WO2011004872A1 - 太陽電池モジュール用保護シート - Google Patents
太陽電池モジュール用保護シート Download PDFInfo
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- WO2011004872A1 WO2011004872A1 PCT/JP2010/061638 JP2010061638W WO2011004872A1 WO 2011004872 A1 WO2011004872 A1 WO 2011004872A1 JP 2010061638 W JP2010061638 W JP 2010061638W WO 2011004872 A1 WO2011004872 A1 WO 2011004872A1
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- WIPO (PCT)
- Prior art keywords
- solar cell
- vapor deposition
- cell module
- layer
- sheet
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- 238000012360 testing method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- HHPPHUYKUOAWJV-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCC1CO1 HHPPHUYKUOAWJV-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- H01L31/049—Protective back sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/02—Polysilicates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a protective sheet for a solar cell module used as a surface protective sheet or a back surface protective sheet of a solar cell module.
- FIG. 3 is a schematic cross-sectional view showing an example of a solar cell module.
- This solar cell module 100 includes a solar cell 101 made of crystalline silicon, a sealing material 102 made of an electrical insulator that seals the solar cell 101, and a surface protection sheet (on the surface of the sealing material 102). Front sheet) 103 and a back surface protection sheet (back sheet) 104 laminated on the back surface of sealing material 102 are schematically configured.
- the solar battery cell 101 and the sealing material 102 are provided with wind, rain, moisture, dust, mechanical While protecting from an impact etc., it is necessary to keep the inside of the solar cell module 100 sealed from the outside air. Therefore, the front sheet 103 and the back sheet 104 are required to have excellent weather resistance, and in particular, low water vapor permeability is required.
- a water-impermeable sheet As a protective sheet for a solar cell module having a low water vapor permeability, a water-impermeable sheet is disclosed in which a base material sheet made of a resin such as polyethylene terephthalate is provided with a vapor-deposited layer that does not substantially allow water to permeate. (For example, refer to Patent Document 1).
- the present invention has been made in view of the above circumstances, and improves the adhesion of the fluororesin layer to the inorganic oxide deposition layer, has high moisture resistance, and is used as a front sheet or a back sheet of a solar cell module.
- An object of the present invention is to provide a solar cell module protective sheet that can be used stably for a long period of time.
- the protective sheet for a solar cell module of the present invention includes a resin sheet, a vapor deposition layer made of an inorganic oxide provided on at least one surface thereof, and a fluororesin layer containing a silane coupling agent laminated on the vapor deposition layer
- the silane coupling agent is preferably alkoxysilane.
- a fluorine containing a resin sheet, a vapor deposition layer made of an inorganic oxide provided on at least one surface thereof, and a silane coupling agent laminated on the vapor deposition layer Since it has a resin layer, the adhesiveness of the fluororesin layer with respect to a vapor deposition layer improves, and it can suppress that a fluororesin layer peels from a vapor deposition layer. Therefore, the state in which the fluororesin layer is laminated on the resin sheet can be maintained, and the moisture and heat resistance is improved. Therefore, the stable long-term use of a photovoltaic cell is attained.
- FIG. 1 is a schematic cross-sectional view showing a first embodiment of a protective sheet for a solar cell module of the present invention.
- a vapor deposition layer 12 made of an inorganic oxide is provided on one surface 11a of a resin sheet 11, and the opposite surface of the vapor deposition layer 12 is in contact with the resin sheet 11.
- a fluororesin layer 13 containing a silane coupling agent is laminated on a side surface (hereinafter referred to as “one surface”) 12a.
- the silane coupling agent contained in the fluororesin layer 13 has an affinity for the vapor deposition layer 12. Therefore, it becomes difficult for the fluororesin layer 13 to be detached from the resin sheet 11.
- the resin sheet 11 what is generally used as a resin sheet in the protection sheet for solar cell modules is selected.
- the resin sheet 11 include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyamide (nylon 6, nylon 66), polyacrylonitrile, polyvinyl chloride, polyethylene terephthalate (PET), polybutylene terephthalate ( PBT), polyethylene naphthalate (PEN), polyoxymethylene, polycarbonate, polyphenylene oxide, polyester urethane, poly m-phenylene isophthalamide, and poly p-phenylene terephthalamide.
- the resin sheet includes known additives such as antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, light stabilizers, heat stabilizers, lubricants, crosslinking agents, and blocking agents.
- antistatic agents such as UV absorbers, plasticizers, lubricants, fillers, colorants, light stabilizers, heat stabilizers, lubricants, crosslinking agents, and blocking agents.
- An inhibitor, an antioxidant and the like can be contained.
