WO2009135929A2 - Method for producing photovoltaic modules in a vacuum laminator having a reduced process vacuum - Google Patents

Method for producing photovoltaic modules in a vacuum laminator having a reduced process vacuum Download PDF

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Publication number
WO2009135929A2
WO2009135929A2 PCT/EP2009/055581 EP2009055581W WO2009135929A2 WO 2009135929 A2 WO2009135929 A2 WO 2009135929A2 EP 2009055581 W EP2009055581 W EP 2009055581W WO 2009135929 A2 WO2009135929 A2 WO 2009135929A2
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WO
WIPO (PCT)
Prior art keywords
plasticizer
polyvinyl acetal
laminate
semiconductor layers
photosensitive semiconductor
Prior art date
Application number
PCT/EP2009/055581
Other languages
German (de)
French (fr)
Other versions
WO2009135929A3 (en
Inventor
Andreas Karpinski
Original Assignee
Kuraray Europe Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Europe Gmbh filed Critical Kuraray Europe Gmbh
Priority to EP09742147A priority Critical patent/EP2288498A2/en
Publication of WO2009135929A2 publication Critical patent/WO2009135929A2/en
Publication of WO2009135929A3 publication Critical patent/WO2009135929A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559—Shape of the cross-section
    • B32B17/10577—Surface roughness
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10871—Making laminated safety glass or glazing; Apparatus therefor by pressing in combination with particular heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/60—In a particular environment
    • B32B2309/68—Vacuum
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the invention relates to a process for the preparation of
  • Photovoltaic modules under elevated temperature and reduced gas ambient pressure using a polyvinyl acetal based film are Photovoltaic modules under elevated temperature and reduced gas ambient pressure using a polyvinyl acetal based film.
  • Photovoltaic modules consist of a photosensitive semiconductor layer, which is provided to protect against external influences with a transparent cover.
  • a photosensitive semiconductor layer monocrystalline solar cells or polycrystalline, thin semiconductor layers can be used on a support.
  • Thin-film solar modules consist of a photosensitive semiconductor layer coated on a mostly transparent plate, e.g. by vapor deposition, vapor deposition, sputtering or wet deposition is applied.
  • Both systems are sandwiched between a pane of glass and a rigid, rear cover plate, e.g. laminated from glass or plastics using a transparent adhesive.
  • Curing resins or crosslinkable systems based on ethylene-vinyl acetate (EVA) are frequently used as transparent adhesives, as disclosed, for example, in DE 41 22 721 C1 or DE 41 28 766 A1.
  • thermosetting adhesive systems are the use of plasticized films based on polyvinyl acetals, such as polyvinyl butyral (PVB) known from the manufacture of laminated glass.
  • PVB polyvinyl butyral
  • the solar cell units are covered with one or more PVB films and bonded under elevated pressure and temperature with the desired covering materials into a laminate.
  • Methods of this kind are e.g. From DE 40 26 165 C2, DE 42 278 60 A1, DE 29 237 70 C2, DE 35 38 986 C2 or US 4,321,418 known.
  • the currently most common method for the production of solar modules is the lamination in Vakuumlaminator.
  • the module is vented in a vacuum chamber and heated by IR radiation, microwave radiation or direct contact with one or more heating plates.
  • EVA-containing modules For the bubble-free production of EVA-containing modules is usually a process vacuum of 1 millibar or less required in the vacuum chamber, as only so the originating from the crosslinking of the EVA reaction products can be safely removed.
  • the object of the present invention was therefore to provide a process for the production of solar modules in vacuum laminator using plasticized interlayer films, which has a significant reduction in the tendency to plasticizer residues.
  • the present invention is therefore a process for the preparation of photovoltaic modules, comprising a laminate of a) a transparent front cover b) one or more photosensitive semiconductor layers or coated therewith carriers c) at least one plasticizer-containing, based on polyvinyl acetal film and d) a rear cover wherein one of the layers a) to d) existing composite body is bonded in a process chamber at a temperature of 120-190 0 C and a gas pressure of 200 to 5 * 10 4 Pa to form a laminate.
  • Process chamber i.e., a vacuum laminator
  • FIG. 1 a) the upper and b) the lower part of the vacuum chamber, which are separated by the membrane c) from each other and can be acted upon with different gas pressures.
  • the module is heated via the heating plate d) either directly or by convection.
  • About the conveyor belts e) of the collapsed composite body or the laminated module f) are transported into or out of the process chamber.
  • the temperature of the process chamber may preferably be 130 to 180 ° C, more preferably 140 to 170 ° C, wherein the temperatures of the process chamber are equated with the temperature of the heat source.
  • a heat source IR radiation, microwave radiation, convection or direct contact with one or more heating plates can be used.
  • the heat sources may be mounted above and / or below the laminate.
  • the temperature of the process chamber may be constant over the process time or varied.
  • Process chamber ie in the lower part of the laminator is preferably more than 2000 Pa, more preferably more than 2 * 10 4th
  • the upper limit of the gas pressure in the process chamber can be specified as 5 * 10 4 Pa. This vacuum can remain constant or varied over the process time.
  • the process times depend on the thickness of the laminate, i. the glass thickness, the thickness of the cover sheets and the thickness of the used vitell. Encapsulant from and usually be 10 to 35 min.
  • the laminates may optionally be additionally applied
  • the applied pressing force can be applied via a membrane (c in Fig. 1) which separates the upper (a in Fig. 1) and the lower part (b in Fig. 1) of the vacuum chamber from each other.
  • a membrane c in Fig. 1 which separates the upper (a in Fig. 1) and the lower part (b in Fig. 1) of the vacuum chamber from each other.
  • the upper part of the process chamber is fully or partially vented or even subjected to an overpressure, so that by the differential pressure between the upper and lower process chamber, a pressure i. a surface load is exerted on the laminate or the module.
  • the surface load necessary for pressing can also be applied hydraulically, pneumatically or mechanically via a stable plate. Also conceivable is a combination of these methods.
  • the laminate can be pressed with a surface load of 1 * 10 4 Pa to 12 * 10 5 Pa.
  • Polyvinyl acetal based films preferably contain uncrosslinked polyvinyl butyral (PVB), which is obtained by acetalization of polyvinyl alcohol with butyraldehyde.
  • PVB polyvinyl butyral
  • crosslinked polyvinyl acetals in particular crosslinked polyvinyl butyral (PVB) is also possible.
  • Suitable crosslinked polyvinyl acetals are described, for example, in EP 1527107 B1 and WO 2004/063231 A1 (thermal self-crosslinking of polyvinyl acetals containing carboxyl groups), EP 1606325 A1 (polyvinyl acetals crosslinked with polyaldehydes) and WO 03/020776 A1 (crosslinked with glyoxylic acid Polyvinyl acetals).
  • Aldehydes having 2-10 carbon atoms e.g., valeraldehyde.
  • polyvinyl alcohol terpolymers of hydrolyzed vinyl acetate / ethylene copolymers can be used in the context of the present invention. These compounds are typically hydrolyzed to greater than 98 mole percent and contain from 1 to 10 weight percent ethylene based units (e.g., "Exceval" type from Kuraray Europe GmbH).
  • hydrolyzed copolymers of vinyl acetate and at least one further ethylenically unsaturated monomer can also be used within the scope of the present invention.
  • polyvinyl alcohols can be used in the context of the present invention, pure or as a mixture of polyvinyl alcohols with different degrees of polymerization or degree of hydrolysis.
