WO2013051403A1 - 太陽電池モジュール用裏面保護シートおよびそれを用いた太陽電池モジュール - Google Patents
太陽電池モジュール用裏面保護シートおよびそれを用いた太陽電池モジュール Download PDFInfo
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- WO2013051403A1 WO2013051403A1 PCT/JP2012/074199 JP2012074199W WO2013051403A1 WO 2013051403 A1 WO2013051403 A1 WO 2013051403A1 JP 2012074199 W JP2012074199 W JP 2012074199W WO 2013051403 A1 WO2013051403 A1 WO 2013051403A1
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- layer
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- solar cell
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- resin
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- 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 present invention relates to a back surface protection sheet for a solar cell module and a solar cell module using the same, and more specifically, in the manufacturing process of the solar cell module, a problem due to thermal deformation occurs due to excellent heat resistance.
- the present invention relates to a back surface protection sheet for a solar cell module having excellent weather resistance and a solar cell module using the same.
- a solar cell module uses a solar cell element such as a crystalline silicon solar cell element or an amorphous silicon solar cell element, a surface protection sheet, a filler sheet such as ethylene / vinyl acetate copolymer resin, a solar cell element, a filling It is manufactured by a method in which a material sheet and a back surface protective sheet layer are laminated in this order, and are vacuum-sucked and thermocompression bonded and integrated.
- a back surface protection sheet that constitutes a solar cell module a plastic substrate that is lightweight and has excellent electrical characteristics and strength has been generally used.
- Patent Document 1 discloses a back surface protection sheet for a solar cell module in which a specific polyolefin resin multilayer film and a biaxially stretched polyethylene terephthalate film are laminated.
- the back surface protection sheet for a solar cell module using a polyolefin-based resin film has thermal adhesiveness to an ethylene / vinyl acetate copolymer (hereinafter abbreviated as EVA) sheet used as an adhesive resin layer of the solar cell module; Heat resistant and contradictory properties are required to suppress deformation due to heat and pressure during molding into a module.
- Patent Document 2 discloses a method of using a film obtained by adding a UV blocking agent or an antioxidant to a polyethylene resin having a density of 0.940 to 0.970 g / cm 3 .
- the thermal adhesiveness is excellent, the heat resistance is insufficient, and the film deforms due to the influence of heat and pressure in the manufacturing process of the solar cell module, so that the film is partially thinned and the power generation element and wiring are transparent, There is a problem that the withstand voltage characteristic is lowered.
- Patent Document 3 describes a back surface protection sheet for a solar cell module including a sheet obtained by laminating a polypropylene resin and a polyethylene resin for the purpose of improving penetration resistance due to solder protrusions of solar cell electrodes.
- the polypropylene resin and the polyethylene resin are simply laminated by coextrusion, they are easily peeled off at the laminated interface, and thus there are great restrictions when used as a back surface protection sheet for solar cell modules.
- the back surface protection sheet for solar cell modules using a polyolefin resin film is prevented from being deteriorated by yellowing, strength reduction, cracking, etc. due to the influence of ultraviolet rays received from the back surface as a solar cell module. It is also important.
- the subject of this invention is related with the back surface protection sheet for solar cell modules which uses the polyolefin-type resin film, and when carrying out thermocompression bonding in the lamination process in the manufacturing process of a solar cell module, the edge part of a photovoltaic element, or adjacent light
- the back protection sheet for the solar cell module is thinly deformed by the influence of wiring members such as electrodes (interconnectors) for connecting the electromotive elements to each other and current collecting electrodes called bus bars for connecting the cell strings to each other.
- wiring members such as electrodes (interconnectors) for connecting the electromotive elements to each other and current collecting electrodes called bus bars for connecting the cell strings to each other.
- a solar cell module back surface protection sheet that is excellent in heat resistance and concealment property so that the photovoltaic element and the wiring member do not see through, and that is less susceptible to yellowing due to the influence of ultraviolet rays on the back surface. It is to provide a solar cell module used.
- the present invention provides a back surface protection for a solar cell module in which a polyolefin-based resin multilayer film, a plastic film, and an ultraviolet absorbing layer having a three-layer structure of A layer / B layer / C layer are laminated in this order.
- a sheet film wherein the A layer is composed of a resin composition obtained by mixing a polyethylene resin and a polypropylene resin, the B layer is composed of a polypropylene resin composition containing white fine particles, and the C layer is composed of a polypropylene resin composition. It is the back surface protection sheet for solar cell modules characterized by becoming.
- the back surface protection sheet for a solar cell module provides an interconnector and cell strings for connecting end portions of solar power generation elements and adjacent photovoltaic elements to each other when thermocompression bonding is performed in a laminating process.
- the solar cell module's back protective sheet is thinly deformed due to the influence of wiring members such as current collector electrodes called bus bars for connecting to the solar power generation elements, interconnectors, and heat resistance that does not allow the bus bars to penetrate. It can be set as the back surface protection sheet for solar cell modules which is excellent in property, and the extent of deterioration, such as yellowing, is small by the influence of the ultraviolet-ray to a back surface, and a solar cell module using the same.
- the back surface protection sheet for solar cell modules of this invention is excellent in thermal adhesiveness with adhesive resins, such as EVA currently used as a sealing material of a solar cell module, and also excellent in the adhesive force between the interlayers in a sheet
- the back surface protective sheet for a solar cell module of the present invention is a back surface for a solar cell module in which a polyolefin-based resin multilayer film, a plastic film, and an ultraviolet absorbing layer having a three-layer structure of A layer / B layer / C layer are laminated in this order. It is a protective sheet.
- the plastic film used in the present invention may be a single layer or a multilayer film obtained by laminating a plurality of films.
- the plastic film used in the present invention is a polyester film such as polyethylene terephthalate (hereinafter abbreviated as PET) or polyethylene naphthalate (hereinafter abbreviated as PEN), a polyolefin film such as polyethylene or polypropylene, a polystyrene film, a polyamide film, a polychlorinated film.
- a polyethylene terephthalate film is preferably used from the viewpoint of mechanical strength, heat resistance, and economy, and a long-term property maintenance is required. Therefore, a hydrolysis-resistant polyethylene terephthalate film (hereinafter, hydrolysis-resistant PET) is required. More preferably, it is abbreviated as film.
- a PEN film is preferred because high hydrolysis resistance is obtained.
- the plastic film used in the present invention is preferably a fluorine resin film from the viewpoint of weather resistance, and a film obtained by laminating a polyester film and a fluorine resin film can also be preferably used.
- the hydrolysis-resistant PET film preferably used as a plastic film has a tensile elongation after storage for 10 hours under high-pressure steam at 140 ° C. that maintains 60% or more of the initial tensile elongation.
- a hydrolysis-resistant PET film having a tensile elongation of 60% or more of the initial tensile elongation after storage for 10 hours under high-pressure steam at 140 ° C. is used as a plastic film constituting the back protective sheet for solar cell modules.
- the weather resistance of the solar cell module back surface-protected sheet can be greatly improved, which can contribute to the performance guarantee of 10 years or more as a solar cell module, which is preferable.
- the hydrolysis-resistant PET film preferably used as a plastic film has an intrinsic viscosity [ ⁇ ] using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component, more preferably 0.70 to 1.20. This is achieved by a biaxially stretched film of PET of 0.75 to 1.00.
