12-tetra (4-tert-octylphenoxy) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, β'-Bis (2,6-diisopropylphenyl) -1.6, 7,12-tetraphenoxyperylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-Bis (2,6-diisopropylphenyl) -1,6- and -1,7-bis (4-tert-octylphenoxy) perylene -3,4: 9,10-tetracarboxylic acid diimide, N, N'-Bis (2,6-diisopropylphenyl) -1,6- and -1,7-bis (2,6-diisopropylphenoxy) -perylene-3,4 : 9,10-tetracarboxylic acid diimide, N- (2,6-diisopropylphenyl) perylene-3,4-dicarboxylic acid imide, N- (2,6-diisopropylphenyl) -9-phenoxyperylene-3,4-dicarboxylic acid imide, N- ( 2,6-diisopropylphenyl) -9- (2,6-diisopropylphenoxy) perylene-3,4-dicarboxylic acid imide, N- (2,6-diisopropylphenyl) -9-cyanoper yleen-3,4-dicarboxylic acid imide, N- (7-tridecyl) -9-phenoxyperylene-3,4-dicarboxylic acid imide, perylene-3,9- and -3,10-dicarboxylic acid diisobutyl ester, 4,10-dicyanoperylene -3,9- and 4,9-dicyanoperylene-3,10-dicarboxylic acid diisobutyl ester and perylene-3,9- and -3,10-dicarboxylic acid di (2,6-diisopropylphenyl) amide.
    Perylene pigments normally absorb radiation with a wavelength between 360 and 630 nm and re-radiate it with a wavelength between 470 and 750 nm. In addition to perylene pigments, other fluorescent pigments with similar structures can be used, such as pigments based on violanthrones and / or iso-violanthrones, such as the structures described in EP-A-073 007. An example of a suitable component is preferably alkoxylated violanthrones and / or iso-violanthrones, such as 6.15-didodecyloxyisoviolanthronedione (9.18).
    Other examples of suitable organic LDS components are naphthalene-type components. These pigments typically have an absorption range of wavelengths between 300 and 420 nm and an emission range of approximately 380 to 520 nm. Examples of naphthalene-type components are the naphthalene carboxylic acid derivatives, for example naphthalene 1,8: 4,5-tetracarboxylic acid diimides, and in particular naphthalene-1,8-dicarboxylic acid imides, preferably 4,5-dialkoxynaphthalene-1,8- dicarboxylic acid monoimides and 4-phenoxynaphthalene-1,8-dicarboxylic acid monoimides. Other naphthalene-type components are, for example, N- (2-ethylhexyl) -4,5-dimethoxynaphthalene-1,8-dicarboxylic acid imide, N- (2,6-diisopropyl-phenyl) -4,5-dimethoxynaphthalene-1,8- dicarboxylic acid imide, N- (7-tridecyl) -4,5-dimethoxy-naphthalene-1,8-dicarboxylic acid imide, N- (2,6-diisopropylphenyl) -4,5-diphenoxynaphthalene-1,8-dicarboxylic acid imide and N, Β-Bis (2,6-diisopropylphenyl) -1.8: 4,5-naphthalene tetracarboxylic acid diimide.
    Other examples are Lumogen F Yellow 083, Lumogen F Orange 240, Lumogen F Red 305 and Lumogen F Violet 570 as available from BASF.
    For example, the following organic LDS components are capable of absorption (of excited wavelengths) of 300 to 360 nm and have an emission spectrum with a maximum around 365 to 400 nm: diphenyloxazole (2,5-diphenyloxazole 1,4-Di [2- (5-phenyloxazolyl) benzene, 4,4'-diphenylstilbene, 3,5,3 ", 5" "tetra-t-butyl-p-quinquefenyl. These components can be obtained, for example, from Synthon Chemicals GmbH and Luminescence Technology Corp .
    For example, the following organic LDS components are capable of emitting the incoming radiation emission at 400 - 460 nm: 2,5-thiopenediyl bis (5-tert-butyl-1,3-benzoxal).
    For example, the following organic LDS components are capable of radiating the incoming radiation at 560 nm: Hostasole 3G naphthalimide (Clariant), Lumogen F Yellow 083 (BASF), Rodamine 110 (Lambdachrome 5700).
    For example, the following organic LDS components are capable of emitting the incoming radiation at 580-640 nm: hostazole GG thioxanthene benzanthione (Clariant), - Lumogen F Red 305 (BASF), benzoin rodamine 6G ethylaminoxanthene (Lambdachrome 5900),
    For example, the following organic LDS components are capable of emitting the incoming radiation at 640-680 nm: cresyl purple diaminobenzol, Sublforhodamine B (Lambdachrome LC6200),
    For example, the following organic LDS components are capable of radiating the incoming radiation at 700-1000 nm: Rodamine 800 (Sigma), Pyridine 2 (Lambdachrome LC7600), DOTC, HITC (Lambdachrome LC7880), Styril 9 (Lambdachrome LC8400) .
    Suitable inorganic LDS components are semiconductor quantum dot materials and nanoparticles that contain Sm3 +, Cr3 +, ZnSe, Eu2 + and Tb3 +, and nanoparticles that contain ZnO; ZnS doped with Mg, Cu, and / or F; CdSe; CdS; TiO 2; Zr3 +, Zr4 +; and / or Eu3 +, Sm3 +, or Tb3 + doped YPO4. A common characteristic of these materials is that they are capable of exhibiting fluorescence. The nanoparticles can be created by any suitable process, for example by the process as described in US7384680. They can have an average diameter of less than 75 nm, more specifically they can have a size of between 3 and 50 nm as determined by Transmission Electron Microscopy (TEM). Possible europium complexes suitable as luminescent components are [Eu (β-diketonate) 3- (DPEPO)] as described in Omar Moudam et al, Chem. Commun., 2009, 6649-6651 by the Royal Society of Chemistry 2009.
    Another example of a suitable inorganic luminescent component are molecular sieves consisting of oligo-atomic metal clusters of 1 to 100 atoms of the following metals (sub-nanometer), Si, Cu, Ag, Au, Ni, Pd, Pt, Rh, Co and Ir or alloys thereof such as Ag / Cu, Au / Ni etc. The molecular sieves are selected from the group consisting of zeolites, porous oxides, silicoaluminophosphates, aluminophosphates, gallophosphates, zinc phosphates, titanosilicates and aluminosilicates, or mixtures thereof. In a concrete application of the present invention, the molecular sieves are selected from large pore zeolites of the group consisting of MCM-22, ferrierite, faujastites X and Y. The molecular sieves in another concrete application of the present invention are materials selected from the group consisting of zeolite 3 A, Zeolite 13X, Zeolite 4A, Zeolite 5 A and ZKF. The oligo-atomic metal clusters are preferably oligo-atomic silver molecules with between 1 and 100 atoms. Illustrative examples of such a molecular sieve based on LDS components are described in WO-A-2009006708, and this publication is hereby incorporated by reference.
    The concentration of the LDS component in the polymer layer will depend on the selected LDS component. Some components are more effective and require a lower concentration in the polymer layer, while other components require a higher concentration because they absorb and re-radiate radiation less efficiently.