  • Polyvinyl acetals still contain in addition to the acetal units
  • the polyvinyl acetals used according to the invention preferably have a polyvinyl alcohol content of less than 22% by weight, 20% by weight or 18% by weight, less than 16% by weight or 15% by weight and in particular less than 14% by weight. A polyvinyl alcohol content of 12% by weight should not be exceeded.
  • Polyvinyl acetal is preferably less than 3% by weight or less than 1% by weight, more preferably less than 0.75% by weight, very preferably less than 0.5% by weight and in particular less than 0.25% by weight.
  • the degree of acetalization can be determined by calculation.
  • the films preferably have a plasticizer content of at most 40% by weight, 35% by weight, 32% by weight, 30% by weight, 28% by weight, 26% by weight, 24% by weight or 22% by weight. on, with a plasticizer content of 15 wt.% Should not be exceeded for reasons of processability of the film (each based on the total film formulation).
  • Films or photovoltaic modules used according to the invention can contain one or more plasticizers.
  • Suitable plasticizers for the films used according to the invention are one or more compounds selected from the following groups:
  • Esters of polyhydric aliphatic or aromatic acids e.g. Dialkyladipates such as Dihexyladipat, Dioctyladipat, Hexylcyclohexyladipat, mixtures of heptyl and nonyl adipates, Diisononyladipat, heptylnonyl adipate and esters of adipic acid with cycloaliphatic or ether-containing ester alcohols, dialkyl sebacates such as dibutyl sebacate and esters of sebacic acid with cycloaliphatic or ether-containing ester alcohols, esters of phthalic acid such as butyl benzyl phthalate or bis-2-butoxyethyl phthalate
  • Esters or ethers of polyhydric aliphatic or aromatic alcohols or oligoether glycols having one or more unbranched or branched aliphatic or aromatic substituents e.g. Esters of di-, tri- or tetraglycols with linear or branched aliphatic or cycloaliphatic carboxylic acids;
  • Esters of di-, tri- or tetraglycols with linear or branched aliphatic or cycloaliphatic carboxylic acids may serve diethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylhexanoate), tri-ethylene glycol bis (2-ethylbu-ta-no-ate) .
  • Phosphates with aliphatic or aromatic ester alcohols e.g. Tris (2-ethylhexyl) phosphate (TOF), triethyl phosphate, diphenyl-2-ethylhexyl phosphate, and / or tricresyl phosphate
  • plasticizers for the films used according to the invention are one or more compounds selected from the following group: di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl adipate (DOA), dihexyl adipate (DHA), dibutyl sebacate (DBS), Triethylene glycol bis-n-heptanoate (3G7), tetraethylene glycol bis-n-heptanoate (4G7), triethylene glycol bis-2-ethylhexanoate (3GO or 3G8) tetraethylene glycol bis-n-2-ethylhexanoate (4GO or 4G8) di-2-butoxy-ethyl adipate (DBEA), di-2-butoxyethoxyethyl adipate (DBEEA) di-2-butoxyethyl sebacate (DBES), di-2-eth-ethyl
  • Cyclohexane-i-dicarboxylic acid diisononyl ester (DINCH) and dipropylene glycol zoate.
  • Glass can be replaced by the addition of adhesion regulators such.
  • adhesion regulators such as WO 03/033583 A1 alkali and / or alkaline earth metal salts of organic acids can be adjusted. Be particularly suitable potassium acetate and / or magnesium acetate have been found. To obtain high adhesion values it may be necessary to use films without the addition of adhesion regulators such as alkali and / or alkaline earth salts.
  • the based on plasticized polyvinyl acetal film preferably has a one-sided or more preferably applied on both sides surface structure with a roughness of Rz between 10 and 180 microns, preferably Rz> 20 microns and Rz ⁇ 180 microns, more preferably Rz> 35 microns and Rz ⁇ 150 ⁇ m and in particular of Rz> 35 ⁇ m and Rz ⁇ 130 ⁇ m.
  • the surface structure of the film can be produced in the extrusion process by the so-called flow or melt fracture method according to EP 0 185 863 B1. This process leads to an irregular, approximately isotropic roughness.
  • the measured value of the roughness is measured here approximately the same across all directions, but the individual elevations and depressions are arranged irregularly in their height and distribution.
  • the surface structure of the film may be formed by embossing, e.g. according to EP 06112163 or EP 06112159. This results in a regular roughness / roughness structure of the surface.
  • the measurement of the surface roughness Rz or the roughness value Rz is carried out according to DIN EN ISO 4287.
  • the measurements indicated were a roughness measuring device of the company Mahr type S2, feed device PGK with mechanical single-use button MFW-250 carried out.
  • the cut-off wavelength Ic is 8 mm, the total measuring distance in the 40 mm, consisting of five individual measuring sections Ie of 8 mm each with a leading and trailing distance Iv or In of 8 mm.
  • Foils are usually 0.38, 0.51, 0.76, 1.14, 1.52 or 2.28 mm.
  • the basic preparation and composition of films based on polyvinyl acetals is z.
  • EP 185 863 B1 EP 1 118 258 B1, WO 02/102591 A1.
  • the photosensitive material in another variant of the invention, the photosensitive organic compound
  • Deposited semiconductor layers on a support for example by vapor deposition, vapor deposition, sputtering or wet deposition. These supported photosensitive semiconductor layers are embedded between two films c) and thus bonded to the covers a) and d).
  • photosensitive semiconductor layer directly to one of the covers a) or d) (eg by vapor deposition, vapor deposition, sputtering or wet separation). Encapsulation is not possible or required in this variant of the invention.
  • one or more photosensitive semiconductor layers b) are applied to a transparent front cover a) or a rear cover d) and by at least one plasticizer-containing, based on polyvinyl acetal film c) glued together.
  • the transparent front cover is usually made of glass or transparent plastics such as ETFE or PMMA.
  • the rear cover of the photovoltaic module can be made of glass, plastic or metal or their composites, wherein at least one of the carriers can be transparent. It is also possible to use one or both covers as a composite glazing (i.e., as a laminate of at least two glass sheets and at least one PVB sheet) or as insulating glazing with a gas gap. Of course, the combination of these measures is possible.
  • the photosensitive semiconductor layers used in the modules need not have any special properties. Mono-, polycrystalline, organic or amorphous systems can be used.
  • Photovoltaic modules produced according to the invention can be used in solar power plants, as a facade component, roof surfaces, conservatory cover, soundproof wall, balcony or parapet element or as part of window surfaces.
  • a thin-film module of size L 130 cm ⁇ W 110 cm with a glass thickness of 3.2 mm with internal longitudinal and transverse contacts and a contact hole on the back glass is laminated in a vacuum laminator.
  • the film used is the product TROSIFOL R40 in a thickness of 0.76 mm.
  • the film was conditioned for at least 12 hours at 23 ° C and a relative humidity of 25%.
  • the edge overhang is 5mm circumferential.
  • the heating plate has a temperature of 150 ° C, the vacuum is less than 100 Pa.
  • the module is first evacuated for 11 min, then the upper process chamber is over Ventilated period from 5 min to 600 mbar. The module is then held under these process conditions for 12 minutes. This gives a bubble-free ready-connected laminate with light

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Electromagnetism (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Thermal Sciences (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention relates to a method for producing photovoltaic modules comprising a laminated structure composed of a) a transparent front cover, b) one or more photosensitive semiconductor layers, c) at least one plasticized, polyvinyl acetal-based film and d) a rear cover. The method according to the invention is characterized in that a layer structure consisting of layers a) to d) is bonded in a process chamber at a temperature of 120 – 190°C and at a gas pressure of 200 to 5*104 Pa to give a laminated structure.