- the intrinsic viscosity [ ⁇ ] is a value measured by dissolving PET with o-chlorophenol as a solvent and a temperature of 25 ° C., and the viscosity is proportional to the degree of polymerization of PET.
- the intrinsic viscosity is 0.70 or more, it is easy to impart hydrolysis resistance and heat resistance, and this is preferable because the hydrolysis resistance of the back surface protection sheet and further the solar cell module is improved. Moreover, when this numerical value is 1.20 or less, melt viscosity becomes low, melt extrusion molding becomes easy, and the film-forming property of the film is improved, which is preferable.
- PET resins may be homo-PET resins or may include a copolymer component.
- the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, adipic acid, and sebacin.
- Dicarboxylic acid components such as acid, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 5-sodium sulfoisophthalic acid can be used.
- an appropriate additive in an amount that does not impair the effects of the present invention, for example, a heat stabilizer, an oxidation stabilizer, an ultraviolet absorber, an anti-glare stabilizer, an organic stabilizer, and the like.
- Lubricants, organic fine particles, fillers, antistatic agents, nucleating agents, dyes, dispersants, coupling agents and the like may be blended.
- the PET resin is dried as necessary, supplied to a known melt extruder, the sheet is extruded from a slit-shaped die, and the PET resin is adhered to a metal drum.
- the film is cooled to a temperature below the glass transition point of to obtain an unstretched film.
- a biaxially stretched film can be obtained from the unstretched film by a known method such as a simultaneous biaxial stretching method or a sequential biaxial stretching method.
- the stretching temperature can be selected arbitrarily from the glass transition point Tg to Tg + 100 ° C.
- the stretching ratio can be selected in the range of 1.6 to 5.0, preferably 1.7 to 4.5 in both the longitudinal direction and the width direction of the film.
- the stretching speed is preferably 1000 to 200000% / min.
- the film is heat-treated after stretching. However, the film can be heat-treated continuously in a heat-treating chamber following the tenter that extends in the width direction, heated in another oven, or heat-treated with a heating roll. As heat treatment conditions, a temperature of 120 to 245 ° C. and a time of 1 to 60 seconds are usually used. Relaxing treatment may be performed for the purpose of improving thermal dimensional stability in the width direction and the longitudinal direction during heat treatment.
- PET film having a tensile elongation of 60% or more after storage at 140 ° C. high pressure steam for 10 hours when the breaking elongation of the film is measured according to JIS C2151 (1996), it is steamed under 140 ° C. high pressure steam conditions.
- PET film has been put on the market that has a 50% elongation reduction time that is more than twice that of non-hydrolytic resistant films.
- “Lumirror” registered by Toray Industries, Inc.) (Trademark) X10S etc. can be preferably used as a plastic film in this invention.
- a PEN film preferably used as a plastic film is a resin polymerized by a known method using 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component. It is a film biaxially stretched by the method.
- the thickness of the hydrolysis-resistant PET film or PEN film is preferably 38 to 300 ⁇ m.
- the thickness of the hydrolysis resistant PET or PEN film is preferably 200 to 250 ⁇ m.
- the fluororesin film preferably used as the plastic film in the present invention is a fluororesin film having a desired thickness by melting the fluororesin, extruding it from the die into a sheet and cooling and solidifying it on a rotary cooling drum. be able to.
- Fluorine-based resins include polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, tetrafluoroethylene / propylene copolymer, tetrafluoroethylene / hexafluoropropylene / propylene copolymer , Ethylene / tetrafluoroethylene copolymer (ETFE), hexafluoropropylene / tetrafluoroethylene copolymer (FEP), or perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, polychlorotrifluoroethylene resin, etc.
- Ethylene / tetrafluoroethylene copolymer Ethylene / tetrafluoroethylene copolymer (ETFE), hexafluoropropylene /
- fluororesins in particular, polyvinyl fluoride, ethylene / tetrafluoroethylene copolymer (ETFE), hexafluoropropylene / tetrafluoroethylene copolymer (FEP), perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer
- ETFE ethylene / tetrafluoroethylene copolymer
- FEP hexafluoropropylene / tetrafluoroethylene copolymer
- FEP hexafluoropropylene / tetrafluoroethylene copolymer
- perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer polychlorotrifluoroethylene polymer is preferable from the viewpoint of melt extrusion moldability for forming a film.
- the adhesion strength after being laminated can be improved by activating the surface of the fluororesin film in the present invention by corona discharge treatment, plasma treatment, flame treatment, chemical treatment or the like.
- plastic film in the present invention a laminate of the above-described polyester film and a fluororesin film can be preferably used.
- the polyolefin resin multilayer film in the present invention has a three-layer structure of A layer / B layer / C layer, and the A layer is made of a resin composition in which a polyethylene resin and a polypropylene resin are mixed.
- the polyethylene resin used in the A layer include high pressure method low density polyethylene, linear low density polyethylene, high density polyethylene, and mixed resins thereof.
- the linear low density polyethylene is a copolymer of ethylene and ⁇ -olefin (hereinafter abbreviated as LLDPE), and is a copolymer of ⁇ -olefin having 4 to 20 carbon atoms, preferably 4 to 8 carbon atoms.
- LLDPE ⁇ -olefin
- These ⁇ -olefins can be used alone or in combination.
- butene-1, hexene-1, octene-1, and the like are preferably used from the viewpoint of polymerization productivity.
- the melting point of the LLDPE of the A layer in the present invention is preferably in the range of 110 to 130 ° C.
- the melting point is 130 ° C. or lower, which is excellent in thermal adhesiveness with EVA, and when it is 110 ° C. or higher, when thermocompression bonding with EVA, the thickness of the sheet is not reduced and the withstand voltage characteristic can be secured, which is preferable. .
- the density of the LLDPE is preferably 0.90 g / cm 3 or more, and if the density is higher than 0.94 g / cm 3 , the dispersibility with the polypropylene-based resin decreases, and a metal roll or a rubber roll In this rubbing, 0.94 g / cm 3 or less is preferable because the resin can easily fall off and cause white powder.
- the content of ⁇ -olefin in LLDPE is preferably 0.5 to 10 mol%, more preferably 2.0 to 8.0 mol%. By adjusting the ⁇ -olefin content to 0.5 to 10 mol%, the density of LLDPE can be in the range of 0.90 g / cm 3 or more and 0.94 g / cm 3 or less.
- the melt index at 190 ° C. (hereinafter abbreviated as MFR) of the LLDPE of the A layer in the present invention is preferably 0.5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes. is there.
- MFR melt index at 190 ° C.
- the MFR is 0.5 g / 10 min or more, uneven lamination with other layers can be made difficult to occur during film formation.
- the MFR is smaller than 10.0 g / 10 min, it becomes difficult to cause poor handling at the time of casting and embrittlement due to an increase in crystallinity.
- the density is preferably in the range of 0.90 to 0.93 g / cm 3 . It is preferable that the density is 0.90 g / cm 3 or more because excellent slipperiness of the film can be ensured and the film handleability during processing is improved. On the other hand, by setting it as 0.93 g / cm ⁇ 3 > or less, the effect which improves the dispersibility of polyethylene-type resin and polypropylene-type resin is easy to be expressed.