    The polymer layer can contain at least one LDS component. The polymer layer can contain a single LDS component or multiple LDS components. If there are multiple LDS components, a combination of components that absorb radiation with a different wavelength and re-radiate with a different longer wavelength is preferred. In this way, a so-called LDS "cascade" can be obtained in which radiation emitted by a component is absorbed by a subsequent component. Such a cascade is called a Photon Absorption Emitting Chain (PAEC; photon absorption emission chain).
    Preferably, the polymer film contains the following co-extruded polymer layers: a first polymer layer (a) contains an LDS component for the absorption of radiation between 280 and 400 nm and re-radiation between 400 and 550 nm. another polymer layer (b) contains an LDS component for the absorption of radiation between 360 and 470 nm and re-irradiation between 410 and 670 nm, and another polymer layer (c) contains an LDS component for the absorption of radiation between 360 and 570 nm and re-irradiation between 410 and 750 nm.
    One or more LDS components may be present in one of the aforementioned layers. Additional layers may exist in the polymer film, the additional layers also containing LDS components or other additives. Preferably, each layer contains only LDS components that can convert a certain wavelength range into a longer wavelength range, and not a cascade of wavelengths; preferably only a single component or a group of similar components.
    Examples of suitable LDS constituents for layer (a) are 2,5-diphenyloxazole (PPO diphenyloxazole), 4,4'-Diphenyl stilbene (DPS), 1,4-Di [2- (5-phenyloxazolyl) benzene (POPOP), 3,5,3 "", 5 "" - Tetra-t-butyl-p-quinquephenyl (QUI-P-quinqaphenyl), 1,8-ANS (1-Anilinonaphthalene-8-sulfonic acid), 1-Anilinonaphthalene-8-sulfonic acid (1,8-ANS), 6,8-Difluoro-7-hydroxy-4-methyl-coumarin pH 9.0, 7-Amino-4-methyl-coumarin pH 7.0, 7-Hydroxy-4-methyl-coumarin, 7-Hydroxy-4-methyl-coumarin pH 9.0, Alexa 350, BFP (Blue Fluorescent Protein), Cascade Yellow, Cascade Yellow antibody conjugate pH 8.0, Coumarin, Dansyl Cadaverine, Dansyl Cadaverine, MeOH, DAPI, DAPI DNA, Dapoxyl (2-aminoethyl) sulphonamide, DyLight 350, Fura -2 Ca 2+, Fura-2, high Ca, Fura-2, no Ca, Hoechst 33258, Hoechst 33258 DNA, Hoechst 33342, Indo-1, Ca free, LysoSensor Yellow pH 3.0,
    LysoSensor Yellow pH 9.0, Marina Blue, Sapphire, and / or SBFI-Na +.
    Examples of suitable LDS constituents for layer (b) are: 7-Diethylaminocoumarin-3-carboxylic acid hydrazide (DCCH), 7-Diethylaminocoumarin-3-carboxylic acid succinimidyl ester, 7-Methoxycoumarin-3-carboxylic acid succinimidyl ester, 7-Hydroxycoumarin-3 -carboxylic acid succinimidyl ester, 7-Diethylamino-3 - (((((2-iodoacetamido) ethyl) amino) carbonyl) coumarin (IDCCfl 7-Diethylamino-3 - (((((2-maleimidyl) ethyl) amino) carbonyl) coumarin ( MDCC), 7-Dimethylamino-4-methyl-coumarin-3-isothiocyanate (DACITC), N- (7-Dimethylamino-4-methyl-coumarin-3-yl) maleimide (DACM), N- (7-Dimethylamino-4-methyl-coumarin-3 -yl) iodoacetamide (DACIA), 7-Diethylamino-3- (4'-maleimidylphenyl) -4-methyl coumarin (CPM), 7-Diethylamino-3 - ((4 '- (iodoacetyl) amino) phenyl) -4-methyl coumarin (DCIA), 7-Dimethylaminocoumarin-4-acetic acid (DMACA), 7-Dimethylaminocoumarin-4-acetic acid succinimidyl ester (DMACASE), Acridine Orange, Alexa 430, Alexa Fluor 430 antibody conjugate pH 7.2, Auramine O, Di-8 ANEPPS, Di-8-ANEPPS lipid, FM 1-43, FM 1- 43 lipid, Fura Red Ca 2+, Fura Red, high Ca, Fura Red, low Ca, Lucifer Yellow and / or CH, SYPRO Ruby (CAS 260546-55-2).
    Examples of suitable LDS constituents for layer (c) are the aforementioned constituents under layer (b) and Rodamine 110, Rodamine 6G ethylaminoxanthene benzoic (available from Lambdachrome), Alexa Fluor 647 R-phycoerythrin streptavidin pH 7.2, Ethidium Bromide, Ethidium homodimer, Ethidium homodimer-1 DNA, FM 4-64, FM 4-64, 2% CHAPS, Nile Red lipid and / or Propidium lodide.
    An example of another possible cascade may first include an LDS component with an absorption range between approximately 280 nm and 365 nm and with an emission range between approximately 380 nm and 430 nm. An example of a suitable LDS component is 3.5.3 "", 5 "" tetra-t-butyl-p-quinquephenyl, with a known maximum absorption of about 310 nm and a maximum emission of about 390 nm. This LDS component can be added at a concentration of, for example, around 33% of the total amount of LDS components in the polymer layer. A second LDS component with an absorption range between approximately 335 and 450 m and with an emission range between approximately 410 to 550 nm. An example of a suitable LDS component is 2,3,5,6-1 H, 4H-tetrahydroquinolizino [9.9a, 1-gh] coumarin, a maximum excitation wavelength of approximately 396 nm and a maximum emission wavelength of at approach 490 nm in a concentration of, for example, around 33% of the total amount of LDS material in the polymer layer. A third LDS component of the cascade can have an absorption range between approximately 450 nm and 550 nm and with an emission range between 560 nm to 700 nm. An example of a suitable LDS component is 1-amino-2-methyl anthraquinone with a maximum absorption around 45Ö nm and a maximum emission at around 600 nm in a concentration of, for example, around 33% of the total amount of LDS material in the polymer layer.
    The total concentration of the LDS components in the polymer matrix depends on the thickness of the film because the efficiency of the down conversion is a function of the number of molecules on which the incident light strikes per unit volume. For example, a polymer layer of approximately 400 to 450 microns may be doped with the constitutive LDS components in the range of 200 to 1000 ppm. A suitable 450 micron polymer layer with a good balance of UV blocking and transmission was obtained, for example, at a concentration of the constitutive LDS components of approximately 500 µm in the final polymer layer.