Description

Beschreibung description
[0001] Verfahren zur Herstellung von Photovoltaikmodulen im Vakuumlaminator mit reduziertem Prozessvakuum. Technisches GebietProcess for the preparation of photovoltaic modules in Vakuumlaminator with reduced process vacuum. Technical area
[0002] Die Erfindung betrifft ein Verfahren zur Herstellung vonThe invention relates to a process for the preparation of
Photovoltaikmodulen unter erhöhter Temperatur und vermindertem Gasumgebungsdruck unter Verwendung einer auf Polyvinylacetal basierenden Folie.Photovoltaic modules under elevated temperature and reduced gas ambient pressure using a polyvinyl acetal based film.
Stand der TechnikState of the art
[0003] Photovoltaikmodule bestehen aus einer photosensitiven Halbleiterschicht, die zum Schutz gegen äußere Einflüsse mit einer transparenten Abdeckung versehen wird. Als photosensitive Halbleiterschicht können monokristalline Solarzellen oder polykristalline, dünne Halbleiterschichten auf einem Träger eingesetzt werden. Dünnschicht-Solarmodule bestehen aus einer photosensitiven Halbleiterschicht, die auf eine meist transparente Platte z.B. durch Aufdampfen, Gasphasenabscheidung, Sputtern oder Nassabscheidung aufgebracht ist.Photovoltaic modules consist of a photosensitive semiconductor layer, which is provided to protect against external influences with a transparent cover. As a photosensitive semiconductor layer, monocrystalline solar cells or polycrystalline, thin semiconductor layers can be used on a support. Thin-film solar modules consist of a photosensitive semiconductor layer coated on a mostly transparent plate, e.g. by vapor deposition, vapor deposition, sputtering or wet deposition is applied.
[0004] Beide Systeme werden zwischen eine Glasscheibe und eine rigide, hintere Abdeckplatte z.B. aus Glas oder Kunststoffen mit Hilfe eines transparenten Klebers laminiert.Both systems are sandwiched between a pane of glass and a rigid, rear cover plate, e.g. laminated from glass or plastics using a transparent adhesive.
[0005] Als transparente Kleber werden häufig aushärtende Gießharze oder vernetzbare, auf Ethylenvinylacetat (EVA) basierende Systeme eingesetzt, so wie beispielsweise in DE 41 22 721 C1 oder DE 41 28 766 A1 offenbart.Curing resins or crosslinkable systems based on ethylene-vinyl acetate (EVA) are frequently used as transparent adhesives, as disclosed, for example, in DE 41 22 721 C1 or DE 41 28 766 A1.
[0006] Eine Alternative zu aushärtenden Klebesystemen ist der Einsatz von weichmacherhaltigen Folien auf Basis von Polyvinylacetalen wie das aus der Verbundglasherstellung bekannte Polyvinylbutyral (PVB). Die Solarzelleneinheiten werden mit einer oder mehreren PVB-Folien bedeckt und diese unter erhöhtem Druck und erhöhter Temperatur mit den gewünschten Abdeckmaterialien zu einem Laminat verbunden. Verfahren dieser Art sind z.B. aus DE 40 26 165 C2, DE 42 278 60 A1 , DE 29 237 70 C2, DE 35 38 986 C2 oder US 4,321 ,418 bekannt.An alternative to thermosetting adhesive systems is the use of plasticized films based on polyvinyl acetals, such as polyvinyl butyral (PVB) known from the manufacture of laminated glass. The solar cell units are covered with one or more PVB films and bonded under elevated pressure and temperature with the desired covering materials into a laminate. Methods of this kind are e.g. From DE 40 26 165 C2, DE 42 278 60 A1, DE 29 237 70 C2, DE 35 38 986 C2 or US 4,321,418 known.
[0007] Neben den Eigenschaften der verwendeten Materialien beeinflusst auch die Qualität der Verbindung zwischen den einzelnen Komponenten die Dauerhaftigkeit und Sicherheit der Solarmodule. Blasenbildung im Modul oder Bereiche schlechter Verklebung beeinflussen die Lebensdauer negativ.In addition to the properties of the materials used also influences the quality of the connection between the individual components the durability and safety of the solar modules. Bubble formation in the module or areas of poor adhesion negatively affect the service life.
[0008] Das zurzeit gängigste Verfahren zur Herstellung von Solarmodulen ist die Lamination im Vakuumlaminator. Hierbei wird das Modul in einer Vakuumkammer entlüftet und durch IR-Strahlung, Mikrowellenstrahlung oder direkten Kontakt mit einer oder mehreren Heizplatten erhitzt.The currently most common method for the production of solar modules is the lamination in Vakuumlaminator. In this case, the module is vented in a vacuum chamber and heated by IR radiation, microwave radiation or direct contact with one or more heating plates.
[0009] Für die blasenfreie Herstellung von EVA enthaltenden Modulen wird in der Regel ein Prozessvakuum von 1 Millibar oder kleiner in der Vakuumkammer gefordert, da nur so die aus der Vernetzung des EVA stammenden Reaktionsprodukte sicher entfernt werden können.For the bubble-free production of EVA-containing modules is usually a process vacuum of 1 millibar or less required in the vacuum chamber, as only so the originating from the crosslinking of the EVA reaction products can be safely removed.
[0010] Werden Klebefolien auf Basis von Polyvinylacetal in solchen Prozessen eingesetzt, so entweichen Teile des Weichmachers aus dem Randbereich der Folie und schlagen sich als öliger Belag auf dem Laminat und in der Vakuumkammer nieder. Dies erhöht die Prozesskosten bzw. verringert die Taktzeiten durch erhöhten Reinigungsaufwand.If adhesive films based on polyvinyl acetal are used in such processes, parts of the plasticizer escape from the edge region of the film and precipitate as an oily coating on the laminate and in the vacuum chamber. This increases the process costs or reduces cycle times due to increased cleaning effort.
Technische AufgabeTechnical task
[0011] Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur Herstellung von Solarmodulen im Vakuumlaminator unter Verwendung von weichmacherhaltigen Zwischenschichtfolien bereit zu stellen, das eine deutliche Reduktion der Neigung zu Weichmacherrückständen aufweist.The object of the present invention was therefore to provide a process for the production of solar modules in vacuum laminator using plasticized interlayer films, which has a significant reduction in the tendency to plasticizer residues.
[0012] Die Erfahrungen bei der Lamination von Solarmodulen mit EVA-Folien zeigen, dass für die Herstellung eines blasenfreien Laminats ein hohes Prozessvakuum von Nöten ist. Dementsprechend wurden bei entsprechender Verwendung von weichmacherhaltigen Polyvinylbutyralfolien die aus der Verarbeitung von EVA-Folien bekannten Prozessparameter übernommen oder nicht weiter spezifiziert, wie z.B. in DE 202006014595 111 , DE 69828921 T2, DE 20302045 111 , DE 69431140 T2, DE 69527715 T2 oder DE 69734631 T2 offenbart.The experience in the lamination of solar modules with EVA films show that for the production of a bubble-free laminate, a high process vacuum is needed. Accordingly, with appropriate use of plasticized polyvinyl butyral films, the process parameters known from the processing of EVA films have been adopted or no further specified, such as e.g. in DE 202006014595 111, DE 69828921 T2, DE 20302045 111, DE 69431140 T2, DE 69527715 T2 or DE 69734631 T2.