- HDPE high density polyethylene
- LLDPE and LDPE low density polyethylene
- the amount of the polypropylene resin is less than 500 parts by weight with respect to 100 parts by weight of the polyethylene resin in the A layer, adhesion with EVA can be secured, and if it exceeds 50 parts by weight, the heat resistance and between the B layers are secured. In order to improve adhesion, it is preferable to mix 50 to 500 parts by weight of a polypropylene resin.
- Heat resistance means that it can withstand a 130 to 170 ° C. laminate performed in a processing step when used as a back surface protection sheet for a solar cell module. More specifically, as described above, in the manufacturing process of the solar cell module incorporating wiring such as a bus bar, the resin constituting the back protective sheet for the solar cell module is deformed by heat and pressure during the lamination. However, it is important to maintain the initial thickness of 80% or more with respect to the total thickness of the A layer / B layer / C layer of the polyolefin resin multilayer film. Since the thickness of the back surface protective sheet directly contributes to the withstand voltage characteristics, the withstand voltage characteristics can be ensured by maintaining the initial thickness. Moreover, it can be set as the solar cell module excellent in design property, without wiring members, such as a bus bar, seeing through.
- polypropylene resins examples include homopolypropylene, ethylene / propylene random copolymers, and ethylene / propylene block copolymers.
- the ethylene content is preferably in the range of 1 to 15 mol%.
- the dispersibility in LLDPE or LDPE, or a mixed resin thereof is improved, and the resin does not easily fall off during rubbing with a metal roll or rubber roll, and generation of white powder can be suppressed.
- Adhesive strength with EVA can be increased.
- the amount is less than 15 mol%, the sheet thickness is not reduced and the concealing property of the bus bar or the like can be improved when thermocompression bonding with EVA.
- the MFR of the polypropylene resin at 230 ° C. is preferably in the range of 1.0 to 15 g / 10 min.
- the MFR is larger than 1.0 g / 10 minutes, the film width is less likely to be lowered (necked down) than the discharge width of the die in the film forming step, and stable production of the film is facilitated.
- MFR is smaller than 15 g / 10min, since the crystallization speed
- the melting point of the polypropylene resin is preferably in the range of 140 ° C. to 170 ° C. from the viewpoints of heat resistance, slipperiness, film handling properties, curl resistance, and thermal adhesion to EVA.
- the melting point 140 ° C. or higher the A layer is excellent in heat resistance, and as a back surface protection sheet for solar cell modules, a decrease in sheet thickness when thermocompression bonding with EVA is suppressed, and withstand voltage characteristics can be secured. preferable.
- the surface average roughness Ra of the layer A is preferably 0.10 to 0.30 ⁇ m because the film handling function during processing is satisfied.
- inorganic or organic particles having an average particle diameter of 1 to 5 ⁇ m are added in an amount of 0.1 to 10% by weight based on the resin component of the layer A for the purpose of improving the handleability and slipperiness of the film. Also good.
- an organic compound lubricant can be added to the A layer resin component.
- the organic compound lubricant include stearamide and calcium stearate.
- the B layer in the present invention is composed of a polypropylene resin composition containing white fine particles.
- the polypropylene-based resin composition referred to here is composed of at least one resin selected from homopolypropylene, a random or block copolymer of ethylene and propylene, or a mixed resin of these resins and polyethylene. From the viewpoint of heat resistance, the polyethylene content is preferably less than 30% by weight of the total resin component.
- the ethylene content is 15 mol% or less.
- the MFR at 230 ° C. of the polypropylene-based resin is preferably in the range of 1.0 to 15 g / 10 minutes from the viewpoint of lamination during coextrusion with the A layer and the C layer described later.
- the MFR is larger than 1.0 g / 10 min, the film melt-extruded from the die in the film forming process is difficult to neck down, and the flatness in the width direction of the film does not deteriorate, so that stable film formation becomes easy. .
- MFR is smaller than 15 g / 10min, the crystallization speed is lowered and the film is difficult to become brittle.
- the white fine particles used in the B layer of the present invention are inorganic fine particles such as calcium carbonate, silica, alumina, magnesium hydroxide, zinc oxide, talc, kaolin clay, titanium oxide, and barium sulfate.
- titanium oxide particles are most preferable, and the rutile type, anatase type, brookite type and the like are known as the crystal type, but the rutile type is preferable from the characteristics such as excellent whiteness, weather resistance and light reflectivity. .
- the titanium oxide particles may be surface-coated with a surface coating agent for the purpose of suppressing the photocatalytic action.
- a surface coating agent for the purpose of suppressing the photocatalytic action.
- the composition of the surface coating agent is not limited, but is preferably an inorganic oxide such as silicon oxide, alumina, or zinc oxide.
- the coating method with the surface coating agent is not particularly limited, and titanium oxide particles whose surface is coated by a known method can be used.
- a light stabilizer such as a hindered amine can be added to the resin.
- the average particle size of the white fine particles used in the present invention is preferably 0.2 to 0.7 ⁇ m, and more preferably 0.25 to 0.35 ⁇ m for the purpose of increasing the reflectance of visible light.
- the addition amount of the white fine particles of the B layer used in the present invention is preferably 5 to 50% by weight with respect to the polypropylene resin, although it depends on the specific gravity. In particular, the range of 10 to 30% by weight with respect to the polypropylene resin is more preferable.
- the addition amount is 5% by weight or more with respect to the polypropylene resin, sufficient whitening and light reflection effect can be obtained, and the wiring material such as a bus bar can be prevented from being transparent and has excellent design.
- the amount is less than 50% by weight, the white fine particles hardly aggregate during film formation and can be stably formed.
- the C layer in the present invention is composed of a polypropylene resin composition, and, like the B layer, one or more resins selected from polypropylene resins such as homopolypropylene, random or block copolymers of ethylene and propylene are used.
- polypropylene resins such as homopolypropylene, random or block copolymers of ethylene and propylene are used.
- the main component contains polypropylene resin in an amount of 70% by weight or more, but it is blocked from the viewpoint of heat resistance, slipperiness, film handling, scratch resistance, and curl resistance.
- a copolymer is most preferred.
- the melting point of the polypropylene resin is preferably in the range of 150 ° C. to 170 ° C. from the viewpoints of heat resistance, slipperiness, film handling, scratch resistance, and curl resistance.
- Excellent heat resistance by setting the melting point to 150 ° C. or higher, maintaining the concealability of bus bars, etc., without reducing the thickness of the sheet due to the temperature and pressure when thermally bonded to EVA as a back surface protection sheet for solar cell modules This is preferable because it can be performed.
- the difference in crystallinity with the B layer is small, curling of the film can be suppressed, and the winding property is improved, and the adhesion to other substrates is also improved.
- the MFR of the polypropylene resin at 230 ° C. is preferably in the range of 1.0 to 15 g / 10 min. By making MFR larger than 1.0 g / 10 minutes, it is difficult to neck down in the film forming process, and stable film formation of the film becomes easy. Further, when the MFR is smaller than 15 g / 10 min, the crystallization speed is lowered and it is difficult to become brittle.