- the thickness of the resin sheet 11 is appropriately set based on the electrical insulation required for the solar cell module, and is usually preferably in the range of 10 ⁇ m to 300 ⁇ m. More specifically, when the resin sheet 11 is a polyester-based sheet, the thickness is preferably in the range of 20 ⁇ m to 300 ⁇ m, and in the range of 30 ⁇ m to 200 ⁇ m, from the viewpoint of light weight and electrical insulation. More preferably, it is most preferably in the range of 50 ⁇ m to 150 ⁇ m.
- the resin sheet is preferably subjected to a surface treatment such as a frame treatment, a corona discharge treatment, a plasma discharge treatment, or an anchor coat treatment in order to improve adhesion with the vapor deposition layer.
- Anchor coating agents include solvent-based or water-based polyester resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, modified styrene resins, modified silicon resins, isocyanate resins, and epoxy.
- Resins, melamine resins, oxazoline group-containing resins, carbodiimide group-containing resins, aziridine resins, alkyl titanates, and the like can be used alone or in combination of two or more. Among these, a combination of a resin having a reactive functional group and a resin having a crosslinking group is preferable in terms of durability and adhesion.
- the anchor coating agent contains a known additive such as an antistatic agent, a light shielding agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a lubricant, an antiblocking agent, an antioxidant, and the like. Can do.
- the thickness of the anchor coat layer is preferably 0.005 to 5 ⁇ m, more preferably 0.01 to 1 ⁇ m. If the thickness is 5 ⁇ m or less, the slipping property is good, and there is almost no peeling from the base film due to the internal stress of the anchor coat layer itself, and if the thickness is 0.005 ⁇ m or more, the thickness is uniform. It is possible to keep the thickness.
- paintability of an anchor coating agent to a base film, and adhesiveness you may perform surface treatments, such as normal chemical treatment and electrical discharge treatment, before application
- the vapor deposition layer 12 will not be specifically limited if it is formed by vapor-depositing an inorganic oxide on the one surface 11a of the resin sheet 11.
- FIG. Examples of the vapor deposition method for forming the vapor deposition layer 12 include chemical vapor deposition methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition, or vacuum vapor deposition, sputtering, and ion plating.
- a physical vapor phase method such as a ting method is used.
- the vacuum deposition method is preferable in consideration of operability and controllability of the layer thickness.
- the vapor deposition layer 12 functions as a moisture-proof layer having a water vapor barrier property. Moreover, the vapor deposition layer 12 can improve the weather resistance of a solar cell module by applying to a solar cell module.
- Examples of the inorganic oxide constituting the vapor deposition layer 12 include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium rim (Na), and boron. At least one of oxides such as (B), titanium (Ti), lead (Pb), zirconium (Zr) and yttrium (Y) is used. Among these, at least one of silicon oxide, aluminum oxide, titanium oxide, and a mixture thereof is preferable. More preferred is silicon oxide and / or aluminum oxide. In particular, silicon oxide is preferable in that high gas barrier properties can be stably maintained.
- the vapor deposition layer 12 may further contain a material other than the inorganic oxide described above.
- x of the elemental composition SiOx of the silicon oxide vapor deposition layer is 1.2 or more and 1.9 or less (1.2 ⁇ x ⁇ 1.9) is preferred. More preferably, it is 1.3 or more and 1.8 or less.
- the degree of oxidation x is small, the fluororesin adhesion is good, but the vapor deposition layer is strongly colored.
- the oxidation degree is 1.2 ⁇ x ⁇ 1.9, more preferably 1.3 ⁇ x ⁇ 1.8, the surface of the vapor deposition layer is easily wetted from the viewpoint of surface tension, and the surface of the vapor deposition layer and the silane coupling agent This is preferable because the affinity of the resin is improved and the adhesion to the fluororesin layer is further improved.
- Elemental composition can be measured using X-ray photoelectron spectroscopy (ESCA) (XPS) analysis.
- the vapor deposition layer 12 may be made of one kind of inorganic oxide or may be made of plural kinds of inorganic oxides.
- the vapor deposition layer 12 may be a vapor deposition layer having a laminated structure in which layers composed of the respective inorganic oxides are sequentially deposited, or a vapor deposition layer in which a plurality of types of inorganic oxides are vapor deposited simultaneously. It may be.
- the thickness of the vapor deposition layer 12 is appropriately set in consideration of the water vapor barrier property, and is changed depending on the type of inorganic oxide used, vapor deposition density, and the like.
- the thickness of the vapor deposition layer 12 is preferably 5 nm to 200 nm, more preferably 10 to 100 nm.
- the fluororesin layer 13 is formed by directly applying a paint containing a fluorine-containing resin to one surface 12a of the vapor deposition layer 12.
- the fluororesin layer 13 can be formed by applying a coating film having a desired thickness.
- the fluororesin layer 13 becomes a moisture-proof layer having a water vapor barrier property when a paint containing a fluorine-containing resin and a silane coupling agent is cured. Moreover, the fluorine resin layer 13 can improve the weather resistance and chemical resistance of a solar cell module by applying to a solar cell module.