Technische LösungTechnical solution
[0013] Überraschenderweise wurde gefunden, dass bei Verwendung von weichmacherhaltiger Folie auf Basis von Polyvinylacetalen auch mit einem erhöhten Gasumgebungsdruck blasenfreie Verbünde hergestellt werden können, wobei gleichzeitig der Weichmacherverlust und damit der ölige Weichmacherbelag auf dem laminat und in der Prozesskammer während des Prozesses reduziert wird.Surprisingly, it was found that when using plasticized film based on polyvinyl acetals with a Bubble-free composites can be produced at elevated gas ambient pressure, whereby at the same time the plasticizer loss and thus the oily plasticizer coating on the laminate and in the process chamber is reduced during the process.
Darstellung der ErfindungPresentation of the invention
[0014] Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von Photovoltaikmodulen, umfassend ein Laminat aus a) einer transparenten Frontabdeckung b) einer oder mehreren photosensitiven Halbleiterschichten oder hiermit beschichteten Trägern c) mindestens einer weichmacherhaltigen, auf Polyvinylacetal basierenden Folie und d) einer rückwärtigen Abdeckung wobei ein aus den Schichten a) bis d) bestehender Schichtkörper in einer Prozesskammer bei einer Temperatur von 120 - 190 0C und einem Gasdruck von 200 bis 5*104 Pa zu einem Laminat verklebt wird.The present invention is therefore a process for the preparation of photovoltaic modules, comprising a laminate of a) a transparent front cover b) one or more photosensitive semiconductor layers or coated therewith carriers c) at least one plasticizer-containing, based on polyvinyl acetal film and d) a rear cover wherein one of the layers a) to d) existing composite body is bonded in a process chamber at a temperature of 120-190 0 C and a gas pressure of 200 to 5 * 10 4 Pa to form a laminate.
[0015] Ein typischer Aufbau einer erfindungsgemäß eingesetztenA typical structure of an inventively used
Prozesskammer (d.h. eines Vakuumlaminators) ist in Fig. 1 dargestellt. Hierbei bedeuten a) den oberen und b) den unteren Teil der Vakuumkammer, die über die Membran c) von einander getrennt sind und mit unterschiedlichen Gasdrücken beaufschlagt werden können. Das Modul wird über die Heizplatte d) entweder direkt oder durch Konvektion aufgeheizt. Über die Transportbänder e) kann der zusammengelegte Schichtkörper bzw. das laminierte Modul f) in bzw. aus der Prozesskammer transportiert werden.Process chamber (i.e., a vacuum laminator) is shown in FIG. In this case, a) the upper and b) the lower part of the vacuum chamber, which are separated by the membrane c) from each other and can be acted upon with different gas pressures. The module is heated via the heating plate d) either directly or by convection. About the conveyor belts e) of the collapsed composite body or the laminated module f) are transported into or out of the process chamber.
[0016] Die Temperatur der Prozesskammer kann bevorzugt 130 bis 180°C, besonders bevorzugt 140 bis 170°C betragen, wobei die Temperaturen der Prozesskammer mit der Temperatur der Heizquelle gleichgesetzt werden. Als Heizquelle kann IR-Strahlung, Mikrowellenstrahlung, Konvektion oder der direkte Kontakt mit einer oder mehreren Heizplatten eingesetzt werden. Die Heizquellen können oberhalb und/oder unterhalb des Laminats angebracht sein. Die Temperatur der Prozesskammer kann über die Prozesszeit konstant sein oder variiert werden. [0017] Der das Laminat bzw. das Modul umgebende Gasdruck in derThe temperature of the process chamber may preferably be 130 to 180 ° C, more preferably 140 to 170 ° C, wherein the temperatures of the process chamber are equated with the temperature of the heat source. As a heat source IR radiation, microwave radiation, convection or direct contact with one or more heating plates can be used. The heat sources may be mounted above and / or below the laminate. The temperature of the process chamber may be constant over the process time or varied. The surrounding the laminate or the module gas pressure in the
Prozesskammer, d.h. im unteren Teil des Laminators beträgt bevorzugt mehr als 2000 Pa, besonders bevorzugt mehr als 2*104. Als obere Grenze des Gasdrucks in der Prozesskammer kann jeweils 5*104 Pa angegeben werden. Dieses Vakuum kann über die Prozesszeit konstant bleiben oder variiert werden.Process chamber, ie in the lower part of the laminator is preferably more than 2000 Pa, more preferably more than 2 * 10 4th The upper limit of the gas pressure in the process chamber can be specified as 5 * 10 4 Pa. This vacuum can remain constant or varied over the process time.
[0018] Die Prozesszeiten hängen von der Dicke des Laminats d.h. der Glasdicke, der Dicke der Deckfolien und der Dicke der verwendeten Zwischenschichtbzw. Einkapselungsfolie ab und betragen in der Regel 10 bis 35 min.The process times depend on the thickness of the laminate, i. the glass thickness, the thickness of the cover sheets and the thickness of the used Zwischenschichtbzw. Encapsulant from and usually be 10 to 35 min.
[0019] Die Laminate können optional mit einer zusätzlich aufgebrachtenThe laminates may optionally be additionally applied
Flächenbelastung verpresst werden. Die eingesetzte Presskraft kann über eine Membran (c in Fig. 1) aufgebracht werden welche den oberen (a in Fig. 1) und den unteren Teil (b in Fig. 1) der Vakuumkammer voneinander trennt. Zum aufbringen des Flächenbelastung auf das Laminat wird der obere Teil der Prozesskammer ganz oder teilweise belüftet oder sogar mit einem Überdruck beaufschlagt, so dass durch den Differenzdruck zwischen oberer und unterer Prozesskammer ein Druck d.h. eine Flächenbelastung auf das Laminat bzw. das Modul ausgeübt wird.Surface load be pressed. The applied pressing force can be applied via a membrane (c in Fig. 1) which separates the upper (a in Fig. 1) and the lower part (b in Fig. 1) of the vacuum chamber from each other. To apply the surface load on the laminate, the upper part of the process chamber is fully or partially vented or even subjected to an overpressure, so that by the differential pressure between the upper and lower process chamber, a pressure i. a surface load is exerted on the laminate or the module.
[0020] Die zum Verpressen notwendige Flächenbelastung kann auch über eine stabile Platte hydraulisch, pneumatisch oder mechanisch aufgebracht werden. Denkbar ist auch eine Kombination dieser Methoden. Im erfindungsgemäßen Verfahren kann das Laminat mit einer Flächenbelastung von 1*104 Pa bis 12*105 Pa verpresst werden.The surface load necessary for pressing can also be applied hydraulically, pneumatically or mechanically via a stable plate. Also conceivable is a combination of these methods. In the process of the invention, the laminate can be pressed with a surface load of 1 * 10 4 Pa to 12 * 10 5 Pa.
[0021] Die erfindungsgemäß eingesetzten, auf weichmacherhaltigemThe inventively used on plasticizer-containing
Polyvinylacetal basierenden Folien, enthalten bevorzugt unvernetztes Polyvinylbutyral (PVB), das durch Acetalisierung von Polyvinylalkohol mit Butyraldehyd gewonnen wird.Polyvinyl acetal based films preferably contain uncrosslinked polyvinyl butyral (PVB), which is obtained by acetalization of polyvinyl alcohol with butyraldehyde.