- the thickness of the polyolefin-based resin multilayer film in the present invention varies depending on the structure of the solar cell used, it is preferably in the range of 10 to 250 ⁇ m, and more preferably in the range of 20 to 200 ⁇ m for the lamination with the film production surface or other substrates. It is preferable from workability. By setting it as 250 micrometers or less, it can be excellent in economical efficiency and the handleability. Furthermore, it is an important object of the invention of the present application, to the heat resistance and concealment to the extent that the solar power generation element, the interconnector, and the bus bar are not transparent because the back protective sheet for the solar cell module is thinly deformed by the influence of the wiring member. In order to obtain an excellent back surface protection sheet for a solar cell module, the thickness of the polyolefin resin multilayer film is preferably 50 to 200 ⁇ m, and more preferably 130 to 200 ⁇ m.
- the polyolefin-based resin multilayer film in the present invention is composed of A layer / B layer / C layer, and the lamination ratio is not particularly limited.
- each of the A layer and the C layer is 5 to It is preferable that 20% and the B layer be in the range of 90 to 60%.
- the method for producing the polyolefin resin multilayer film in the present invention will be specifically described.
- the manufacturing method of a film is not limited to this.
- the resin used for the A layer a resin mixture in which 50 to 500 parts by weight of a polypropylene resin is mixed with 100 parts by weight of LLDPE having a melting point of 110 ° C. to 130 ° C. is used.
- the resin used for the B layer 5 to 50% by weight of rutile titanium oxide having an average particle size of 0.3 ⁇ m as white fine particles as a polypropylene resin having a melting point of 140 ° C. to 170 ° C., an antioxidant
- a resin mixture prepared by mixing “Sumilizer GP” in a range of 0.05 to 0.35 wt% is used.
- a polypropylene resin having a melting point of 150 to 170 ° C. was used as the resin used for the C layer.
- Each of the resins prepared in this way is supplied to a single-screw melt extruder and melted in the range of 220 to 280 ° C., respectively.
- a multi-manifold type T die or a feed block installed on top of the T die is used for A layer / B layer / C layer type
- These three kinds of three-layer laminations are performed and discharged from a T die onto a rotating metal roll with the C layer side set to the metal roll surface side to obtain an unstretched film.
- the surface temperature of the rotating metal roll is preferably controlled to 20 to 60 ° C., because the C layer does not stick to the metal roll and the crystallinity is improved.
- the ultraviolet absorbing layer in the present invention is composed of a resin composition obtained by blending an ultraviolet absorbent with a binder resin such as an acrylic resin, or a resin obtained by copolymerizing an ultraviolet absorbent and a light stabilizer with an acrylic resin or the like.
- a resin composition obtained by blending an ultraviolet absorbent with a binder resin such as an acrylic resin
- a resin obtained by copolymerizing an ultraviolet absorbent and a light stabilizer with an acrylic resin or the like are from the viewpoint of adhesion to a plastic film as a substrate and the weather resistance of the ultraviolet absorbing layer itself. preferable.
- Examples of the ultraviolet absorber copolymerized with the acrylic resin include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers.
- examples of the light stabilizer copolymerized with the acrylic resin include hindered amine-based light stabilizers.
- a white pigment to the ultraviolet absorbing layer in the present invention in order to improve the weather resistance of the resin of the ultraviolet absorbing layer.
- the white pigment is oxidized. Titanium is preferred.
- the thickness of the ultraviolet absorbing layer is preferably 0.2 to 5 ⁇ m, more preferably 1 to 4 ⁇ m, and particularly preferably 1 to 3 ⁇ m.
- the UV-absorbing layer thicker than 0.2 ⁇ m, it is easy to form a uniform coating film without causing phenomena such as repellency or film breakage during coating, adhesion to the base plastic film, and above all UV-blocking performance Can be fully expressed.
- the thickness of the ultraviolet absorbing layer is 5 ⁇ m or less, and the ultraviolet ray cutting performance is sufficiently developed. Even if it is thicker than this, there are concerns that the coating method is restricted and the production cost is increased.
- the ultraviolet absorbing layer in the present invention has an effect of protecting the resin base material, it is formed on the outermost layer of the back surface protective sheet film for solar cell modules.
- the adhesive used for laminating the plastic film and the polyolefin resin multilayer film is not particularly limited, but an isocyanate cross-linking adhesive is generally used.
- an isocyanate cross-linking adhesive is generally used.
- the adhesive agent excellent in hydrolysis resistance it is preferable to use the adhesive agent excellent in hydrolysis resistance.
- the solvent used for the adhesive in the present invention is preferably a solvent having no active hydrogen such as esters, ketones, aliphatics, and aromatics.
- esters include ethyl acetate, propyl acetate, and butyl acetate.
- ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- aliphatic group include n-heptane, n-hexane, cyclohexane and the like.
- aromatics include toluene and xylene. Of these, ethyl acetate, propyl acetate, and methyl ethyl ketone are particularly preferable from the viewpoints of solubility and coating suitability.
- the thickness of the adhesive layer is preferably 0.1 to 10 ⁇ m, and more preferably 2 to 6 ⁇ m from the viewpoint of cost and adhesiveness.
- a gravure / roll coating method, a roll coating method, a reverse coating method, a kiss coating method, a coating method such as others, or a printing method is applied to a plastic film.
- Other plastic films or laminates can be laminated using a known technique such as dry lamination using an adhesive.
- the plastic film can be subjected to a surface treatment for improving adhesiveness such as corona treatment or plasma treatment, if necessary.
- the plastic film uses a gravure roll coating method, a roll coating method, a reverse coating method, a kiss coating method, a coating method such as others, or a printing method on the surface opposite to the surface to which the adhesive is applied.
- FIG. 1 is a schematic sectional side view of an example of producing a back surface protective sheet (10) for a solar cell module.
- the adhesion strength between the plastic film and the polyolefin-based resin multilayer film is preferably 2N / 15 mm or more.
- the adhesion strength between these films is 2 N / 15 mm or more, sufficient interlaminar strength of the laminated films is obtained, and delamination hardly occurs at the time of processing a solar cell module or by an accelerated test, and is 6 N / 15 mm or more. Is more preferable.
- FIG. 2 shows a schematic sectional side view of an example in which a solar cell module is produced.
- the thickness of the back protective sheet for solar cell module is preferably in the range of 200 to 400 ⁇ m.
- a high partial discharge voltage can be secured, and sufficient rigidity can be secured, and bending defects during handling can be significantly reduced.
- the thickness 400 ⁇ m or less while maintaining necessary and sufficient rigidity and withstand voltage characteristics, the length per roll when winding on the roll can be increased, and the productivity is excellent. can do. More preferably, it is in the range of 250 to 350 ⁇ m.
- a solar cell module is manufactured by thermocompression molding and mounting a frame.
- the solar cell module surface protective sheet (24) constituting the solar cell module is physically or transparently such as sunlight permeability, insulation, weather resistance, heat resistance, light resistance, water resistance, moisture resistance, and antifouling property. It preferably has chemical strength.
- the surface protective sheet include glass plates, polyamide resins (various nylons), polyester resins, cyclic polyolefin resins, polystyrene resins, (meth) acrylic resins, polycarbonate resins, acetal resins, and others.
- Various resin films or sheets such as can be used.
- the adhesive resin layer 1 (22) preferably has weather resistance, heat resistance, and transparency.