    The polymer material of the different polymer layers of the polymer film can be: ethylene vinyl acetate (EVA), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), alkyl methacrylate, alkyl acrylate copolymers such as, for example, polymethacrylate, poly-n-butyl acrylate (PMMA-PnBA), elastomers, e.g. SEBS, SEPS, SIPS, Polyurethanes, functionalized polyolefins, lonomers, thermoplastic polydimethylsiloxane copolymers, or mixtures thereof. Ethylene vinyl acetate (EVA), polyvinyl butyral (PVB), silicones, polymethyl methacrylate (PMMA), alkyl acrylate copolymers such as, for example, polymethacrylate poly-n-butyl acrylate (PMMA-PnBA) are used. Preferably, at least one of the polymer layers consists of an ethylene vinyl acetate polymer. These polymers have advantages because they provide a suitable matrix for the LDS component (s). In addition, the resulting film can easily be used in a thermal lamination process to make an end product containing the polymer film. Other possible polymers are polymethyl methacrylate (PMMA), polyvinyl butyral (PVB), polyvinylidene fluoride (PVDF), polycarbonate (PC), polyurethane, silicones or mixtures thereof.
    Another preferred polymer is Ethylene-vinyl alcohol copolymers, hereinafter referred to as "EVOH", which is known to have strong oxygen barrier properties, transparency, oil-repellent and antistatic properties, mechanical strength and the like, and therefore for different types of packaging materials EVOH can be advantageously prepared by saponification of ethylene vinyl acetate polymer.
    The polymer is preferably an ethylene / vinyl acetate copolymer (EVA) consisting of copolymerized units of ethylene and vinyl acetate. The EVA can have a melt flow rate (melt flow rate; MFR) in the range of 0.1 to 1000 g / 10 minutes, better 0.3 to 300 g / 10 minutes, but even better 0.5 to 50 g / 10 minutes as determined in accordance with ASTM D1238 at 190 ° C and 2.16 kg.
    The ethylene vinyl acetate preferably has an acetate content of between 12 and 45 wt%, more preferably between 20 and 40 wt% and even better between 25 wt% or up to 40 wt%.
    The EVA can be a single EVA or a mixture of two or more different EVA polymers. By different EVA polymers it is meant that the copolymers have different comonomer ratios and / or average molecular weight and / or a different distribution of molecular weight. Accordingly, the EVA polymer may also contain polymers that have the same comonomer ratios, but a different MFR due to a different molecular weight distribution.
    Ideally, the EVA polymers contain beneficial monomers other than ethylene and vinyl acetate, such as alkyl acrylate, where the alkyl group of the alkyl acrylate can contain 1 to 6 or 1 to 4 carbon atoms, and can be selected from methyl groups, ethyl groups, and branched or unbranched propyl, butyl, pentyl, and hexyl groups.
    The EVA copolymers used in these can also contain other known additives. The additives may contain adjuvants, flow promoting additives, lubricants, dyes, flame retardants, impact modifiers, nucleating agents, anti-blocking agents such as silica, thermal stabilizers, dispersing agents, surfactants, chelating agents, coupling agents, reinforcing additives such as glass fibers, fillers and the like.
    The polymer layers consisting of ethylene-vinyl acetate copolymer preferably consist of one or more organic peroxides, which allow cross-linking of the ethylene-vinyl acetate copolymer, and thus increase the bond strength, moisture penetration resistance, while maintaining high transparency, if desired. maintained. Organic peroxides that decompose at a temperature of at least 110 ° C to generate radicals can be used advantageously as the aforementioned organic peroxide. The organic peroxide or combination of peroxides are generally selected for film forming temperature, composition preparation conditions, curing (bonding) temperature, heat resistance of the object to be bonded and storage stability. According to the ideal realization of the present invention, the peroxide is chosen so that it does not essentially decompose at the resin processing temperature, in particular during co-extrusion and / or further extrusion and pelletization, and is only activated at the formation temperature or lamination temperature of the solar cell. "Essential non-decomposing" according to the present invention means a half-life of at least 0.1 to 1 hour at co-extrusion temperature. Examples of organic peroxides include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, 3-di-tert-butyl peroxide, dicumyl peroxide, 2,5- dimethyl-2,5-di (2-ethylhaxanoyl peroxy) hexane, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, tert-butyl cumyl peroxide, [alpha], [alpha] '- bis (tert-butyl peroxyisopropyl benzene, [alpha], [alpha] '- bis (tert-butyl peroxy) diisopropylbenzene, n-butyl-4,4-bis (tert-butyl peroxy) butane, 2,2-bis (tert-butyl peroxy) butane, 1, 1-bis (tert-butyl peroxy) cyclohexane, 1,1-bis (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, tert-butyl peroxybenzoate, benzoyl peroxide, and 1,1-di (tert-hexyl peroxy) -3, 3,5-trimethylcyclohexane. Of these, 2,5-dimethyl-2,5-di (2-ethylhexanoyl peroxy) hexane and 1,1-di (tert-hexyl peroxy) -3,3,5-trimethylcyclohexane are particularly preferred. The amount of organic peroxide in the film layers is preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.2 to 1.8 parts by weight based on 100 parts by weight of ethylene-vinyl acetate copolymer.
    The polymer layer preferably consists of two or optionally 2-12 co-extruded polymer layers, in which two or more polymer layers contain an LDS component. Such a multi-layer is made by co-extruding and orienting a film consisting of the different layers simultaneously.
    The polymers used for the different layers may differ, provided that the difference in melt flow index (MFI) of the polymers under the conditions of co-extruding is less than 4 points and preferably less than 2 points. When different polymers have a different MFI in, for example, a standard condition are combined, the extrusion temperature of the different polymers is preferably adjusted so that the MFI under the conditions of co-extruding are within the aforementioned ranges. A polymer film with at least 3 layers consists of two outer layers and at least one inner layer. The melt flow index (MFI) of the inner polymer layer at the extrusion temperature of the inner polymer layer is equal to or in the range of -2 to plus 2 MFI points of the MFI of the outer layers at extrusion temperature or temperatures of the outer layers. Preferably, the MFI of an inner polymer layer differs in a range of 0.5 to 10 from the MFI of an outer polymer layer or both outer polymer layers at a temperature TL, wherein TL is the lamination temperature of a vacuum lamination process for preparing a solar panel comprising polymer film according to the invention. Typical temperatures for the lamination are in the range of 135 to 165 ° C, preferably 145 to 155 ° C.
    Preferably, one or both outer polymer layers have a melting point T1 of at least 10 ° C below the melting point T2 of at least one of the inner polymer layers. Preferably, the melting point T1 is between 10 and 50 ° C lower than the melting point T2, even better between 10 and 35 ° C lower. Applicants discovered that shrinkage of the polymer film under lamination conditions can be significantly less when such a high melting point inner polymer layer forms part of the polymer film. Even better is when the MFI of both outer layers is higher than the MFI of at least one inner polymer layer as measured at lamination temperature. Applicants discovered that such a polymer film can be used advantageously to make a solar panel in a thermal lamination process in which the photovoltaic cells are sufficiently encapsulated by the outer layer of the polymer film while at the same time no or extremely slight shrinkage occurs. This is advantageous because then less or no adhesion of the polymer layer is required when the polymer film is prepared. Shrinkage of the polymer film must be avoided or reduced to prevent the film from damaging the vulnerable silicon photovoltaic cells while laminating a solar panel. Applicants discovered that for a preferred combination of polymeric materials for the layers of the polymer film, the lamination temperature was applied when the polymer film is combined with, for example, a photovoltaic cell, higher than the temperature at which the inner layer is extruded when the polymer film is prepared, and wherein the temperature at which the inner layer is extruded when the polymer film is prepared is in turn higher than the temperature at which at least one of the outer layers is extruded during preparation of the polymer film.