[0022] Der Einsatz von vernetzten Polyvinylacetalen, insbesondere vernetztem Polyvinylbutyral (PVB) ist ebenso möglich. Geeignete vernetzte Polyvinylacetale sind z.B. in EP 1527107 B1 und WO 2004/063231 A1 (thermische Selbstvernetzung von Carboxylgruppenhaltigen Polyvinylacetalen), EP 1606325 A1 (mit Polyaldehyden vernetzte Polyvinylacetale) und WO 03/020776 A1 (mit Glyoxylsäure vernetzte Polyvinylacetale) beschrieben.The use of crosslinked polyvinyl acetals, in particular crosslinked polyvinyl butyral (PVB) is also possible. Suitable crosslinked polyvinyl acetals are described, for example, in EP 1527107 B1 and WO 2004/063231 A1 (thermal self-crosslinking of polyvinyl acetals containing carboxyl groups), EP 1606325 A1 (polyvinyl acetals crosslinked with polyaldehydes) and WO 03/020776 A1 (crosslinked with glyoxylic acid Polyvinyl acetals).
[0023] Es ist auch möglich, die Acetalisierung mit anderen oder mehrerenIt is also possible to acetalize with others or more
Aldehyden mit 2-10 Kohlenstoffatomen (z.B. Valeraldehyd) durchzuführen.Aldehydes having 2-10 carbon atoms (e.g., valeraldehyde).
[0024] Als Polyvinylalkohol können im Rahmen der vorliegenden Erfindung auch Terpolymere aus hydrolysierten Vinylacetat/Ethylen-Copolymeren eingesetzt werden. Diese Verbindungen sind in der Regel zu mehr als 98 Mol% hydrolysiert und enthalten 1 bis 10 Gew. auf Ethylen basierende Einheiten (z.B. Typ „Exceval" der Kuraray Europe GmbH).As polyvinyl alcohol terpolymers of hydrolyzed vinyl acetate / ethylene copolymers can be used in the context of the present invention. These compounds are typically hydrolyzed to greater than 98 mole percent and contain from 1 to 10 weight percent ethylene based units (e.g., "Exceval" type from Kuraray Europe GmbH).
[0025] Als Polyvinylalkohol können im Rahmen der vorliegenden Erfindung weiterhin auch hydrolysierte Copolymere aus Vinylacetat und mindestens einem weiteren ethylenisch ungesättigten Monomer eingesetzt werden.As polyvinyl alcohol, hydrolyzed copolymers of vinyl acetate and at least one further ethylenically unsaturated monomer can also be used within the scope of the present invention.
[0026] Die Polyvinylalkohole können im Rahmen der vorliegenden Erfindung rein oder als Mischung von Polyvinylalkoholen mit unterschiedlichem Polymerisationsgrad oder Hydrolysegrad eingesetzt werden.The polyvinyl alcohols can be used in the context of the present invention, pure or as a mixture of polyvinyl alcohols with different degrees of polymerization or degree of hydrolysis.
[0027] Polyvinylacetale enthalten neben den Acetaleinheiten noch ausPolyvinyl acetals still contain in addition to the acetal units
Vinylacetat und Vinylalkohol resultierende Einheiten. Die erfindungsgemäß verwendeten Polyvinylacetale weisen bevorzugt einen Polyvinylalkoholanteil von weniger als 22 Gew.%, 20 Gew.% oder 18 Gew.%, weniger als 16 Gew.% oder 15 Gew.% und insbesondere weniger als 14 Gew.% auf. Ein Polyvinylalkoholanteil von 12 Gew.% sollte nicht unterschritten werden.Vinyl acetate and vinyl alcohol resulting units. The polyvinyl acetals used according to the invention preferably have a polyvinyl alcohol content of less than 22% by weight, 20% by weight or 18% by weight, less than 16% by weight or 15% by weight and in particular less than 14% by weight. A polyvinyl alcohol content of 12% by weight should not be exceeded.
[0028] Der Polyvinylacetatgehalt des erfindungsgemäß eingesetztenThe polyvinyl acetate content of the invention used
Polyvinylacetals liegt bevorzugt unter 3 Gew.% oder unter 1 Gew.%, besonders bevorzugt unter 0,75 Gew.%, ganz besonders bevorzugt unter 0,5 Gew.% und insbesondere unter 0,25 Gew.%.Polyvinyl acetal is preferably less than 3% by weight or less than 1% by weight, more preferably less than 0.75% by weight, very preferably less than 0.5% by weight and in particular less than 0.25% by weight.
[0029] Aus dem Polyvinylalkoholanteil und dem Restacetatgehalt kann der Acetalisierungsgrad rechnerisch ermittelt werden.From the polyvinyl alcohol content and the residual acetate content, the degree of acetalization can be determined by calculation.
[0030] Bevorzugt weisen die Folien einen Weichmachergehalt von maximal 40 Gew.%, 35 Gew.%, 32 Gew.%, 30 Gew.%, 28 Gew.%, 26 Gew.%, 24 Gew.% oder 22 Gew.% auf, wobei ein Weichmachergehalt von 15 Gew.% aus Gründen der Verarbeitbarkeit der Folie nicht unterschritten werden sollte (jeweils bezogen auf die gesamte Folienformulierung). Erfindungsgemäß verwendete Folien bzw. Photovoltaikmodule können einen oder mehrere Weichmacher enthalten.The films preferably have a plasticizer content of at most 40% by weight, 35% by weight, 32% by weight, 30% by weight, 28% by weight, 26% by weight, 24% by weight or 22% by weight. on, with a plasticizer content of 15 wt.% Should not be exceeded for reasons of processability of the film (each based on the total film formulation). Films or photovoltaic modules used according to the invention can contain one or more plasticizers.
[0031] Geeignete Weichmacher für die erfindungsgemäß eingesetzten Folien sind eine oder mehrere Verbindungen ausgewählt aus den folgenden Gruppen:Suitable plasticizers for the films used according to the invention are one or more compounds selected from the following groups:
- Ester von mehrwertigen aliphatischen oder aromatischen Säuren, z.B. Dialkyladipate wie Dihexyladipat, Dioctyladipat, Hexylcyclohexyladipat, Mischungen aus Heptyl- und Nonyl-adipaten, Diisononyladipat, Heptylnonyl-adipat sowie Ester der Adipinsäure mit cycloaliphatischen oder Etherbindungen enthaltenden Esteralkoholen, Dialkylsebazate wie Dibutylsebazat sowie Ester der Sebazinsäure mit cycloaliphatischen oder Etherbindungen enthaltenden Esteralkoholen, Estern der Phthalsäure wie Butylbenzylphthalat oder Bis-2-butoxyethylphthalatEsters of polyhydric aliphatic or aromatic acids, e.g. Dialkyladipates such as Dihexyladipat, Dioctyladipat, Hexylcyclohexyladipat, mixtures of heptyl and nonyl adipates, Diisononyladipat, heptylnonyl adipate and esters of adipic acid with cycloaliphatic or ether-containing ester alcohols, dialkyl sebacates such as dibutyl sebacate and esters of sebacic acid with cycloaliphatic or ether-containing ester alcohols, esters of phthalic acid such as butyl benzyl phthalate or bis-2-butoxyethyl phthalate
- Ester oder Ether von mehrwertigen aliphatischen oder aromatischen Alkoholen oder Oligoetherglykolen mit einem oder mehreren unverzweigten oder verzweigten aliphatischen oder aromatischen Substituenten, wie z.B. Estern von Di-, Tri- oder Tetraglykolen mit linearen oder verzweigten ali-phatischen oder cycloaliphatischen Carbonsäuren; Als Beispiele für letztere Gruppe können dienen Diethylenglykol-bis-(2-ethyl-hexanoat), Triethylenglykol-bis-(2-ethyl-hexanoat), Tri-ethylen-glykol-bis-(2-ethylbu-ta-no-at),Esters or ethers of polyhydric aliphatic or aromatic alcohols or oligoether glycols having one or more unbranched or branched aliphatic or aromatic substituents, e.g. Esters of di-, tri- or tetraglycols with linear or branched aliphatic or cycloaliphatic carboxylic acids; As examples of the latter group may serve diethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylhexanoate), tri-ethylene glycol bis (2-ethylbu-ta-no-ate) .