- the filler layer for example, ethylene / vinyl acetate copolymer, ionomer resin, ethylene / acrylic acid copolymer, or acid-modified polyolefin resin, polyvinyl butyral resin, silicone resin, One type or a mixture of two or more types of resins such as epoxy resins, (meth) acrylic resins, and the like can be used.
- the solar power generation element (25) as a photovoltaic element constituting the solar cell module is conventionally known, for example, a crystalline silicon solar power generation element such as a single crystal silicon type solar power generation element or a polycrystalline silicon type solar power generation element
- a crystalline silicon solar power generation element such as a single crystal silicon type solar power generation element or a polycrystalline silicon type solar power generation element
- Amorphous silicon solar power generation devices of single junction type or tandem structure type, III-V compound semiconductor solar power generation devices such as gallium arsenide (GaAs) and indium phosphorus (InP), cadmium tellurium (CdTe) and copper indium selenide II-VI compound semiconductor solar power generation elements such as (CuInSe 2 ), organic solar power generation elements, and the like
- GaAs gallium arsenide
- InP indium phosphorus
- CdTe cadmium tellurium
- CuInSe 2 copper indium selenide II-VI compound semiconductor solar power generation elements
- the adhesive resin layer 2 (23) laminated under the photovoltaic element constituting the solar cell module can be made of the same material as the adhesive resin layer 1 (22).
- the adhesive resin layer 2 (23) preferably has adhesiveness with the back surface protective sheet.
- These adhesive resin layers have thermoplasticity in order to fulfill the function of maintaining the smoothness of the back surface of the solar power generation element as the photovoltaic element, and further protect the solar power generation element as the photovoltaic element. For this reason, it is preferable to have excellent scratch resistance, shock absorption and the like.
- An aluminum mold is suitable as the frame of the solar cell module.
- the melting point of the resin used is the highest melting peak when the temperature is raised from 20 ° C. at a rate of 10 ° C./minute using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60) and heated to 300 ° C. The temperature was taken as the melting point.
- the plates (34) were laminated in this order, and after installation on a solar cell module laminator (LM-50X50-S) manufactured by NPC, vacuum time was 5 minutes, control time was 1 minute, press time was 9 minutes, Thermocompression bonding was performed at a temperature of 142 ° C. After crimping, the module was cooled to room temperature to produce a pseudo module.
- Heat resistance test Observation of thickness of polyolefin resin multilayer film
- the pseudo module after the heat resistance test was cut with a blade, and the cut surface of the back protective sheet for the solar cell module in the interconnector portion was magnified 200 times with a polarizing microscope (Nikon Corporation ECLIPSE E400POL). Observation was made, and the change in the thickness of the entire polyolefin-based resin multilayer film was determined to be “+” or more according to the following criteria.
- Thickness change is less than -5% +: Thickness change is -5% or more and less than -20%-: Thickness change is -20% or more [Measurement of adhesive strength between back surface protection sheet for solar cell module and EVA]
- the polyolefin-based resin multilayer film (11) surface of the back protective sheet for solar cell module (10) faces the EVA sheet 2 (43) and the release film (45).
- Back surface protection sheet (10) / release film (45) / EVA sheet 2 (43) / EVA sheet 1 (42) / glass plate (44) are laminated in this order, and manufactured by NPC Corporation, Sun After being installed in a battery module laminator (LM-50 ⁇ 50-S), thermocompression bonding was performed under the conditions of a vacuum time of 5 minutes, a control time of 1 minute, a press time of 9 minutes, and a temperature of 142 ° C. After crimping, the module was cooled to room temperature to produce a pseudo module. Using the pseudo module, the adhesive strength between the back protection sheet for solar cell modules and EVA was measured as follows.
- the film was peeled at a peeling speed of 100 mm / min, the adhesive strength was evaluated, and “+” or more was determined to be acceptable according to the following criteria.
- UV resistance evaluation Using an I-super UV tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd., ultraviolet irradiation (ultraviolet irradiation cumulative amount 206 kWh / m 2 ) was performed at 63 ° C. ⁇ 30% RH atmosphere at an ultraviolet intensity of 160 mW / cm 2 for 24 hours.
- the color system b * values before and after that were measured. When the difference in b * value was less than 6, it was judged as “++”, and when it was less than 30, it was judged as “+”, and when it was more than 30, it was judged as “-”.
- Titanium oxide master batch A Rutile with an average particle size of 200 nm, surface-treated with 40% by weight of homopolypropylene having a melting point of 162 ° C. and a density of 0.900 g / cm 3 , and an inorganic oxide mainly composed of one or more of silicon, aluminum, zinc and the like Titanium oxide master batch A was produced by melt-kneading 60 wt% of type titanium oxide (FTR-700 manufactured by Sakai Chemical Industry Co., Ltd.) at 240 ° C. with a twin-screw extruder and then strand cutting.
- FTR-700 type titanium oxide manufactured by Sakai Chemical Industry Co., Ltd.
- Method for producing titanium oxide master batch B Melting point 122 ° C., density 0.922 g / cm 3 , MFR 7 g / 10 min LLDPE 40% by weight and average surface-treated with one or more inorganic oxides such as silicon, aluminum, zinc and zirconium 60% by weight of rutile titanium oxide (FTR-700 manufactured by Sakai Chemical Industry Co., Ltd.) with a particle size of 200 nm is melt-kneaded at 210 ° C. with a twin screw extruder, and then strand-cut to produce a titanium oxide master batch B. did.
- FTR-700 rutile titanium oxide
- Example 1 The resin used for the A layer has a melting point of 127 ° C., a density of 0.940 g / cm 3 , an MFR of 5.0 g / 10 minutes, 80 parts by weight of LLDPE, a melting point of 112 ° C., a density of 0.912 g / cm 3 , and an MFR of 4.0 g / 20 parts by weight of LDPE for 10 minutes (total 100 parts by weight of polyethylene resin) and polypropylene resin, melting point 150 ° C., density 0.900 g / cm 3 , MFR 7 g / 10 min ethylene content 4 mol%
- EPC propylene random copolymer
- a titanium oxide master batch A 30 is used with respect to 100 parts by weight of a homopolypropylene (hereinafter abbreviated as H-PP) having a melting point of 160 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / 10 min. Resin mixed with parts by weight was used. The addition amount of titanium oxide as a coloring agent is 13.8% by weight.
- H-PP homopolypropylene
- an ethylene / propylene block copolymer (hereinafter abbreviated as B-PP) having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4.0 g / 10 min, and an ethylene content of 7 mol%. ) was used.
- the polyolefin resin multilayer film was wound with a corona discharge treatment performed on the C layer side so that the wetting tension on the surface of the C layer was 40 mN / m.
- HALS HYBRID POLYMER (registered trademark) BK1 (solid content concentration), a coating agent produced by Nippon Shokubai Co., Ltd., characterized in that an ultraviolet absorber and a light stabilizer (HALS) are cross-linked to an acrylic polyol resin : 40 wt%, acrylic resin) were mixed together with white fine particles, plasticizer and solvent, and dispersed using a bead mill, to obtain a main coating material for forming a resin layer having a solid content concentration of 50 wt%.