    The inner polymer layer described above preferably consists of an optionally hydrogenated polystyrene block copolymer with butadiene, isoprene and / or butylene / ethylene copolymers, for example SIS, SBS and / or SEBS; a polymethacrylate polyacrylate block copolymer, a polyolefin, a polyolefin copolymer or terpolymer, or an olefin copolymer or terpolymer, with copolymerizable functionalized monomers such as methacyrylic acid (ionomer). Examples are a poly methyl metacrylate n-butyl acrylate block copolymer, as described in WO2012057079, and commercially available as "Kurarity" from Kuraray Corp. A further example contains a polyolefin, preferably a polyethylene or polypropylene, such as an LDPE type. Polyolefins such as polyethylene and polypropylene suitable for the inner sublayer include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, metallocene-derived low density polyethylene homopolypropylene, and polypropylene copolymer.
    The polymer composition of at least one of the layer (s) with an LDS component is preferably selected so that the light-absorbing and emitting activity of the LDS component is not affected under accelerated weathering according to ISO 4892 part 2, method A, cycle 2 for at least 100 hours. At least one of the polymer layers can have favorable high humidity and / or gas barrier properties, e.g. such as in polyolefin films and / or ethylene vinyl alcohol copolymers (EVOH). Combinations thereof can also be used, depending on the desired properties.
    Coextrusion is a known process for skilled personnel and uses two or more extruders to ensure a constant volume throughput of different molten viscous polymers through a single extrusion head (die) that extrudes the materials into the desired film-like form. The thickness of the layers can be controlled by the relative speeds and dimensions of the individual extruders that apply the polymer material.
    It may be preferable to add additives to at least one of the outer layers of the polymer film that improve the adhesive strength of the polymer film to glass. In some applications, the polymer film is applied directly to a glass layer and good adhesion of the polymer film is required in such a case. When the polymer film is applied between two layers of glass, it is preferred that both outer layers of the polymer film have good bonding strength to glass. Possible additives such as silane coupling agents can be added to the EVA copolymer to improve the bond strength with the glass layer or layers. Useful illustrative silane coupling agents include [gamma] chloropropylmethoxysilane, vinyl methoxysilane, vinyl triethoxy silane, vinyl tris ([beta] methoxy ethoxy) silane, [gamma] vinylbenzyl propyl methoxysilane, N- [beta] - (N-vinylbenzylaminoethyl) - [gamma] ethoxil ethoxil ethoxil ethoxil ethoxil ] -methacryloxypropyltrimethoxysilaan, vinyltriacetoxysilane, Y- glycidoxypropyltrimethoxysilane, [gammaj-glycidoxypropyltriethoxysilane, [beta] - (3,4-epoxycyclohexyl) ethylthmethoxysilaan, methacryloxypropyltriethoxysilane, vinylthchlorosilaan, methacryloxypropyltrimethoxysilane, [gamma] -mercaptopropylmethoxysilaan, [gammaj-aminopropyltriethoxysilane, N- [betaj- (aminoethyl) - [gamma] - aminopropyltrinethoxysilane, and / or mixtures of two or more thereof.
    The silane coupling agents are preferably processed in the relevant polymer layer. For a polymer layer consisting of an ethylene vinyl acetate polymer, the silane coupling agents are preferably processed in a ratio of 0.001 to about 4% by weight, or more preferably 0.005 to about 1% by weight, based on the total weight of the polymer.
    The polymer film of the present invention is especially suitable for converting the shorter wavelength solar radiation into longer wavelength radiation, with a wavelength range in which photovoltaic cells convert radiation into electricity more efficiently. The invention thus also focuses on the use of the polymer film according to the invention for improving the performance of a photovoltaic cell by LDS of sunlight.
    The polymer film is preferably used according to the invention as part of a solar panel that contains a photovoltaic cell. The photovoltaic cell can consist of at least one of the following materials: CdS, CdTe; Si, preferably p-doped Si or crystalline Si or amorphous Si or multi-crystalline Si; In P; GaAs; Cu 2 S; Copper Indium Gallium Diselenide (CIGS). A solar panel can be prepared by stacking different glass layers, the polymer film according to the invention, the photovoltaic cell, one or more additional encapsulating layers and a back layer, and then causing the stack formed to undergo a lamination process.
    The optimum photovoltaic performance of a PV cell will differ for each type of PV cell and thus the degree of conversion required by the LDS components of different PV cells will differ. Preferably, the polymer layer containing an LDS component of the polymer layer furthest removed from the photovoltaic cell contains an LDS component with the property that it can at least partially absorb UV radiation (between 10 and 400 nm) and radiation with a higher wavelength.
    The invention also focuses on a solar panel consisting of the polymer film according to the invention and a photovoltaic cell. Preferably, the polymer layer containing an LDS component of the polymer layer furthest removed from the photovoltaic cell contains an LDS component with the property that it can at least partially absorb UV radiation and re-irradiate radiation of a higher wavelength. Such a solar panel preferably has a layer sequence of a glass layer, the polymer film, a photovoltaic cell, an encapsulating layer and a back layer. The encapsulating layer can be a highly modern encapsulating layer, for example a thermally curable polymer layer such as the previously described EVA copolymer. The suitable photovoltaic cell is a crystalline silicon cell, CdTe, aSi, micromorphic Si or Tandem junction aSi. The back layer can be a hard polymer, such as for example a layer of PET or more preferably a glass layer. When thin-film photovoltaic cells are used, or, for example, CIGS and CIS-type cells, the solar panel may contain a glass top layer, the polymer layer of the present invention, the thin-film photovoltaic cell and a strong support such as, for example, glass.
    Preferably the glass layer that receives the incoming radiation has a thickness of between 1.5 and 4 mm and where the glass layer is used as a back layer has a thickness of 1.5 and 4 mm and in which the total thickness of the solar panel is less than 9 mm . The glass layer can be, for example, float glass or rolling glass. The glass can optionally be thermally treated. Suitable thermally tempered thin glass layers with such a thickness can be obtained, for example, via Saint Gobain Glass. The glass layer can be sodium-free glass, for example alumina silicate or borosilicate glass.
    For mass production, it is preferable to use soda lime glass or borosilicate glass. The soda lime glass can contain between 67-75% S102 (by weight), between 10-20%; Na 2 O, between 5-15% CaO, between 0-7% MgO, between 0-5% Al 2 O 3; between 0-5% K 2 O, between 0-1.5% Li 2 O and between 0-1%, BaO. Such a glass will have a suitable transparency of more than 90%. The glass has preferably undergone a thermal cure treatment.
    The surface of the glass layer, in particular the surface that does not adjoin the polymer film and collects the incoming radiation, is coated with a suitable anti-reflective layer. The anti-reflective layer will limit the radiation that is reflected on the glass surface. Limiting the reflection will increase the radiation that passes through the glass element, which consequently improves the efficiency of the glass element to emit radiation. The coating is preferably applied to a glass layer, namely the glass layer which is in direct contact with the incoming radiation, i.e. sunlight. The side adjacent to the polymer film can optionally be provided with such a coating. A suitable anti-reflective coating consists of a layer of porous silica. The porous silica can be applied by a sol-gel process as described, for example, in US-B-7767253. The porous silica may consist of solid silica particles present in a silica-based binder. Such a coating is available from DSM, the Netherlands, as Khepri Coat ™. Processes to prepare glass layers with an anti-reflective coating are described, for example, in WO-A-2004104113 and WO-A-2010100285.