Tetra-ethylen-glykol-bis-n-heptanoat, Triethylengly-kol-bis-n-heptanoat, Triethylenglykol-bis-n-hexanoat, Tetraethylen-glykol-dimethyl-ether und/oder DipropylenglykolbenzoatTetraethylene glycol bis-n-heptanoate, triethylene glycol bis-n-heptanoate, triethylene glycol bis-n-hexanoate, tetraethylene glycol dimethyl ether and / or Dipropylenglykolbenzoat
- Phosphate mit aliphatischen oder aromatischen Esteralkoholen wie z.B. Tris(2-ethylhexyl)phosphat (TOF), Triethylphosphat, Diphenyl-2-ethylhexylphosphat, und/oder TrikresylphosphatPhosphates with aliphatic or aromatic ester alcohols, e.g. Tris (2-ethylhexyl) phosphate (TOF), triethyl phosphate, diphenyl-2-ethylhexyl phosphate, and / or tricresyl phosphate
- Ester der Zitronensäure, Bernsteinsäure und/oder Fumarsäure. [0032] Besonders geeignet als Weichmacher für die erfindungsgemäß eingesetzten Folien sind eine oder mehrere Verbindungen ausgewählt aus der folgende Gruppe Di-2-ethylhexylsebacat (DOS), Di-2-ethylhexyladipat (DOA), Dihexyladipat (DHA), Dibutylsebacat (DBS), Triethylenglykol-bis-n-heptanoat (3G7), Tetraethylenglykol-bis-n-heptanoat (4G7), Triethylenglykol-bis-2-ethylhexanoat (3GO bzw. 3G8) Tetraethylenglykol-bis-n-2-ethylhexanoat (4GO bzw. 4G8) Di-2-butoxy-ethyl-adipat (DBEA), Di-2-butoxyethoxyethyladipat (DBEEA) Di-2-butoxyethylsebacat (DBES), Di-2-ethylhexylphthalat (DOP), Triethylenglykol-bis-isononanoat, Triethylenglykol-bis-2-propylhexanoat, Tris(2-ethylhexyl)phosphat (TOF),- esters of citric acid, succinic acid and / or fumaric acid. Particularly suitable plasticizers for the films used according to the invention are one or more compounds selected from the following group: di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl adipate (DOA), dihexyl adipate (DHA), dibutyl sebacate (DBS), Triethylene glycol bis-n-heptanoate (3G7), tetraethylene glycol bis-n-heptanoate (4G7), triethylene glycol bis-2-ethylhexanoate (3GO or 3G8) tetraethylene glycol bis-n-2-ethylhexanoate (4GO or 4G8) di-2-butoxy-ethyl adipate (DBEA), di-2-butoxyethoxyethyl adipate (DBEEA) di-2-butoxyethyl sebacate (DBES), di-2-ethylhexyl phthalate (DOP), triethylene glycol bis-isononanoate, triethylene glycol bis-2-propylhexanoate, tris (2-ethylhexyl) phosphate (TOF),
Cyclohexan-i ^-dicarbonsäure-diisononylester (DINCH) und Dipropylenglykolbenzoat.Cyclohexane-i-dicarboxylic acid diisononyl ester (DINCH) and dipropylene glycol zoate.
[0033] Das Haftungsvermögen von Folien auf Basis von Polyvinylacetalen anThe adhesion of films based on polyvinyl acetals
Glas kann durch die Zugabe von Haftungsregulatoren wie z. B. die in WO 03/033583 A1 offenbarten Alkali- und/oder Erdalkalisalze von organischen Säuren eingestellt werden. Als besonders geeignet haben sich Kaliumacetat und/oder Magnesiumacetat herausgestellt. Zum Erhalt von hohen Haftungswerten kann es erforderlich sein, Folien ohne Zusatz von Haftungsregulatoren wie Alkali- und/oder Erdalkalisalze einzusetzen.Glass can be replaced by the addition of adhesion regulators such. B. the disclosed in WO 03/033583 A1 alkali and / or alkaline earth metal salts of organic acids can be adjusted. Be particularly suitable potassium acetate and / or magnesium acetate have been found. To obtain high adhesion values it may be necessary to use films without the addition of adhesion regulators such as alkali and / or alkaline earth salts.
[0034] Die auf weichmacherhaltigem Polyvinylactetal basierende Folie weist bevorzugt eine einseitig oder besonders bevorzugt beidseitig aufgebrachte Oberflächenstruktur mit einer Rauhigkeit von Rz zwischen 10 und 180 μm, bevorzugt Rz > 20 μm und Rz < 180 μm, besonders bevorzugt Rz > 35 μm und Rz < 150 μm und insbesondere von Rz > 35 μm und Rz < 130 μm auf.The based on plasticized polyvinyl acetal film preferably has a one-sided or more preferably applied on both sides surface structure with a roughness of Rz between 10 and 180 microns, preferably Rz> 20 microns and Rz <180 microns, more preferably Rz> 35 microns and Rz < 150 μm and in particular of Rz> 35 μm and Rz <130 μm.
[0035] Die Oberflächenstruktur der Folie kann im Extrusionsprozess durch das so genannte Fließ- oder Schmelzbruchverfahren entsprechend der EP 0 185 863 B1 erzeugt werden. Dieses Verfahren führt zu einer unregelmäßigen, annähernd isotropen Rauhigkeit. Der Messwert der Rauhigkeit ist hier über alle Richtungen gemessen annähernd gleich, wobei die einzelnen Erhebungen und Vertiefungen jedoch unregelmäßig in ihrer Höhe und Verteilung angeordnet sind.The surface structure of the film can be produced in the extrusion process by the so-called flow or melt fracture method according to EP 0 185 863 B1. This process leads to an irregular, approximately isotropic roughness. The measured value of the roughness is measured here approximately the same across all directions, but the individual elevations and depressions are arranged irregularly in their height and distribution.
[0036] Alternativ kann die Oberflächenstruktur der Folie durch Prägeverfahren z.B. gemäß EP 06112163 oder EP 06112159 aufgebracht werden. Hierbei ergibt sich eine regelmäßige Rauhigkeit/Rauhigkeitsstruktur der Oberfläche.Alternatively, the surface structure of the film may be formed by embossing, e.g. according to EP 06112163 or EP 06112159. This results in a regular roughness / roughness structure of the surface.
[0037] Die Messung der Oberflächenrauhigkeit Rz oder des Rauhigkeitswerts Rz erfolgt nach DIN EN ISO 4287. Die angegebenen Messungen wurden mit einem Rauhigkeitsmessgerät der Fa. Mahr Typ S2, Vorschubgerät PGK mit mechanischem Einkufentaster MFW-250 durchgeführt. Die Grenzwellenlänge Ic beträgt 8 mm, die Gesamtmessstrecke Im 40 mm, bestehend aus fünf Einzelmessstrecken Ie zu je 8 mm mit einer Vorlauf- und Nachlaufstrecke Iv bzw. In von jeweils 8 mm.The measurement of the surface roughness Rz or the roughness value Rz is carried out according to DIN EN ISO 4287. The measurements indicated were a roughness measuring device of the company Mahr type S2, feed device PGK with mechanical single-use button MFW-250 carried out. The cut-off wavelength Ic is 8 mm, the total measuring distance in the 40 mm, consisting of five individual measuring sections Ie of 8 mm each with a leading and trailing distance Iv or In of 8 mm.