- the paint containing a fluorine-containing resin and a silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention and forms the fluorine resin layer 13 after drying and curing, and is dissolved in a solvent or dispersed in water. There is no particular limitation as long as it can be applied to one surface 12a of the vapor deposition layer 12.
- the fluorine-containing resin contained in the paint is not particularly limited as long as it does not impair the effects of the present invention and contains a fluorine, but can be cross-linked by dissolving in a solvent (organic solvent or water) of the paint. Used.
- a fluorine-containing resin contained in the paint it is preferable to use a fluoroolefin resin having a curable functional group.
- the curable functional group include a hydroxyl group, a carboxyl group, an amino group, and a glycidyl group, and a hydroxyl group is preferable from the viewpoint of good curability.
- a fluoroolefin resin having a hydroxyl group can be obtained by copolymerizing a monomer containing a hydroxyl group.
- a monomer containing a hydroxyl group hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable.
- copolymerizable monomers that form fluoroolefin resins include vinyl acetate, vinyl propionate, butyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, Vinyl esters of carboxylic acids such as vinyl cyclohexyl carboxylate and vinyl benzoate, and alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether are used.
- fluoroolefin resin “LUMIFLON (trade name, manufactured by Asahi Glass Co., Ltd.)”, “CEFRAL COAT (trade name, manufactured by Central Glass Co., Ltd.)”, “FLUONATE (trade name, manufactured by DIC Corporation)”, etc.
- CTFE chlorotrifluoroethylene
- TFE tetrafluoroethylene
- “LUMIFLON” is an amorphous resin containing CTFE, several kinds of specific alkyl vinyl ethers and hydroxyalkyl vinyl ethers as main structural units.
- a resin having a monomer unit of hydroxyalkyl vinyl ether such as “LUMIFLON” is preferable because it is excellent in solvent solubility, cross-linking reactivity, substrate adhesion, pigment dispersibility, hardness and flexibility.
- "ZEFFLE” is a copolymer of TFE and organic solvent-soluble hydrocarbon olefins, especially those containing hydrocarbon olefins with highly reactive hydroxyl groups, solvent-soluble, cross-linking reactivity, adhesion to substrates This is preferable because of its excellent properties and pigment dispersibility.
- the coating material may contain a crosslinking agent, a catalyst and a solvent in addition to the above-described fluorine-containing resin, and may further contain an inorganic compound such as a pigment and a filler if necessary.
- the solvent contained in the paint is not particularly limited as long as it does not impair the effects of the present invention.
- MEK methyl ethyl ketone
- MIBK methyl isobutyl ketone
- MIBK methyl isobutyl ketone
- toluene xylene
- methanol isopropanol
- ethanol isopropanol
- ethanol A solvent containing any one or more organic solvents selected from the group consisting of heptane, ethyl acetate, isopropyl acetate, n-butyl acetate and n-butyl alcohol is preferably used.
- the solvent is any selected from xylene, cyclohexanone, or MEK.
- a solvent containing one or more organic solvents is preferred.
- the pigment and filler contained in the paint are not particularly limited as long as the effects of the present invention are not impaired.
- titanium dioxide, carbon black, perylene pigment, mica, polyamide powder, boron nitride, zinc oxide, aluminum oxide Silica or the like is used.
- Ti-Pure R105 trade name, EI du Pont de Nemours and Company
- CAB-O-SIL TS-720 trade name, manufactured by Cabot
- is a hydrophobic silica in which the hydroxyl group of the silica surface is modified by the surface treatment of dimethyl silicone is preferably used.
- the protective sheet for the solar cell module of the present invention needs to be transparent, particularly excellent in light transmittance in the visible light region, and has a low content of pigments and fillers. Is preferred.
- the backsheet it is not necessary to be transparent, and it is preferable to color it white with a white pigment such as titanium oxide in order to provide reflectivity and improve power generation efficiency.
- the coating film forming the fluororesin layer 13 is preferably cured with a crosslinking agent in order to improve weather resistance and scratch resistance.
- the crosslinking agent is not particularly limited as long as the effects of the present invention are not impaired, and metal chelates, isocyanates, or melamines are preferably used. Assuming that the solar cell module protective sheet 10 is used outdoors for a long period of time, aliphatic isocyanates are preferred as the crosslinking agent from the viewpoint of weather resistance.
- the composition of the coating is not particularly limited as long as the effects of the present invention are not impaired, and for example, it is prepared by mixing a fluoroolefin resin, a pigment, a crosslinking agent, a catalyst, a silane coupling agent and a solvent.
- the composition ratio of the composition is preferably such that the solid content of the fluoroolefin resin, pigment, crosslinking agent, catalyst, silane coupling agent, etc. is 80 to 20% by mass, assuming that the entire coating is 100% by mass. More preferable is 30% by mass.