    The glass surface that captures the incoming radiation can also have a relief structure to more efficiently capture incoming radiation, as described, for example, in WO2005111670.
    A solar panel as described above can be obtained by a stack consisting of the following layers: a glass layer (a), a polymer film according to the present invention (b), a layer (c) containing a photovoltaic cell, a polymer encapsulation layer (d) ; and a glass layer (e), to undergo a thermal lamination process at an elevated lamination temperature.
    The laminating temperature can be between 115 and 175 ° C and the environment: the stack preferably has a pressure of less than 30 mbar, more preferably less than 1 mbar. In this process, the stack is preferably in a vacuum laminator and pressure bonded under conversion heat at a temperature in the range of 115 to 175 ° C, preferably 140 to 165 ° C, ideally 145 to 155 ° C. The laminate is preferably also degassed. The compression lamination pressure is preferably in the range between 0.1 and 1.5 kg / cm 2. The lamination time is typically somewhere between 5 and 25 minutes. This heating allows, for example, cross-linking of the ethylene-vinyl acetate copolymer in the polymer film according to the invention and in the encapsulating layer, the photovoltaic cell, the polymer film and the encapsulating layer being strongly joined to hermetically seal the photovoltaic cell and the solar panel to obtain.
    Applicants have discovered that when the MFI at lamination temperature deviates between the outer sublayers and an inner layer, even less shrinkage occurs. The invention therefore also focuses on a preferred process for manufacturing the solar panel in which the first and / or second polymer encapsulation layer consists of 3 or more multiply co-extruded thermoplastic polymer sub-layers consisting of two outer sub-layers and at least one inner sub-layer and in which the MFI of the inner sublayer deviates within a range of between 0.5 and 10 points from the MFI of one or both outer sublayers of the same layer.
    In an even better manufacturing process, the polymer film according to the invention consists of 3 or more multi-co-extruded thermoplastic polymer sub-layers consisting of two outer sub-layers and at least one inner sub-layer, in which the multi-co-extruded thermoplastic polymer layer is obtained by co-extrusion of different polymer materials extruded at an extrusion temperature selected for each sublayer such that the greatest difference in melt flow index (MFI) of the polymers of the sublayers at extrusion temperature as applied for each sublayer is lower than 5 MFI points, preferably lower than 3 MFI points, in which the lamination temperature TL is higher then the extrusion temperature TC of an inner sublayer and wherein the temperature TC is higher than the extrusion temperature TA of an outer sublayer and / or TB of the other outer sublayer.
    The invention is directed to a glass element. Glass elements are known, for example, as covers for greenhouses. Sunlight easily passes through the glass roof of such a greenhouse and photosynthesis of at least one plant species takes place. But glass elements are also used as a transparent and protective layer of a solar panel.
    The element can be used advantageously to improve the efficiency of a light-induced process such as, but just limited to, photosynthesis or energy generation through the photovoltaic effect. This object is achieved by the following glass element, consisting of two layers of glass, in which a transparent polymer layer is present between the two layers of glass and in which the polymer layer contains at least one LDS component adapted to at least partially absorb radiation of a certain wavelength and re-radiating with a wavelength longer than the wavelength of the absorbed radiation.
    The applicants discovered that when such a glass element is used as the roof of a greenhouse, the photosynthesis of at least one plant species can be improved because part of the shorter wavelength radiation is converted to a wavelength more suitable for photosynthesis. In this way, more photosynthesis can take place at a given solar intensity. The applicants discovered that when such a glass element is used as a cover plate of a photovoltaic system, more energy can be generated at a given solar intensity.
    Another advantage is that the glass layers prevent the penetration of water into the polymer layer. Small amounts of water can adversely affect the stability of certain LDS components, in particular the organic LDS components. By using two glass layers, the LDS component is the polymer layer effectively protected against degradation caused by water.
    Further benefits are discussed when the preferred use is described below.
    The glass element can be used for various applications where it is desirable to filter radiation of a certain wavelength and to be transparent to radiation with a longer wavelength. A preferred use is in which the glass element is used to change the properties of sunlight and in which the adjusted sunlight thus obtained after it has passed the glass element is used to grow plants or more generally in which the adjusted sunlight is used in a photosynthesis process. The invention also focuses on a building, such as a greenhouse, with a roof consisting of a glass element according to the invention.
    Another preferred use of the glass element is to change the properties of sunlight in a process to generate electricity. Ideally, the electricity generation process uses a photovoltaic cell that is capable of generating an electrical current using the adjusted sunlight. The photovoltaic cell is preferably placed in the vicinity or next to the glass element, suitably connected to the glass element. Many photovoltaic cells have a poor spectral response to the shorter wavelengths, for example the radiation in the UV range. By absorbing and re-radiating radiation in the shorter wavelength ranges with a higher wavelength, optionally by means of a cascade as described above, it is possible to make effective use of the energy in the radiation with these shorter wavelengths in the form of radiation with a higher wavelength on which the photovoltaic cells deliver their optimum photovoltaic pretension. The optimum photovoltaic performance of a photovoltaic cell will differ for each type of photovoltaic cell. Indeed, various Internai Quantum Efficiency (IQE) plots are obtained for a wavelength range between 300 and 1100 for cSi screen printed cells, depending on the type of cSi cells, surface texture and cell surface treatment.
    The glass layer before and after the polymer layer containing the LDS component and the photovoltaic cell will provide a barrier against moving components from the polymer layers to the photovoltaic cell or from the photovoltaic cell to the polymer layer. A solar panel will be used for many years and during its lifetime, LDS components or other additives present in the polymer layer can decompose into fragments that can be harmful to the photovoltaic cell. Examples of such elements or components are amines, chlorides, sodium and sulfur-containing components. The glass layer, when used as a face plate, will prevent such components from spreading and reaching the photovoltaic cell and thus ensuring a longer life of the photovoltaic cell itself. The glass element thus offers the use of organic LDS components, which can decompose in these harmful fragments, in combination with a photovoltaic cell. Furthermore, components of the photovoltaic cell can move toward the polymer layer, which can result in degradation of the polymer and / or the LDS components. The glass layer in fact avoids such displacement. In this way, the increased use of incandescent light for different photovoltaic cells will also be useful for existing production lines, simply by replacing the face plate.
    The photovoltaic cell can consist of at least one of the following materials: CdS, CdTe; Si, preferably p-doped Si or crystalline Si or amorphous Si or multi-crystalline Si or multiple junction Si; In P; GaAs; Cu 2 S; Copper Indium Gallium Diselenide (CIGS). A solar panel can be prepared by stacking different glass layers, the photovoltaic cell, one or more additional encapsulating layers and a back layer, and by subsequently subjecting the formed stack to a lamination process. In this way the glass element is formed simultaneously with the solar cell itself.