- HALS HYBRID a coating agent produced by Nippon Shokubai Co., Ltd., characterized in that an ultraviolet absorber and a light stabilizer (HALS) are cross-linked to an acrylic polyol resin : 40 wt%, acrylic resin) were mixed together with white fine particles, plasticizer and solvent, and dispersed using a bead mill, to obtain a main coating material for forming a resin layer having a solid content concentration of 50 wt%.
- “Desmodur” (registered trademark) N3300 (solid content concentration: 100% by weight) manufactured by Sumika Bayer Urethane Co., Ltd., which is a nurate type hexamethylene diisocyanate, is used as the main coating material for the resin layer forming coating obtained by the above-described method.
- the pre-calculated diluent was mixed so that the weight ratio to the ratio of 33/8 was 33/8, and the coating agent had a solid content concentration of 20% by weight (resin solid content concentration): n-propyl acetate Was measured and stirred for 15 minutes to obtain a coating material for forming an ultraviolet absorbing layer having a solid content concentration of 20% by weight (resin solid content concentration).
- titanium oxide particles JR-709 manufactured by Teika Co., Ltd.
- an epoxy plasticizer manufactured by DIC (“Eposizer” W-121) is used as the plasticizer. It was used.
- a hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10S (125 ⁇ m) manufactured by Toray Industries, Inc.) was prepared as a plastic film.
- the UV absorbing layer forming paint was applied using a dry laminator (Okazaki Machine Industry Co., Ltd. dry laminator OG / DL-130TA-AF with one-color printing) at 150 ° C.
- the film was dried for 30 seconds, and an ultraviolet absorbing layer was provided so that the coating amount after drying was 4.0 g / m 2 .
- “Lumirror” registered trademark
- X10S registered trademark
- the thickness of the back protective sheet for the solar cell module was 285 ⁇ m.
- the laminated film was aged at a temperature of 40 ° C. for 72 hours to accelerate the curing reaction of the adhesive layer, and used as the back surface protective sheet for solar cell modules of the present invention.
- the evaluation results are shown in Table 1.
- Example 2 As the polyethylene resin used in the A layer, the LDPE used in Example 1 was used alone, and a resin obtained by mixing 150 parts by weight of the LDPE with 150 parts by weight of EPC used in Example 1 as a polypropylene resin was used. It was.
- the resin used for the B layer has a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, an ethylene content of 7 mol%, and 100 parts by weight of B-PP with a melting point of 150 ° C. and a density of 0.900 g / A resin prepared by mixing cm 3 , MFR 7 g / 10 min, 100 parts by weight of EPC having an ethylene content of 4 mol%, and 20 parts by weight of titanium oxide master batch A was used. The amount of titanium oxide that is white fine particles is 5.5% by weight.
- a resin used for the C layer a resin obtained by mixing 100 parts by weight of H-PP with a melting point of 162 ° C., a density of 0.900 g / cm 3 and an MFR of 7 g / 10 min with respect to 100 parts by weight of B-PP used in Example 1. was used.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 1.
- Example 3 As a polyethylene resin used in the A layer, a polypropylene resin having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% with respect to 100 parts by weight of LLDPE used in Example 1. A resin mixed with 200 parts by weight of B-PP was used.
- the resin used for the B layer a resin in which 300 parts by weight of titanium oxide master batch A was mixed with 100 parts by weight of EPC used in Example 2 was used.
- the amount of titanium oxide that is white fine particles is 45.0% by weight.
- EPC100 As a resin used for the C layer, EPC100 having a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 min, and an ethylene content of 4 mol% with respect to 100 parts by weight of H-PP used in Example 2. Resin mixed with parts by weight was used.
- a back protective sheet for a solar cell module was obtained in the same manner as in Example 1 except that the polyolefin resin multilayer film prepared in this way was used.
- the evaluation results are shown in Table 1.
- Example 4 The resin used for the A layer and the C layer was the same as in Example 1.
- Example 2 As the resin used for the B layer, instead of B-PP used in Example 2, it was carried out except that 40 parts by weight of LDPE having a melting point of 112 ° C., a density of 0.912 g / cm 3 , and an MFR of 4.0 g / 10 min was used. Same as Example 2. The addition amount of titanium oxide as white fine particles was 7.5% by weight, and the content of polyethylene was 27% by weight of the total resin components.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 1.
- Example 5 As the resin used for the A layer, the same resin as in Example 1 was used except that 60 parts by weight of EPC used in Example 1 was used.
- the thickness of the back protective sheet for the solar cell module was 235 ⁇ m.
- Example 6 As the resin used for the A layer, the same resin as in Example 1 was used, except that 400 parts by weight of EPC used in Example 1 was used.
- the evaluation results are shown in Table 1.
- Example 7 As the resin used for the A layer, the same resin as in Example 1 was used except that the EPC used in Example 1 was 600 parts by weight.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 1.
- Example 8 As the polyethylene resin used for the A layer, a resin in which 100 parts by weight of EPC same as that used in Example 1 as a polypropylene resin is mixed with 100 parts by weight of HDPE having a melting point of 134 ° C. and a density of 0.952 g / cm 3 is used. The same resin as in Example 1 was used except that.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the resin of each of the A layer, B layer, and C layer prepared in this way was used.
- the evaluation results are shown in Table 1.
- Example 9 The resin used for the B layer was the same as that of Example 4 except that 60 parts by weight of EPC used in Example 4, 40 parts by weight of LDPE, and 20 parts by weight of titanium oxide master batch A were used.
- the polyethylene concentration in layer B was 37% by weight, and the polyethylene concentration was relatively high.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 1.
- Example 10 A back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that PEN film “Teonex” Q51 (125 ⁇ m) manufactured by Teijin DuPont Films Ltd. was used as the plastic film. The evaluation results are shown in Table 2.
- Example 11 As the plastic film, a fluororesin film (FEP easy adhesion film “Toyoflon” (registered trademark) FL (100 ⁇ m) manufactured by Toray Film Processing Co., Ltd.) was used. In the same manner as in Example 1, an ultraviolet absorbing layer was formed on one side of the fluororesin film and laminated with a polyolefin resin multilayer film to prepare a back protective sheet for a solar cell module. The evaluation results are shown in Table 2.
- FEP easy adhesion film “Toyoflon” registered trademark
- FL 100 ⁇ m
- Example 12 Hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10 (125 ⁇ m) manufactured by Toray Industries, Inc.) and fluorine-based resin film (Toyoflon, an ETFE easy-adhesive film manufactured by Toray Film Processing Co., Ltd.) as plastic films
- An ultraviolet absorbing layer was laminated on the ETFE side using a laminate of (registered trademark) EL (100 ⁇ m).
- it was bonded to a polyolefin-based multilayer laminated film to obtain a back surface protective sheet for a solar cell module.
- Table 2 The evaluation results are shown in Table 2.
- Example 13 Using the same polyolefin raw material of A layer / B layer / C layer as in Example 1, the blending amount of titanium oxide master batch A of B layer is increased to 50 parts by weight, and the extrusion amount is decreased to a polyolefin resin having a thickness of 50 ⁇ m A multilayer film was prepared. The amount of titanium oxide added to layer B was 20.0% by weight. A 250 ⁇ m hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10) manufactured by Toray Industries, Inc.) is used as a plastic film and laminated with the above 50 ⁇ m polyolefin resin multilayer film for a solar cell module It was set as the back surface protection sheet. The evaluation results are shown in Table 2.