- the composition ratio of each component in the solid content is preferably 40 to 95% by mass, more preferably 45 to 90% by mass, and more preferably 45% to 90% by mass when the total solid content is 100% by mass.
- the content of the coupling agent is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass.
- the content of the pigment is preferably 20 to 50% by mass, more preferably 30 to 40% by mass when the total solid content is 100% by mass.
- the catalyst for example, dibutyl dilaurate tin and dioctyl dilaurate tin are used, and this catalyst is used for promoting the crosslinking between “LUMIFLON” and isocyanate in a solvent.
- the coating material As a method of applying the coating material to the one surface 12a of the vapor deposition layer 12, a known method is used.
- the coating may be applied with a bar coater (rod coater) so as to have a desired thickness.
- the drying temperature of the coating applied to the one surface 12a of the vapor deposition layer 12 may be any temperature that does not impair the effects of the present invention. From the viewpoint of reducing the thermal deformation of the resin sheet 11, it is in the range of 50 to 130 ° C. Preferably there is.
- the thickness of the fluororesin layer 13 formed by curing the coating is not particularly limited as long as the effects of the present invention are not impaired. However, from the viewpoint of weather resistance and light weight, 5 ⁇ m to 50 ⁇ m is preferable, and 8 ⁇ m to 40 ⁇ m is more preferable. 10 ⁇ m to 30 ⁇ m is most preferable.
- alkoxysilane can be selected.
- An alkoxysilane is a silane compound in which a compound in which oxygen is bonded to an alkyl group (—OC n H 2n + 1 ) is a silicon side chain.
- alkoxysilane all the side chains may be the above compounds, some of the side chains may be the above compounds, and other side chains may be other compounds.
- a silane coupling agent is a compound in which a hydrogen atom bonded to silane is substituted with another atom or atomic group, and has silicon as a nucleus.
- the fluororesin layer 13 contains silicon and has an affinity for the inorganic oxide of the vapor deposition layer 12. In particular, when the vapor deposition layer 12 contains silicon oxide, the fluororesin layer 13 is a vapor deposition layer. 12 shows a good affinity.
- alkoxysilane examples include 3-glycidyloxypropyltrimethoxysilane represented by the following chemical formula (1), 3-acetoxypropyltrimethoxysilane represented by the following chemical formula (2), and phenyl represented by the following chemical formula (3). Trimethoxysilane and tetraethoxysilane represented by the following chemical formula (4) are preferable, and 3-glycidyloxypropyltrimethoxysilane is particularly preferable among these.
- 3-glycidyloxypropyltrimethoxysilane those having an epoxy group such as 3-glycidylpropylmethyldiethoxysilane, 3-glycidylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Is particularly preferred.
- These alkoxysilanes may be used alone or in combination of two or more.
- the fluororesin layer 13 contains a silane coupling agent, the fluororesin layer 13 can be prevented from peeling from the vapor deposition layer 12. Therefore, the state in which the fluororesin layer 13 is laminated on the resin sheet 11 can be maintained, good water repellency due to the fluororesin layer 13 is effectively exhibited, and the moisture and heat resistance is increased. Therefore, the stable long-term use of a photovoltaic cell is attained.
- the protective sheet 10 for solar cell modules in which the vapor deposition layer 12 was provided in the one surface 11a of the resin sheet 11 was illustrated, the protective sheet for solar cell modules of this invention is not limited to this.
- vapor deposition layers may be provided on both surfaces (one surface and the other surface) of the resin sheet.
- a fluororesin layer containing a silane coupling agent is laminated on one side of the vapor deposition layer (the side opposite to the side in contact with the resin sheet) Is done.
- fluorine containing a silane coupling agent on one surface of the vapor deposition layer (the surface opposite to the surface in contact with the resin sheet) A resin layer is laminated.
- FIG. 2 is a schematic cross-sectional view showing a second embodiment of the solar cell module protective sheet of the present invention.
- the solar cell module protective sheet 20 of this embodiment is applied to the front sheet and back sheet of the solar cell module, as in the first embodiment.
- the heat bondable layer 14 is provided in the protection sheet 20 for solar cell modules.
- the heat-adhesive layer 14 is disposed on a surface (hereinafter referred to as “the other surface”) 11 b opposite to the surface on which the fluororesin layer 13 of the resin sheet 11 is laminated via the adhesive layer 15. Are stacked.
- the thermal adhesiveness in the thermal adhesive layer 14 is a characteristic that expresses adhesiveness by heat treatment.
- the resin constituting the thermal adhesive layer 14 is not particularly limited as long as it is a resin having thermal adhesiveness.
- the temperature of the heat treatment is preferably in the range of 50 to 200 ° C.
- the resin constituting the thermal adhesive layer 14 for example, a resin composed of a polymer mainly composed of ethylene vinyl acetate (EVA) or polyolefin is preferable, and a resin composed of a polymer mainly composed of EVA is more preferable. .