    A preferred photovoltaic cell is a thin film cadmium telluride (CdTe) photovoltaic cell. This type of photovoltaic cell shows an optimum photovoltaic effect at a wavelength between 500 and 800 nm. By combining such a PV cell with the glass element according to the invention, it was discovered that it is possible to make more effective use of the lower wavelength radiation from sunlight. The LDS components present in the glass element absorb the lower wavelength radiation and re-emit it with the aforementioned wavelength range at which the CdTe photovoltaic cell has a maximum IQE. Preferably, one or more LDS components or a cascade of LDS components are present in the polymer layer of the glass element that absorb radiation with a wavelength below 500 nm and emit radiation with a wavelength between 500 and 800 nm. The previously described LDS cascade is preferably present in the glass element.
    The invention therefore also focuses on a CdTe photovoltaic solar cell consisting of the glass element according to the invention, (a) a transparent electrode layer, (b) an n-type semiconductor layer, (c) an absorber, cadmium telluride (CdTe), and (d ) and rear contact. Layers (a) - (d) are sequentially applied to the glass element according to the invention. The glass element is preferably equipped with the anti-reflective coating described above on one side and with the aforementioned layers on the opposite side. The glass layer with the anti-reflective coating is preferably thicker than the glass layer adjacent to the layers (a) - (d).
    The transparent electrode layer (a) may, for example, consist of tin oxide (SnO2) or doped tin oxide, for example fluorine, zinc or cadmium doped tin oxide, indium tin oxide (ITO), zinc oxide (ZnO) and a cadmium stannate (Cd2 SnnO4). The buffer layer 205 can be formed, for example, with a thickness of up to about 1.5 microns or about 0.8-1.5 microns and can contain ZnO and SnO2 in a stoichiometric ratio of about one in two (1: 2). Tin oxide is preferably used.
    The n-type semiconductor layer (b) can be CdS, SnO 2, CdO, ZnO, AnSe, GaN, ln 2 O 2, CdSnO, ZnS, CdZnS or another suitable n-type semiconductor material and preferably CdS. Layer (b) can be formed by chemical bath deposition or by sputtering and can have a thickness of about 0.01 to about 0.1 µm.
    The cadmium telluride (CdTe) layer (c) can be applied by screen printing, spraying, close-spaced sublimation, electro-deposition, vapor transport deposition, sputtering, and evaporation.
    The rear contact layer may consist of any suitable conductive material or compositions thereof. Suitable materials include, for example, but are not limited to graphite, metallic silver, nickel, copper, aluminum, titanium, palladium, chromium, molybdenum alloys of metallic silver, nickel, copper, aluminum, titanium, palladium, chromium, and molybdenum and any combination thereof. The rear contact layer (d) is preferably a combination of graphite, nickel and aluminum alloys.
    The layers (a) - (d) can be encapsulated by an additional glass layer (e). Encapsulating glass layer (e) can be a rigid structure suitable for use with the CdTe photovoltaic cell. The encapsulating glass layer (e) may consist of the same material as the glass used in the glass element or it may be a different material. In addition, encapsulating layer (e) may contain openings or structures to enable wiring and / or connection to the CdTe photovoltaic cell.
    Applying the aforementioned layers to the glass element according to the invention to obtain the ideal CdTe photovoltaic solar cell can be carried out by the various methods known in the art. Examples of such methods and variations in the different layers are described in US-A-2011/0308593, EP-A-2430648, US-A-2012073649, US-A-2011259424 and so on.
    The glass element can also be combined with wafer-based cells based on monocrystalline silicon (c-Si), poly- or multi-crystalline silicon (poly-Si or mc-Si) and ribbon silicon. Preferably, the solar cell containing such a wafer-based PV cell contains the glass element according to the invention at the front so that it captures the incoming radiation, a polymer layer, a layer consisting of a wafer-based PV cell and a back layer.
    The backing layer can be a multi-layered film, typically consisting of at least three layers that can be prepared with different polymeric materials.
    The back layer preferably comprises a so-called white reflector. The presence of a white reflector is advantageous because it reflects radiation to the photovoltaic cell and thus improves the efficiency of the cell.
    Possible back layers contain fluoropolymer layers. Instead of a fluoropolymer layer, a second glass layer can be used at the rear of the solar cell.
    Possible back layers include fluoropolymer layers. Instead of a fluoropolymer layer, a second glass plate can be applied to the rear of the solar cell. This offers a solar cell that has a glass front and back. The glass layer for use as a rear side preferably has a thickness of less than 3 mm. The glass layers can be described as above. The use of a glass front as a rear offers an advantage because it provides structural strength to the panel, so that no aluminum frame is required. The glass back will also offer an absolute barrier towards water penetration and the like, which extends the life of the panel. The use of the glass layer makes it possible to prevent the use of a back layer with a fluoropolymer.
    The glass element can be prepared according to the invention by a stack of first glass layers, the polymer layer and the second glass layer are made according to a thermal laminating process. In such a process, the polymer layer becomes smoother and connects to the glass layers, while optionally gas is forced away by a vacuum.
    The following examples illustrate the invention:
    Comparative example 1
    A mono-layer EVA film was produced as follows: A commercially available ethylene vinyl acetate copolymer with 33% vinyl acetate content and an MFI of about 45 g / 10 min was used. A commercially available fluorescent perylene dye that absorbs light at a wavelength of 578 nm and emits at a wavelength of 613 nm was mixed with the EVA material, at a concentration of 0.05% by weight, in a manner as described, for example, in US - B-7727418.
    The film material further contained about 1% by weight of methacryloxypropyl trimethoxysilane as an adhesion promoter, and about 1% by weight of tert-butyl peroxy 2-ethylhexyl carbonate peroxide as a crosslinking agent.
    The material was mixed homogeneously, and a thin plate of about 500 µm thick was pressed at a temperature of 110 ° C from each mixture.
    The resulting plate was then laminated between two glasses with the following lamination protocol on a Meier flat bed vacuum laminator:
    Temperature: 145 ° C; Vacuum time: 300 seconds; press ramp up: 30 seconds and press time: 400 sec.
    The two samples were then placed in a UV weathering chamber, and subjected to an accelerated aging test, using the test cycle described as ISO 4892 part 2, method A, Cycle 2, title "Methods of Plastics Exposure to laboratory light sources - Xenon Are lamps". .
    After 50 hours of exposure, the sample showed discoloration. A UV / VIS spectrometry was taken, which showed that the sample no longer showed the absorption characteristic of the perylene dye.
    Example 1
    A 3-layer co-extruded film was prepared with the following composition:
    Layer 1: EVA + 1% methacryloxypropyl trimethoxysilane 1% by weight tert-butyl peroxy 2-ethylhexyl at a thickness of 200 µm and further comprising a commercial light-stabilizing package containing a combination of HALS and antioxidants that protect the EVA polymer matrix against degradation .
    Layer 2: PMMA + 0.05% perylene dye, at a thickness of 50 µm.
    Layer 3: EVA + 1% methacryloxypropyl trimethoxysilane 1% by weight tert-butyl peroxy 2-ethylhexyl, at a thickness of 200 µm, further comprising the light stabilization package of Layer 1.