[0038] Die Dicke der auf weichmacherhaltigem Polyvinylacetal basierendenThe thickness of the plasticized polyvinyl acetal based
Folien liegt üblicherweise bei 0.38, 0.51 , 0.76, 1.14, 1.52 oder 2.28 mm. Die prinzipielle Herstellung und Zusammensetzung von Folien auf Basis von Polyvinylacetalen ist z. B. in EP 185 863 B1 , EP 1 118 258 B1 WO 02/102591 A1. EP 1 118 258 B1 oder EP 387 148 B1 beschrieben.Foils are usually 0.38, 0.51, 0.76, 1.14, 1.52 or 2.28 mm. The basic preparation and composition of films based on polyvinyl acetals is z. In EP 185 863 B1, EP 1 118 258 B1, WO 02/102591 A1. EP 1 118 258 B1 or EP 387 148 B1.
[0039] In einer Variante des erfindungsgemäßen Verfahrens erfolgt dieIn a variant of the method according to the invention takes place
Herstellung der Photovoltaikmodule durch Laminierung der transparenten Frontabdeckung a), den photosensitiven Halbleiterschichten b) und der rückwärtigen Abdeckung d) durch Einbetten der photosensitiven Halbleiterschichten zwischen mindestens zwei Folien c). Hierdurch werden die photosensitiven Halbleiterschichten mit den Abdeckungen a) und d) verklebt.Production of the photovoltaic modules by laminating the transparent front cover a), the photosensitive semiconductor layers b) and the back cover d) by embedding the photosensitive semiconductor layers between at least two foils c). As a result, the photosensitive semiconductor layers with the covers a) and d) are bonded.
[0040] In einer anderen Variante der Erfindung sind die photosensitivenIn another variant of the invention, the photosensitive
Halbleiterschichten auf einen Träger aufgebracht (z.B. durch Aufdampfen, Gasphasenabscheidung, Sputtern oder Nassabscheidung). Diese geträgerten photosensitiven Halbleiterschichten werden zwischen zwei Folien c) eingebettet und so mit den Abdeckungen a) und d) verklebt.Deposited semiconductor layers on a support (for example by vapor deposition, vapor deposition, sputtering or wet deposition). These supported photosensitive semiconductor layers are embedded between two films c) and thus bonded to the covers a) and d).
[0041] In diesen Varianten verschmelzen die weichmacherhaltigen, aufIn these variants, the plasticizer-containing, merge
Polyvinylacetal basierenden Folien c) miteinander, so dass ein blasen- und schlierenfreier Einschluss der photosensitiven Halbleiterschicht erhalten wird.Polyvinyl acetal-based films c) with each other, so that a bubble and schlierenfreier inclusion of the photosensitive semiconductor layer is obtained.
[0042] Es ist auch möglich, die photosensitive Halbleiterschicht direkt auf eine der Abdeckungen a) oder d) aufzubringen (z.B. durch Aufdampfen, Gasphasenabscheidung, Sputtern oder Nassabscheidung). Eine Einkapselung ist in dieser Variante der Erfindung nicht möglich bzw. erforderlich. In einem solchen Modul sind daher eine oder mehrere photosensitive Halbleiterschichten b) auf eine transparente Frontabdeckung a) oder eine rückwärtige Abdeckung d) aufgebracht und durch mindestens einer weichmacherhaltigen, auf Polyvinylacetal basierenden Folie c) miteinander verklebt.It is also possible to apply the photosensitive semiconductor layer directly to one of the covers a) or d) (eg by vapor deposition, vapor deposition, sputtering or wet separation). Encapsulation is not possible or required in this variant of the invention. In such a module, therefore, one or more photosensitive semiconductor layers b) are applied to a transparent front cover a) or a rear cover d) and by at least one plasticizer-containing, based on polyvinyl acetal film c) glued together.
[0043] Erfindungsgemäß eingesetzte Folien füllen während des[0043] Films used according to the invention fill during the
Laminierprozesses die an den photosensitiven Halbleiterschichten bzw. deren elektrischen Verbindungen vorhandenen Hohlräume aus.Laminierprozesses the existing on the photosensitive semiconductor layers or their electrical connections cavities.
[0044] Die transparente Frontabdeckung besteht in der Regel aus Glas oder transparenten Kunststoffen wie ETFE oder PMMA. Die rückwärtige Abdeckung des Photovoltaikmoduls kann aus Glas, Kunststoff oder Metall oder deren Verbünden bestehen, wobei mindestens einer der Träger transparent sein kann. Es ist ebenfalls möglich, einen oder beide Abdeckungen als Verbundverglasung (d. h. als Laminat aus mindestens zwei Glasscheiben und mindestens einer PVB-Folie) oder als Isolier-verglasung mit einem Gaszwischenraum auszuführen. Selbstverständlich ist auch die Kombination dieser Maßnahmen möglich.The transparent front cover is usually made of glass or transparent plastics such as ETFE or PMMA. The rear cover of the photovoltaic module can be made of glass, plastic or metal or their composites, wherein at least one of the carriers can be transparent. It is also possible to use one or both covers as a composite glazing (i.e., as a laminate of at least two glass sheets and at least one PVB sheet) or as insulating glazing with a gas gap. Of course, the combination of these measures is possible.
[0045] Die in den Modulen eingesetzten photosensitiven Halbleiterschichten müssen keine besonderen Eigenschaften besitzen. Es können mono-, polykristalline, organische oder amorphe Systeme eingesetzt werden.The photosensitive semiconductor layers used in the modules need not have any special properties. Mono-, polycrystalline, organic or amorphous systems can be used.
[0046] Erfindungsgemäß hergestellte Photovoltaikmodule können in Solarkraftwerken, als Fassadenbauteil, Dachflächen, Wintergartenabdeckung, Schallschutzwand, Balkon- oder Brüstungselement oder als Bestandteil von Fensterflächen verwendet werden.Photovoltaic modules produced according to the invention can be used in solar power plants, as a facade component, roof surfaces, conservatory cover, soundproof wall, balcony or parapet element or as part of window surfaces.