- EVA ethylene vinyl acetate
- a sealing resin made of EVA is often used as a sealing material constituting a solar cell module.
- the thermal adhesive layer 14 is a resin made of a polymer mainly composed of EVA, sealing is performed. The compatibility and adhesion between the material and the thermal adhesive layer 14 can be improved.
- the thickness of the heat-adhesive layer 14 is not particularly limited as long as the effect of the present invention is not impaired, and is appropriately adjusted according to the type of the heat-adhesive layer 14.
- the thickness of the thermal adhesive layer 14 is preferably in the range of 1 ⁇ m to 200 ⁇ m, for example. More specifically, when the heat-adhesive layer 14 is EVA, it is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably in the range of 50 ⁇ m to 150 ⁇ m, from the viewpoint of light weight and electrical insulation. The most preferable range is 80 ⁇ m to 120 ⁇ m.
- the adhesive layer 15 is composed of an adhesive having adhesiveness to the resin sheet 11 and the thermal adhesive layer 14.
- the adhesive constituting the adhesive layer 15 is not particularly limited as long as it does not impair the effects of the present invention, and acrylic adhesive, urethane adhesive, epoxy adhesive, ester adhesive, and the like are used. . These adhesives may be used individually by 1 type, and may be used in combination of 2 or more type.
- the thermal adhesive layer 14 is provided in addition to the solar cell module protective sheet 10 of the first embodiment.
- the solar cell module protective sheet 20 can be easily thermally bonded.
- the solar cell module protective sheet 20 in which the thermal adhesive layer 14 is provided on the other surface 11b of the resin sheet 11 with the adhesive layer 15 interposed therebetween is exemplified, but the solar cell of the present invention.
- the protective sheet for modules is not limited to this.
- the thermal adhesive layer may be directly laminated on the other surface 11 b of the resin sheet 11.
- Example 1 [Formation of vapor deposition layer]
- a PET film having a thickness of 12 ⁇ m was used, and a metal oxide silicon dioxide (SiO 2 ) film was formed on one surface of the PET film by a vapor deposition method so as to have a thickness of 50 nm. A layer was formed.
- the vapor deposition of silicon dioxide was performed under the following conditions.
- a paint is prepared according to the blending ratio shown in Tables 1 and 2, and a paint containing a fluorine-containing resin is applied to one side of the vapor deposition layer using a bar coater so that the thickness after drying is 13 ⁇ m.
- a fluororesin layer was formed by drying at 1 ° C. for 1 minute to prepare a protective sheet 10 for a solar cell module (Experimental Examples 1 to 25).
- the upper part in Table 1 and Table 2 shows the composition of the coating material containing the fluororesin layer, and all the numerical values represent mass%.
- LUMIFLON LF200 (trade name, manufactured by Asahi Glass Co., Ltd.) used for forming the fluororesin layer is a CTFE-based copolymer
- Sumijour N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd.) is an isocyanate-based crosslinking agent (curing agent).
- Ti-Pure R105 (trade name, manufactured by EI du Pont de Nemours and Company) is titanium oxide
- CAB-O-SIL TS-720 (trade name, manufactured by Cabot Corporation) is a hydrophobic silica. It is.
- Example 2 As the resin sheet, using a PEN film having a thickness of 12 [mu] m, and supplies the film in a vacuum deposition apparatus under a vacuum of 1x10 -4 Torr, the electron beam heating method of 10 kw, 100 nm and 99.9% pure silicon monoxide / Heat deposition was performed at a speed of s to obtain a silicon oxide deposition layer.
- a bag was prepared in which about 20 g of anhydrous calcium chloride was put as a hygroscopic agent and the four sides were sealed. placed in a humidity of 90% of the constant temperature and humidity apparatus, up to 30 days as a measure of the mass increase rate becomes substantially constant, the mass was measured (0.1 mg unit) was calculated water vapor transmission rate (g / m 2 / 24h) .
- the value of the water vapor transmission rate indicates that the protective sheet for solar cell module of the present invention has a very low water vapor transmission rate.
- Example 3 Next, the vapor deposition layer was formed as in Example 2 and the fluororesin layer was formed in the same manner as in Example 1 except that the fluororesin was formed according to the components and blending ratios of the paints shown in Table 3. And the adhesiveness of the fluororesin layer was measured. The results are shown in Table 3.
- Experimental examples 26 to 29 correspond to experimental examples 7 to 10, respectively, and experimental examples 30 to 35 correspond to experimental examples 20 to 25, respectively. From comparison of these corresponding experimental examples, the protective sheet for solar cell module having silicon oxide having an oxidation number lower than 2 as a vapor deposition layer is more fluoropolymer layer 14 than the protective sheet for solar cell module having silicon dioxide as a vapor deposition layer. It was found that the peeling rate was further smaller and the adhesion of the fluororesin layer 14 to the vapor deposition layer 12 was good.