    The resulting sample showed high stability of the perylene 500 dye after hours of UV weathering, while also typically encapsulating properties, such as adhesion, cross-linking, flow and encapsulation behavior, were provided by the EVA envelope layers on the outer layers of the sample .
    Comparative example 2
    A zeolite with nanoclusters of silver (Ag) was mixed in an EVA matrix in a concentration of 6%. Two samples were produced. One sample was stored in a dry environment, controlled by a drying agent, while the second sample was stored under ambient conditions.
    After 2 days, the sample stored in ambient conditions showed a slight discoloration, while the first sample, stored in controlled humidity, did not show this effect. After 20 days, the sample stored in ambient conditions showed severe discolorations to brown and had lost transparency. The remaining transparency was lower than 10% in a wavelength range of 250-800 nm. The sample under controlled humidity showed only a slight discoloration.
    Comparative example 3
    A further monolayer polymer film as in Comparative Example 2 was prepared and laminated between two glasses with the same laminating cycle as discussed in Example 1. The glass / glass sample was placed in a wet heat-weathering chamber at 85 ° C and 85% relative humidity. A discoloration was visible at the edges of the glass plates after only 50 hours of moist heat testing.
    Comparative example 4
    Comparative Example 3 was repeated, but using a glass / encapsulating agent / polymeric back layer construction. The thus obtained element was also placed in the weathering chamber. This sample quickly changed to completely dark brown, illustrating the lower performance of the polymeric back layer as a moisture barrier compared to the glass back plate of Comparative Example 4.
    Example 3
    To maintain the typical EVA encapsulation properties, a multilayer film was prepared consisting of two 200 µm EVA layers as the outer layer and a thin middle layer consisting of a polymer with better moisture barrier properties. The polymer that was selected was a low density polyethylene. The melt index of the selected polyethylene is selected such that at the extrusion temperature of 110 DEG C. the melt index was comparable to the melt flow index of EVA polymer at the same temperature. The Ag / zeolite powder was mixed in the polyethylene layer. The resulting film exhibited the characteristic encapsulation properties of a standard EVA monolayer, but also protection of the Ag / zeolite in the middle layer because it was embedded in a polymer with better moisture properties.
    A glass / multi-layer encapsulant / PEF backing layer element was prepared which did not show significant discoloration after 500 hours in the wet heat test.
    Example 4
    A glass / multi-layer / glass element was prepared, and an edge seal was also applied. This element showed no discoloration after 500 hours in the moist heat test. This construction keeps most of the moisture out of the module, and it is expected that the multilayer polymer plate will be a second line of protection and protect against moisture ingress, particularly through the junction box.
    权利要求:
    Claims (45)
    [1]

    A polymer film comprising a plurality of co-extruded polymer layers, wherein at least one of these layers comprises an LDS component for at least partially absorbing radiation with a certain wavelength and re-irradiating radiation at a longer wavelength than the wavelength of the absorbed radiation.
    [2]
    A polymer film according to claim 1, wherein two or more layers of the polymer film contain an LDS component.
    [3]
    A polymer film according to claim 2, wherein an LDS component present in a first polymer layer, the LDS component of which can absorb more radiation at a lower wavelength than the LDS component present in a subsequent layer.
    [4]
    A polymer film according to claim 3, wherein the first polymer layer contains an LDS component for at least partially absorbing UV radiation and re-irradiating in a higher wavelength.
    [5]
    Polymer film according to any of claims 1 to 4, comprising at least two co-extruded polymer layers and wherein the one or more different LDS constituents present in a first layer will absorb radiation at a wavelength lower than the one or more different LDS constituents in the next layer.
    [6]
    A polymer film according to any of claims 1 to 5, wherein the two or more different LDS components are selected to form a cascade and wherein the cascade is determined that a compound in the cascade retransmits radiation in a wavelength region where a subsequent compound emits radiation and at least one LDS component partially absorbs radiation with a certain wavelength and retransmits radiation at a longer wavelength than the wavelength of the absorbed radiation.
    [7]
    A polymer film according to any one of claims 1 to 6, wherein a first polymer layer contains an LDS component for absorbing radiation between 280-400 nm and re-irradiation between 400-550 nm, another polymer layer contains an LDS component for absorbing radiation between 360-470 nm and re-irradiation between 410-670 nm, and a polymer layer comprises an LDS component for absorbing radiation between 360-570 nm and re-irradiation between 410-750 nm.
    [8]
    A polymer film according to any of claims 1 to 7, wherein at least one of the polymer layers is an ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), alkyl methacrylate, alkyl acrylate copolymers, polyurethanes, functionalized polyolefins , ionomers, thermoplastic polydimethylsiloxane copolymers, or mixtures thereof.
    [9]
    A polymer film according to any of claims 1 to 8, wherein the polymeric composition of the layer containing the LDS component is selected such that the light-absorbing and emitting activities of the LDS component is not affected under accelerated weathering conditions, in accordance with ISO 4892 part 2, method A, cycle 2 for at least 100 hours.
    [10]
    A polymer film according to any of the procedure claims, wherein at least one of the polymer layers has high humidity and / or gas barrier properties.
    [11]
    A polymer film according to claim 8, wherein at least one of the polymer layers contains an ethylene vinyl acetate polymer, preferably wherein the ethylene vinyl acetate has an acetate content of 12% to 45% by weight.
    [12]
    A polymer film according to claim 11, wherein the LDS component present in multiple co-extruded layers of an ethylene vinyl acetate polymer with an acetate content of 12% to 45% by weight.
    [13]
    A polymer plate according to any of claims 1 to 9, wherein at least one of the outer polymer layers contains a silane coupling agent.
    [14]
    14. Polymer plate according to any of claims 1 to 13, wherein the plate consists of two outer polymer layers and at least one inner polymer layer and wherein one outer polymer layer or both outer polymer layers have a melting point T1 that is at least 10 ° C below the melting point T2 of at least one inner polymer layer lies.
    [15]
    A polymer plate according to claim 14, wherein the melting point T1 is 10 to 100 ° C lower than melting point T2.
    [16]
    A polymer plate according to any of claims 14 or 15, wherein the polymer plate is obtained by co-extrusion of different polymeric materials, wherein the polymeric materials are extruded at an extrusion temperature for each sublayer selected so that, at the extrusion temperature as used for each sublayer, the largest difference in melt flow index of the polymers of the sublayer is less than 3 MFI points.
    [17]
    A polymer plate according to any of claims 14 to 16, wherein the inner polymer layer comprises an optionally hydrogenated polystyrene block copolymer with butadiene, isoprene and / or butylene / ethylene copolymer (SIS, SBS and / or SEBS); a copolymer of ethylene-vinyl alcohol (EVOH), a polymethyl methacrylate-polyacrylate block copolymer, a polyolefin, a polyolefin copolymer or terpolymer, or a copolymer of olefin or terpolymer, with copolymerizable functionalized monomers such as methacrylic acid (ionomer).
    [18]
    A polymer plate according to any of claims 14 to 17, wherein at least one of the outer layers contains an ethylene vinyl acetate copolymer, wherein the ethylene vinyl acetate preferably has an acetate content of more than 18% by weight.