- the thickness of the back protective sheet for the solar cell module was 310 ⁇ m.
- the thickness of the polyolefin resin multilayer film is as thin as 50 ⁇ m, transparency was observed, but it was at a practical level, and since the thickness of the hydrolysis-resistant biaxially stretched PET film was as thick as 250 ⁇ m, it was difficult to comply with the UL746A standard. It was able to be set as the back surface protection sheet for solar cell modules excellent in flammability.
- Example 14 Using the same polyolefin raw material of A layer / B layer / C layer as in Example 1, the extrusion amount was reduced to produce a 125 ⁇ m olefin resin multilayer film.
- a 125 ⁇ m hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10, manufactured by Toray Industries, Inc.) is used as a plastic film and laminated with the 125 ⁇ m polyolefin resin multilayer film to protect the back surface of the solar cell module. A sheet was used. The evaluation results are shown in Table 2.
- the thickness of the back protective sheet for the solar cell module was 260 ⁇ m. Since the thickness of the olefin-based resin multilayer film was as thin as 125 ⁇ m, the occurrence of see-through was observed, but the level was satisfactory.
- Example 15 A solar cell was produced in the same manner as in Example 1, except that the plastic film was a 100 ⁇ m hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10 manufactured by Toray Industries, Inc.). It was set as the back surface protection sheet for modules. The evaluation results are shown in Table 2.
- the thickness of the back protective sheet for the solar cell module was 260 ⁇ m.
- Example 16 In the same manner as in Example 14, the amount of extrusion was increased to produce a polyolefin resin multilayer film having a thickness of 175 ⁇ m.
- a plastic film is made into a 75 ⁇ m hydrolysis-resistant biaxially stretched PET film (“Lumirror” (registered trademark) X10, manufactured by Toray Industries, Inc.), and laminated with the above-mentioned 175 ⁇ m polyolefin-based resin multilayer film to protect the back surface of the solar cell module.
- a sheet was used. The evaluation results are shown in Table 2.
- the thickness of the back protective sheet for the solar cell module was 260 ⁇ m.
- Example 1 A polyolefin resin multilayer film is formed in the same manner as in Example 1 without laminating an ultraviolet absorbing layer on a hydrolysis-resistant biaxially stretched PET film of plastic film (“Lumirror” (registered trademark) X10S (125 ⁇ m) manufactured by Toray Industries, Inc.) It laminated
- the evaluation results are shown in Table 2. The difference in b * value according to the UV resistance evaluation greatly increased and could not withstand practical use.
- the thickness of the back protective sheet for the solar cell module was 280 ⁇ m.
- a resin used for the B layer a resin in which 30 parts by weight of a titanium oxide master batch B was mixed with 100 parts by weight of LDPE having a melting point of 112 ° C., a density of 0.912 g / cm 3 , and an MFR of 4.0 g / 10 minutes was used. .
- the amount of white oxide titanium oxide added is 13.8% by weight, and the content of polyethylene is 100% by weight of the total resin component.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 2.
- Example 3 A back protective sheet for a solar cell module was prepared in the same manner as in Example 1 including the B layer and C layer resins except that the LLDPE used in Example 1 alone was used as the resin for the A layer. The evaluation results are shown in Table 2.
- LLDPE As a resin used for the C layer, LLDPE having a melting point of 127 ° C., a density of 0.940 g / cm 3 , an MFR of 5.0 g / 10 minutes, and an ethylene content of 5 mol% was used alone.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the respective resins of the A layer, B layer, and C layer prepared in this way were used.
- the evaluation results are shown in Table 2.
- Example 5 A back protective sheet for a solar cell module was prepared in the same manner as in Example 1 including B layer and C layer resin except that EPC used alone in Example 1 was used as the resin for the A layer. The evaluation results are shown in Table 2. Adhesion with EVA was insufficient.
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Abstract
Description
プラスチックフィルムとポリオレフィン系樹脂多層フィルムとの密着強度は、2N/15mm以上が好ましい。これらフィルム間の密着強度が、2N/15mm以上であると、積層したフィルムの層間強度が十分得られ、太陽電池モジュール加工時あるいは促進試験等による層間剥離が起こり難く、6N/15mm以上であることがより好ましい。
密度は、(ASTM) D1505にて測定した。
[MFRの測定方法]
LLDPE、LDPEの溶融指数(MFR)は、ASTM D1238に則り190℃、2.16kg荷重にて、また、ホモポリプロピレン、エチレン・プロピレンブロック共重合体、エチレン・プロピレンランダム共重合体のMFRは230℃ 2.16kg荷重にて測定した。