- a fluorine containing a resin sheet, a vapor deposition layer made of an inorganic oxide provided on at least one surface thereof, and a silane coupling agent laminated on the vapor deposition layer Since it has a resin layer, the adhesiveness of the fluororesin layer with respect to a vapor deposition layer improves, and it can suppress that a fluororesin layer peels from a vapor deposition layer. Therefore, the present invention is extremely useful industrially.
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Abstract
Description
図3は、太陽電池モジュールの一例を示す概略断面図である。
この太陽電池モジュール100は、結晶シリコンからなる太陽電池セル101と、太陽電池セル101を封止する電気絶縁体からなる封止材102と、封止材102の表面に積層された表面保護シート(フロントシート)103と、封止材102の裏面に積層された裏面保護シート(バックシート)104とから概略構成されている。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
図1は、本発明の太陽電池モジュール用保護シートの第一の実施形態を示す概略断面図である。
この実施形態の太陽電池モジュール用保護シート10は、樹脂シート11の一方の面11aに無機酸化物からなる蒸着層12が設けられ、この蒸着層12の樹脂シート11と接している面とは反対側の面(以下、「一方の面」と言う。)12a上に、シランカップリング剤を含有したフッ素樹脂層13が積層されている。
また、上記樹脂シートは、公知の添加剤、例えば帯電防止剤、光遮断剤、紫外線吸収剤、可塑剤、滑剤、フィラー、着色剤、光安定剤、熱安定剤、潤滑剤、架橋剤、ブロッキング防止剤、酸化防止剤等を含有することができる。
なお、上記樹脂シートには、蒸着層との密着性向上のため、フレーム処理、コロナ放電処理、プラズマ放電処理、アンカーコート処理などの表面処理を施すことが好ましい。
アンカーコート剤としては、溶剤性又は水性のポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂、ビニルアルコール系樹脂、エチレンビニルアルコール系樹脂、ビニル変性樹脂、変性スチレン樹脂、変性シリコン樹脂、イソシアネート樹脂、エポキシ樹脂、メラミン樹脂、オキサゾリン基含有樹脂、カルボジイミド基含有樹脂、アジリジン系樹脂、及びアルキルチタネート等を単独、あるいは2種以上組み合わせて使用することができる。中でも、反応性官能基を持つ樹脂と架橋基を持つ樹脂との組み合わせが耐久性、密着性の点で好ましい。
また、上記アンカーコート剤は、公知の添加剤、例えば、帯電防止剤、光線遮蔽剤、紫外線吸収剤、光安定剤、熱安定剤、潤滑剤、ブロッキング防止剤、酸化防止剤等を含有することができる。
アンカーコート層の厚さは0.005~5μm、更に0.01~1μmであることが好ましい。5μm以下の厚さであれば、滑り性が良好であり、アンカーコート層自体の内部応力による基材フィルムからの剥離も殆どなく、また、0.005μm以上の厚さであれば、均一な厚さを保つことができ好ましい。
また、基材フィルムへのアンカーコート剤の塗布性、接着性を改良するため、アンカーコート剤の塗布前にフィルムに通常の化学処理、放電処理などの表面処理を施してもよい。
蒸着層12を形成する蒸着方法としては、例えば、プラズマ化学気相成長法、熱化学気相成長法、光化学気相成長法などの化学気相法、または、真空蒸着法、スパッタリング法、イオンプレーティング法などの物理気相法が用いられる。これらの方法の中でも、操作性や層厚の制御性を考慮した場合、真空蒸着法が好ましい。
また、本発明の課題の蒸着層とフッ素樹脂層の密着性を改善するためには、酸化ケイ素蒸着層の元素組成SiOxのxが1.2以上かつ1.9以下(1.2≦x≦1.9)であることが好ましい。更に好ましくは1.3以上1.8以下である。酸化度xが小さいとフッ素樹脂密着性は良いが、蒸着層の着色が強くなる。酸化度が1.2≦x≦1.9更に好ましくは1.3≦x≦1.8であると、表面張力の点から蒸着層の表面が濡れ易く、蒸着層表面とシランカップリング剤との親和性が良くなり、フッ素樹脂層との密着性が更に良くなるので好ましい。
元素組成は、X線光電子分光(ESCA)(XPS)分析法を用い、測定することが可能である。
蒸着層12が複数種の無機酸化物からなる場合、各無機酸化物からなる層が順に蒸着された積層構造の蒸着層であってもよく、複数種の無機酸化物が同時に蒸着された蒸着層であってもよい。
塗料に含まれるフッ素含有樹脂としては、硬化性官能基を有するフルオロオレフィン樹脂を用いることが好ましい。