    [19]
    A method for manufacturing a polymer sheet according to any of claims 1 to 18, comprising the steps of: (i) providing one or more base blend of polymeric materials for each polymer layer, and (ii) co-extruding the base blend of polymeric materials into layers that form the polymer sheet.
    [20]
    The method of claim 19, further comprising producing one or more base mixtures from polymeric materials and additives, and forming the material from the base mixture into particles for use in co-extrusion.
    [21]
    Use of one or more base mixtures containing the polymeric material and the additives for the preparation of a polymer plate according to any of claims 1 to 18.
    [22]
    A part comprising two glass layers, wherein a transparent polymer layer is present between the two glass layers and wherein the polymer layer contains a polymer plate according to any of claims 1 to 18.
    [23]
    Component according to claim 22, wherein the glass of the glass layer is of borosilicate or of lime sodium.
    [24]
    Component according to one of claims 22 or 23, wherein the total thickness of the glass component is less than 5 mm.
    [25]
    The part according to any of claims 22 to 24, wherein at least one of the glass layers has a thickness of 0.1 to 2 mm.
    [26]
    The part of claim 25, wherein one of the glass layers has a thickness of between 0.1 and 4 mm and the other glass layer has a thickness of between 0.1 and 2 mm.
    [27]
    Component according to any of claims 22 to 26, wherein at least one glass layer has a surface that is not facing the polymer layer and that is covered with an anti-reflective coating.
    [28]
    The element of any one of claims 22 to 27, wherein at least one of the glass layers has an embossed surface that is not facing the polymer layer.
    [29]
    Use of the part according to any of claims 22 to 28 for changing the properties of sunlight in a method for growing plants.
    [30]
    Use of the part according to any of claims 22 to 29 for changing the properties of sunlight in a method of generating electricity.
    [31]
    A building comprising a component according to any of claims 22 to 28.
    [32]
    A photovoltaic module comprising a layer consisting of a photovoltaic cell and a covering layer comprising the part according to any of claims 22 to 28.
    [33]
    The photovoltaic module of claim 32, wherein the photovoltaic cell is a thin film cell of cadmium telluride.
    [34]
    A photovoltaic solar cell containing the glass element according to any of claims 22 to 28, (a) a transparent electrode layer, (b) an n-type semiconductor layer, (c) an absorbent layer of cadmium telluride and (d) a contact layer on the rear end.
    [35]
    Use of the polymer plate according to any of claims 1 to 18 to improve the performance of a photovoltaic cell by luminescent downshifting of sunlight.
    [36]
    A solar panel containing a polymer plate according to any of claims 1 to 18, and a photovoltaic cell.
    [37]
    The solar panel of claim 36, wherein a polymeric layer furthest away from the photovoltaic cell contains a luminescent downshifting mixture for at least partially absorbing UV radiation and re-irradiating radiation at a higher wavelength.
    [38]
    The solar panel according to any of claims 36 or 37, wherein the panel has a sequence of layers of a glass layer, the polymer plate, a photovoltaic cell, an encapsulating layer, and a back side.
    [39]
    A solar panel according to claim 38, wherein the rear side consists of a glass layer.
    [40]
    A solar panel according to claim 39, wherein the glass layer facing the incoming radiation has a thickness of between 1.5 and 4 mm and wherein the glass layer used for the rear has a thickness of 1.5 and 4 mm and the total thickness of the solar panel being less than 9 mm.
    [41]
    A solar panel according to any one of claims 36 to 40, wherein the glass layer facing the incoming radiation is provided with an anti-reflective coating.
    [42]
    A method of manufacturing a solar panel by exposing to a high lamination temperature a stack consisting of the following layers: a glass layer (a), a polymer sheet according to any of claims 1-18 (b), a layer (c) containing a photovoltaic cell, a polymeric encapsulating layer (d); and a glass layer (e).
    [43]
    A method according to claim 42, wherein the polymer sheet consists of c or more various, co-extruded thermoplastic polymer sublayers consisting of two outer sublayers and at least one inner sublayer and wherein the MFI of the inner sublayer differs by 0.5 to 10 points at the lamination temperature of the MFI of one or both sublayers of the same layer.
    [44]
    A method according to any of claims 42 or 43, wherein the polymer plate (b) consists of 3 or more composite co-extruded thermoplastic polymeric sublayers consisting of two outer sublayers and at least one inner sublayer, the polymer plate (b) being obtained by co -extrusion of various polymeric materials, these polymeric materials being extruded at an extrusion temperature for each sublayer selected so that the greatest difference in melt flow index of the polymers of the sublayer, at the extrusion temperature as applied for each sublayer, is lower then 5 MFI points, wherein the lamination temperature TL is higher than the extrusion temperature TC of an inner sublayer; and wherein the temperature TC is higher than the extrusion temperature TA of an outer sublayer and / or TB of the other outer sublayer.
    [45]
    The method of any one of claims 42 to 44, wherein the lamination temperature is between 115 and 175 ° C and wherein the pressure of the environment of the stack is less than 30 mBar.
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    同族专利:
    公开号 | 公开日
    CN104619490A|2015-05-13|
    JP6417320B2|2018-11-07|
    CN104540677B|2018-05-22|
    IN2014DN10539A|2015-08-21|
    IN2014DN10540A|2015-08-21|
    KR20150020207A|2015-02-25|
    EP2849943A2|2015-03-25|
    ES2733319T3|2019-11-28|
    KR20150013796A|2015-02-05|
    TR201909846T4|2019-07-22|
    WO2013171275A2|2013-11-21|
    WO2013171275A3|2014-07-17|
    US20150129018A1|2015-05-14|
    WO2013171272A3|2014-08-07|
    EP2850664A2|2015-03-25|
    CN108608703B|2021-03-16|
    US20150144191A1|2015-05-28|
    US20180323323A1|2018-11-08|
    CN104619490B|2018-10-09|
    JP2015522945A|2015-08-06|
    CN104540677A|2015-04-22|
    EP2850664B1|2019-06-19|
    CN108608703A|2018-10-02|
    WO2013171272A2|2013-11-21|
    BE1021307B1|2015-10-27|
    JP2015523920A|2015-08-20|
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    法律状态:
    2018-04-09| FG| Patent granted|Effective date: 20151030 |
    2018-04-09| PD| Change of ownership|Owner name: BOREALIS AG; AT Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CESSION; FORMER OWNER NAME: NOVOPOLYMERS N.V. Effective date: 20171019 |
    优先权:
    申请号 | 申请日 | 专利标题
    NL2008837|2012-05-16|
    NL2008839A|NL2008839C2|2012-05-16|2012-05-16|Glass element.|
    NL2008838A|NL2008838C2|2012-05-16|2012-05-16|Polymer sheet.|
    NL2008840A|NL2008840C2|2012-05-16|2012-05-16|Multilayer encapsulant film for photovoltaic modules.|
    NL2008841A|NL2008841C2|2012-05-16|2012-05-16|Multilayer backsheet for photovoltaic modules.|
    NL2008837A|NL2008837C2|2012-05-16|2012-05-16|Solar panel.|
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