BeispieleExamples
VergleichsbeispielComparative example
[0047] Ein Dünnschichtmodul der Größe L 130cm x B 110cm mit einer Glasdicke 3,2mm mit innenliegenden Längs- und Querkontakten und einer Kontaktbohrung auf dem Rückglas wird in einem Vakuumlaminator laminiert. Als Folie wird das Produkt TROSIFOL R40 in einer Dicke von 0,76 mm gewählt. Die Folie wurde mindestens 12 Stunden bei 23°C und einer relativen Luftfeuchtigkeit von 25% konditioniert. Der Randüberstand beträgt dabei 5mm umlaufend. Die Heizplatte hat eine Temperatur von 150°C, das Vakuum beträgt weniger als 100 Pa. Das Modul wird zuerst 11 min evakuiert, dann wird die obere Prozesskammer über einen Zeitraum von 5 min auf 600 mbar belüftet. Anschließend wird das Modul für 12 min unter diesen Prozessbedingungen gehalten. [0048] Man erhält ein blasenfreies fertig verbundenes Laminat mit leichtemA thin-film module of size L 130 cm × W 110 cm with a glass thickness of 3.2 mm with internal longitudinal and transverse contacts and a contact hole on the back glass is laminated in a vacuum laminator. The film used is the product TROSIFOL R40 in a thickness of 0.76 mm. The film was conditioned for at least 12 hours at 23 ° C and a relative humidity of 25%. The edge overhang is 5mm circumferential. The heating plate has a temperature of 150 ° C, the vacuum is less than 100 Pa. The module is first evacuated for 11 min, then the upper process chamber is over Ventilated period from 5 min to 600 mbar. The module is then held under these process conditions for 12 minutes. This gives a bubble-free ready-connected laminate with light
Weichmacherbelag auf der Oberfläche. Eine gaschromatographischeSoftener coating on the surface. A gas chromatographic
Bestimmung des Weichmachergehaltes der Folie am überstehenden Rand ergab einen Weichmacherverlust von über 3 Gew.%. Erfindungsgemäßes Beispiel [0049] Ein identisches Dünnschichtmodul wurde unter gleichenDetermination of the plasticizer content of the film at the protruding edge resulted in a plasticizer loss of more than 3% by weight. Inventive Example An identical thin film module was made equal
Prozessbedingungen wie im Vergleichsbeispiel laminiert, nur wurde dasProcess conditions as in Comparative Example laminated, only was the
Vakuum auf 3000 Pa eingestellt. [0050] Man erhält ein blasenfreies Laminat ohne sichtbaren Belag vonVacuum set to 3000 Pa. A bubble-free laminate without visible coating of
Weichmacher auf der Glasoberfläche. Eine gaschromatographischePlasticizer on the glass surface. A gas chromatographic
Bestimmung des Weichmachergehaltes der Folie am überstehenden Rand ergab einen Weichmacherverlust von unter 1 Gew.%. Determination of the plasticizer content of the film at the protruding edge resulted in a plasticizer loss of less than 1% by weight.

Claims

Ansprüche claims
1. Verfahren zur Herstellung von Photovoltaikmodulen, umfassend ein Laminat aus a) einer transparenten Frontabdeckung b) einer oder mehreren photosensitiven Halbleiterschichten c) mindestens einer weichmacherhaltigen, auf Polyvinylacetal basierenden Folie und d) einer rückwärtigen Abdeckung dadurch gekennzeichnet, dass ein aus den Schichten a) bis d) bestehender Schichtkörper in einer Prozesskammer bei einer Temperatur von 120 - 190 °C und einem Gasdruck von 200 bis 5*104 Pa zu einem Laminat verklebt wird.1. A method of producing photovoltaic modules, comprising a laminate of a) a transparent front cover b) one or more photosensitive semiconductor layers c) at least one plasticizer-containing polyvinyl acetal-based film and d) a rear cover characterized in that one of the layers a) to d) existing laminate is bonded in a process chamber at a temperature of 120-190 ° C and a gas pressure of 200 to 5 * 10 4 Pa to form a laminate.
2. Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass das Laminat mit einer Flächenbelastung von 1*104 Pa bis 12*105 Pa verpresst wird.2. The method according to claim 1, characterized in that the laminate is pressed with a surface load of 1 * 10 4 Pa to 12 * 10 5 Pa.
3. Verfahren nach Anspruch 1 oder 2 dadurch gekennzeichnet, dass die weichmacherhaltigen, auf Polyvinylacetal basierenden Folien c) einen Weichmachergehalt von maximal 40 Gew.% aufweisen.3. The method according to claim 1 or 2, characterized in that the plasticizer-containing, polyvinyl acetal-based films c) have a plasticizer content of not more than 40 wt.%.
4. Verfahren nach einem der Ansprüche 1 bis 3 dadurch gekennzeichnet, dass das Polyvinylacetal einen Polyvinylacetatgehalt von weniger als 3 Gew.% aufweist.4. The method according to any one of claims 1 to 3, characterized in that the polyvinyl acetal has a polyvinyl acetate content of less than 3 wt.%.
5. Verfahren nach einem der Ansprüche 1 bis 4 dadurch gekennzeichnet, dass das Polyvinylacetal einen Polyvinylalkoholanteil von weniger als 22 Gew.% aufweist.5. The method according to any one of claims 1 to 4, characterized in that the polyvinyl acetal has a polyvinyl alcohol content of less than 22 wt.%.
6. Verfahren nach einem der Ansprüche 1 bis 5 dadurch gekennzeichnet, dass die weichmacherhaltigen auf Polyvinylacetal basierenden Folien c) einen ein- oder beidseitigen Rauhigkeitswert Rz zwischen 10 μm und 180 μm aufweisen.6. The method according to any one of claims 1 to 5, characterized in that the plasticizer-containing polyvinyl acetal based films c) have a one- or two-sided roughness value Rz between 10 microns and 180 microns.
7. Verfahren nach einem der Ansprüche 1 bis 6 dadurch gekennzeichnet, dass eine oder mehrere photosensitive Halbleiterschichten b) zwischen mindestens zwei weichmacherhaltige, auf Polyvinylacetal basierende Folien c) eingebettet und mit der transparenten Frontabdeckung a) und der rückwärtigen Abdeckung d) verklebt werden.7. The method according to any one of claims 1 to 6, characterized in that one or more photosensitive semiconductor layers b) embedded between at least two plasticizer-containing polyvinyl acetal based films c) and bonded to the transparent front cover a) and the rear cover d).
8. Verfahren nach einem der Ansprüche 1 bis 6 dadurch gekennzeichnet, dass eine oder mehrere photosensitive Halbleiterschichten b) auf einen Träger aufgebracht und dieser zwischen mindestens zwei weichmacherhaltige, auf Polyvinylacetal basierende Folien c) eingebettet und mit der transparenten Frontabdeckung a) und der rückwärtigen Abdeckung d) verklebt wird.8. The method according to any one of claims 1 to 6, characterized in that one or more photosensitive semiconductor layers b) applied to a carrier and this between at least two plasticizer-containing, on Polyvinyl acetal based films c) embedded and bonded to the transparent front cover a) and the rear cover d).
9. Verfahren nach einem der Ansprüche 1 bis 6 dadurch gekennzeichnet, dass eine oder mehrere photosensitive Halbleiterschichten b) auf eine transparente Frontabdeckung a) oder eine rückwärtige Abdeckung d) aufgebracht sind und durch mindestens eine weichmacherhaltige, auf Polyvinylacetal basierende Folie c) miteinander verklebt sind.9. The method according to any one of claims 1 to 6, characterized in that one or more photosensitive semiconductor layers b) are applied to a transparent front cover a) or a rear cover d) and are glued together by at least one plasticizer-containing, based on polyvinyl acetal film c) ,
10. Verwendung von Photovoltaikmodulen, hergestellt nach einem Verfahren gemäß den Ansprüchen 1 bis 9 in Solarkraftwerken, als Fassadenbauteil, Dachflächen, Wintergartenabdeckung, Schallschutzwand, Balkon- oder Brüstungselement oder als Bestandteil von Fensterflächen . 10. Use of photovoltaic modules, produced by a method according to claims 1 to 9 in solar power plants, as a facade component, roof surfaces, conservatory cover, soundproof wall, balcony or parapet or as part of windows.
PCT/EP2009/055581 2008-05-09 2009-05-08 Method for producing photovoltaic modules in a vacuum laminator having a reduced process vacuum WO2009135929A2 (en)

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