硬化性官能基としては、水酸基、カルボキシル基、アミノ基、グリシジル基などが挙げられ、硬化性が良好である点から水酸基が好ましい。
水酸基を有するフルオロオレフィン樹脂は、水酸基を含有するモノマーを共重合することにより得られる。
水酸基を含有するモノマーとしては、4-ヒドロキシブチルビニルエーテル、2-ヒドロキシエチルビニルエーテルなどのヒドロキシアルキルビニルエーテルが好ましい。
「ZEFFLE」は、TFEと有機溶媒可溶性の炭化水素オレフィンとの共重合体であり、なかでも反応性の高い水酸基を備えた炭化水素オレフィンを含むものが、溶剤可溶性、架橋反応性、基材密着性および顔料分散性に優れるので好ましい。
このような溶媒のなかでも、塗料中の含有成分の溶解性および塗膜中への残留性の低さ(低い沸点温度)の観点から、溶媒としては、キシレン、シクロヘキサノンまたはMEKから選択されるいずれか1種または2種以上の有機溶媒を含む溶媒が好ましい。
なお、本発明の太陽電池モジュール用保護シートは、フロントシートの場合は、透明であること、特に可視光領域の光の透過性に優れることが必要であり、顔料や充填剤の含量の少ないものが好ましい。バックシートの場合は、透明である必要はなく、逆に反射性を持たせ、発電効率を向上させるため、酸化チタンなどの白色顔料で白色に着色するのが好ましい。
架橋剤としては、本発明の効果を損なうものでなければ特に限定されず、金属キレート類、イソシアネート類またはメラミン類が好適に用いられる。太陽電池モジュール用保護シート10を屋外において長期間使用することを想定した場合、耐候性の観点から、架橋剤としては、脂肪族のイソシアネート類が好ましい。
この組成物の組成比は、塗料全体を100質量%としたとき、フルオロオレフィン樹脂、顔料、架橋剤、触媒、シランカップリング剤などの固形分の含有率が80~20質量%が好ましく、70~30質量%がより好ましい。
また、上記の固形分における各成分の組成比は、固形分全体を100質量%としたとき、フルオロオレフィン樹脂の含有率は40~95質量%が好ましく、45~90質量%がより好ましく、シランカップリング剤の含有率は0.1~10質量%が好ましく、0.2~5質量%がより好ましい。また、この組成物が顔料を含む場合、固形分全体を100質量%としたとき、顔料の含有率は20~50質量%が好ましく、30~40質量%がより好ましい。
蒸着層12の一方の面12aに塗布した塗料の乾燥温度は、本発明の効果を損なわない温度であればよく、樹脂シート11の熱変形を低減する観点からは、50~130℃の範囲であることが好ましい。
図2は、本発明の太陽電池モジュール用保護シートの第二の実施形態を示す概略断面図である。
図2において、図1に示した太陽電池モジュール用保護シート10と同じ構成要素には同一の符号を付して説明を省略する。
この実施形態の太陽電池モジュール用保護シート20は、第一の実施形態と同様に、太陽電池モジュールのフロントシート及びバックシートに適用される。
太陽電池モジュール用保護シート20においては、第一の実施形態の太陽電池モジュール用保護シート10の構造に加えて、熱接着性層14が設けられている。
一般に、太陽電池モジュールを構成する封止材としては、EVAからなる封止樹脂が多用されているが、熱接着性層14がEVAを主成分とするポリマーからなる樹脂であることにより、封止材と熱接着性層14との適合性および接着性を向上させることができる。
接着層15を構成する接着剤としては、本発明の効果を損なわないものであれば特に制限されず、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、エステル系接着剤などが用いられる。これらの接着剤は1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
[蒸着層の形成]
樹脂シートとして、厚み12μmのPETフィルムを用い、このPETフィルムの片面に、蒸着法により、金属酸化物の二酸化ケイ素(SiO2)を厚み50nmとなるように成膜して、二酸化ケイ素からなる蒸着層を形成した。
二酸化ケイ素の蒸着は、以下の条件で行った。
プラズマ生成ガス:アルゴン
ターゲット材料:二酸化ケイ素
ガス流量:アルゴン 100scm
電力値:RF 2000W
チャンバー内圧:0.2Pa
表1および表2に示す配合比に従って塗料を作製し、蒸着層の一方の面に、バーコーターを用いて、乾燥後の厚みが13μmとなるようにフッ素含有樹脂を含む塗料を塗布し、130℃にて1分間乾燥することによりフッ素樹脂層を形成し、太陽電池モジュール用保護シート10を作製した(実験例1~25)。
表1および表2における上段部分はフッ素樹脂層を含む塗料の組成を示し、いずれの数値も質量%を表す。
フッ素樹脂層の形成に用いたLUMIFLON LF200(商品名、旭硝子社製)はCTFE系共重合体であり、スミジュールN3300(商品名、住化バイエルウレタン社製)はイソシアネート系の架橋剤(硬化剤)であり、Ti-Pure R105(商品名、E.I.du Pont de Nemours and Company製)は酸化チタンであり、CAB-O-SIL TS-720(商品名、キャボット社製)は疎水性シリカである。
実験例1~25で作製した太陽電池モジュール用保護シートについて、日本工業規格JIS K5600-5-6「塗料一般試験方法-第5部:塗膜の機械的性質-第6節:付着性(クロスカット法)」に準拠して、フッ素樹脂層の密着性を評価した。
フッ素樹脂層の表面(外面)に、1mm間隔で切り込みを入れ、100個(縦10個×横10個)の碁盤目を形成し、その碁盤目にセロハンテープ(商品名:CT-24、ニチバン社製)を貼着した後、セロハンテープを剥離した際、碁盤目において剥離せずに残ったフッ素樹脂層の数を調べた。
また、実験例1~25で作製した太陽電池モジュール用保護シートについて、温度121℃、相対湿度100%、圧力2atmの条件下に24時間放置して環境試験を行った後、同様に密着性試験を行った。
結果を表1および表2に示す。
樹脂シートとして、厚み12μmのPENフィルムを用い、このフィルムを真空蒸着装置に供給し、1x10-4Torrの真空下、10kwの電子ビーム加熱方式により、純度99.9%の一酸化ケイ素を100nm/sの速度で加熱蒸着させて、酸化ケイ素蒸着層を得た。
蒸着層の元素組成は、サーモフィッシャーサイエンティフィック社製XPS分析装置K-Alpha機を用いて分析し、SiOx(x=1.7)であった。
水蒸気透過率は、3x10-2g/m2/24hであった。
[水蒸気透過率の測定方法]
得られた酸化ケイ素蒸着樹脂シートについて、蒸着側に50μm厚の未延伸ポリプロピレンフィルムをドライラミネートにて積層し、JIS Z0222「防湿包装容器の透湿度試験方法」、JIS Z0208「防湿包装材料の透湿度試験方法(カップ法)」の諸条件に順じ、次の手法で評価した。
透湿面積10.0cmx10.0cm角の上記の蒸着樹脂シートのラミネート積層体を2枚用い、吸湿剤として無水塩化カルシウム約20gを入れ四辺を封じた袋を作成し、その袋を温度40℃相対湿度90%の恒温恒湿装置に入れ、質量増加率がほぼ一定になる目安として30日間まで、質量測定(0.1mg単位)し、水蒸気透過率(g/m2/24h)を算出した。
上記の水蒸気透過率の値は、本発明の太陽電池モジュール用保護シートは水蒸気透過率が非常に低いことを示すものである。
次に、蒸着層の形成を実施例2のようにして行い、表3に示す塗料の成分及び配合比にしたがってフッ素樹脂を形成した他は、実施例1と同様にしてフッ素樹脂層の形成、及びフッ素樹脂層の密着性の測定を行った。
その結果を、表3に示す。
Claims (5)
- 樹脂シート、その少なくとも一方の面に設けられた無機酸化物を含む蒸着層、及び前記蒸着層上に積層された、シランカップリング剤を含有するフッ素樹脂層を有する太陽電池モジュール用保護シート。
- 前記シランカップリング剤は、エポキシ基を有するアルコキシシランである請求項1に記載の太陽電池モジュール用保護シート。
- 前記蒸着層が酸化ケイ素及び/又は酸化アルミニウムからなる、請求項1または2に記載の太陽電池モジュール用保護シート。
- 前記酸化ケイ素がSiOx(但し、1.2≦x≦1.9)である、請求項3に記載の太陽電池モジュール用保護シート。
- 前記蒸着層が、SiOx(但し、1.2≦x≦1.9)で表される酸化ケイ素を含む、請求項1または2に記載の太陽電池モジュール用保護シート。
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JP6288902B2 (ja) * | 2011-07-13 | 2018-03-07 | 東洋アルミニウム株式会社 | 反射性を有する太陽電池用裏面保護シート |
JP2015070234A (ja) * | 2013-09-30 | 2015-04-13 | 大日本印刷株式会社 | 太陽電池モジュール用の透明保護シート |
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- 2010-07-08 US US13/376,299 patent/US8586181B2/en not_active Expired - Fee Related
- 2010-07-08 WO PCT/JP2010/061638 patent/WO2011004872A1/ja active Application Filing
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EP2704209A4 (en) * | 2011-04-26 | 2015-03-25 | Youl Chon Chemical Co Ltd | REAR LAYER FOR SOLAR CELL MODULE AND SOLAR CELL MODULE USING THE SAME |
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Also Published As
Publication number | Publication date |
---|---|
CN102473770A (zh) | 2012-05-23 |
TW201110381A (en) | 2011-03-16 |
US20120094131A1 (en) | 2012-04-19 |
US8586181B2 (en) | 2013-11-19 |
JPWO2011004872A1 (ja) | 2012-12-20 |
EP2453485A1 (en) | 2012-05-16 |
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