使用する樹脂の融点は示差走査熱量計(島津製作所製、DSC-60)を用いて、20℃から10℃/分の速度で昇温し、300℃まで加熱した際の融解ピークの最も高いピーク温度を融点とした。
太陽電池モジュール裏面保護シートのポリオレフィン系樹脂多層フィルム面について、分光光度計(日立製作所製 U-3410)に、φ60積分球(日立製作所社製、130-0632)および10度傾斜スペーサーを取り付けた状態で560nmの絶対反射率を3回測定した平均値を求めて反射率とした。
図3に示すように、太陽電池モジュール用裏面保護シート(10)のポリオレフィン系樹脂多層フィルム(11)面がEVAシート2(33)と向かい合う方向で、太陽電池モジュール用裏面保護シート(10)/EVAシート2(33)(サンビック(株)製、PV-45FR000 厚さ450μm)/インターコネクター(35)(2mm幅×厚さ0.6mm)/EVAシート1(32)(厚さ450μm)/ガラス板(34)をこの順に積層し、(株)エヌ・ピー・シー製、太陽電池モジュールラミネーター(LM-50X50-S)に設置後、真空時間5分、制御時間1分、プレス時間9分、温度142℃の条件にて加熱圧着した。圧着後、室温冷却し、疑似モジュールを作製した。
5:10枚全てでインターコネクターの透けがない。
4:10枚中1枚でインターコネクターの僅かな透けがあり、残りは透けがない。
3:10枚中2枚以上でインターコネクターの僅かな透けがあるが、明らかな透けはない。
2:10枚中1枚でインターコネクターの明らかな透けがある。
1:10枚中2枚以上でインターコネクターの明らかな透けがある。
耐熱性試験後の疑似モジュールへ刃物で切り込みを入れて、インターコネクター部分の太陽電池モジュール用裏面保護シートの切断面を偏光顕微鏡((株)ニコン製ECLIPSE(エクリプス)E400POL)で200倍の倍率で観察し、ポリオレフィン系樹脂多層フィルム全体の厚さの変化を下記の基準により「+」以上を合格と判定した。
++:厚さ変化が-5%未満
+ :厚さ変化が-5%以上-20%未満
- :厚さ変化が-20%以上
[太陽電池モジュール用裏面保護シートとEVAとの接着強度測定]
図4に示すように、太陽電池モジュール用裏面保護シート(10)のポリオレフィン系樹脂多層フィルム(11)面がEVAシート2(43)と離型フィルム(45)に向かい合う方向で、太陽電池モジュール用裏面保護シート(10)/離型フィルム(45)/EVAシート2(43)/EVAシート1(42)/ガラス板(44)をこの順に積層し、(株)エヌ・ピー・シー製、太陽電池モジュールラミネーター(LM-50×50-S)に設置後、真空時間5分、制御時間1分、プレス時間9分、温度142℃の条件にて加熱圧着した。圧着後、室温冷却し、疑似モジュールを作製した。当該疑似モジュールを用いて、太陽電池モジュール用裏面保護シートとEVAの接着強度を下記の通り測定した。
++:剥離強度が50N/10mm以上
+ :剥離強度が50N/10mm未満、40N/10mm以上
- :剥離強度が40N/10mm未満、20N/10mm以上
--:剥離強度が20N/10mm未満。
岩崎電気社製アイスーパーUVテスターSUV-W151を用いて、63℃×30%RH雰囲気にて紫外線強度160mW/cm2で24時間紫外線照射(紫外線照射積算量206kWh/m2)を行った。その前後の表色系b*値の測定を行った。b*値の差が6未満の場合を「++」で合格、30未満6以上の場合を「+」で合格、30以上を「-」で不合格と判定した。
融点162℃、密度0.900g/cm3のホモポリプロピレン40重量%と、珪素、アルミニウム、亜鉛などの1種あるいは複数種を主成分とする無機酸化物で表面処理された平均粒子径200nmのルチル型酸化チタン(堺化学工業(株)製FTR-700)60重量%とを二軸押出機にて240℃で溶融混練した後、ストランドカットし、酸化チタンマスタバッチAを製造した。
融点122℃、密度0.922g/cm3、MFR7g/10分のLLDPE40重量%と、珪素、アルミニウム、亜鉛、ジルコニウムなどの1種あるいは複数種を主成分とする無機酸化物で表面処理された平均粒子径200nmのルチル型酸化チタン(堺化学工業(株)製FTR-700)60重量%とを二軸押出機にて210℃で溶融混練した後、ストランドカットし、酸化チタンマスタバッチBを製造した。
A層に使用する樹脂として、融点127℃、密度0.940g/cm3、MFR5.0g/10分のLLDPE 80重量部に対し、融点112℃、密度0.912g/cm3、MFR4.0g/10分のLDPEを20重量部(ポリエチレン系樹脂合計100重量部)、及びポリプロピレン系樹脂として、融点150℃、密度0.900g/cm3、MFR7g/10分のエチレン含有量4モル%のエチレン・プロピレンランダム共重合体(以下、EPCと略称する)100重量部を混合した樹脂を用いた。
A層に使用するポリエチレン系樹脂として、実施例1で用いたLDPEを単独で使用し、該LDPE 100重量部に対し、ポリプロピレン系樹脂として実施例1で用いたEPC150重量部を混合した樹脂を用いた。
A層に使用するポリエチレン系樹脂として、実施例1で用いたLLDPE100重量部に対し、ポリプロピレン系樹脂として融点160℃、密度0.900g/cm3、MFR4g/10分、エチレン含有量7モル%のB-PP200重量部を混合した樹脂を用いた。
A層、C層に使用する樹脂は実施例1と同じにした。
A層に使用する樹脂として、実施例1で用いたEPCを60重量部とした以外は、実施例1と同じ樹脂を用いた。
A層に使用する樹脂として、実施例1で用いたEPCを400重量部とした以外は、実施例1と同じ樹脂を用いた。
A層に使用する樹脂として、実施例1で用いたEPCを600重量部とした以外は、実施例1と同じ樹脂を用いた。
A層に使用するポリエチレン系樹脂として、融点134℃、密度0.952g/cm3のHDPE100重量部に対し、ポリプロピレン系樹脂として実施例1で使用したものと同じEPC100重量部を混合した樹脂を用いた以外は、実施例1と同じ樹脂を用いた。
B層に使用する樹脂として、実施例4で用いたEPCを60重量部、同LDPEを40重量部、酸化チタンマスタバッチAを20重量部とした以外は実施例4と同じとした。B層中のポリエチレン濃度は37重量%となり、ポリエチレンの濃度が比較的大きいものとした。
プラスチックフィルムとして帝人デュポンフィルム(株)製PENフィルム“テオネックス”Q51(125μm)を用いた以外は実施例1と同様の方法で太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
プラスチックフィルムとしてフッ素系樹脂フィルム(東レフィルム加工(株)製FEP易接着フィルム「トヨフロン」(登録商標)FL(100μm))を使用した。実施例1と同様に、該フッ素系樹脂フィルムの片面に紫外線吸収層を形成し、ポリオレフィン系樹脂多層フィルムと積層し、太陽電池モジュール用裏面保護シートを作成した。その評価結果を表2に示す。
プラスチックフィルムとして耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10(125μm))とフッ素系樹脂フィルム(東レフィルム加工(株)製ETFE易接着フィルム「トヨフロン」(登録商標)EL(100μm))を張り合わせたものを用い、ETFE側に紫外線吸収層を積層した。実施例1と同様にポリオレフィン系多層積層フィルムと貼り合わせ、太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
実施例1と同じA層/B層/C層のポリオレフィン原料を用い、B層の酸化チタンマスタバッチAの配合量を50重量部に増やし、押出量を減少させて厚さ50μmのポリオレフィン系樹脂多層フィルムを作製した。B層の酸化チタンの添加量は20.0重量%であった。プラスチックフィルムとして250μmの耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10)を使用し、上記の50μmのポリオレフィン系樹脂多層フィルムと積層して太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
実施例1と同じA層/B層/C層のポリオレフィン原料を用い、押出量を減少させて125μmのオレフィン系樹脂多層フィルムを作製した。プラスチックフィルムとして125μmの耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10)を用い、上記125μmのポリオレフィン系樹脂多層フィルムと積層して太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
実施例1において、プラスチックフィルムを100μmの耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10)のとしたこと以外は実施例1と同様の方法で太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
実施例14と同様にして押出量を増大させて175μmのポリオレフィン系樹脂多層フィルムを作製した。プラスチックフィルムを75μmの耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10)とし、上記の175μmのポリオレフィン系樹脂多層フィルムと積層して太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
プラスチックフィルムの耐加水分解性二軸延伸PETフィルム(東レ(株)製「ルミラー」(登録商標)X10S(125μm))に紫外線吸収層を積層せず、実施例1と同様にポリオレフィン樹脂多層フィルムと積層し太陽電池モジュール用裏面保護シートとした。その評価結果を表2に示す。
耐紫外線性評によるb*値の差が大きく増大し実用に耐えないものであった。
A層、C層に使用する樹脂は実施例1と同じにした。
A層に使用する樹脂として、実施例1で用いたLLDPE単独とした以外は、B層、C層樹脂含め実施例1と同様にして太陽電池モジュール用裏面保護シートを作成した。その評価結果を表2に示す。
A層、B層に使用する樹脂は実施例1と同じにした。
A層に使用する樹脂として、実施例1で用いたEPC単独とした以外は、B層、C層樹脂含め実施例1と同様にして太陽電池モジュール用裏面保護シートを作成した。その評価結果を表2に示す。
EVAとの密着性が不十分であった。
11:ポリオレフィン系樹脂多層フィルム
12:ポリオレフィン系樹脂多層フィルムのA層
13:ポリオレフィン系樹脂多層フィルムのB層
14:ポリオレフィン系樹脂多層フィルムのC層
15:接着剤層
16:プラスチックフィルム
17:紫外線吸収層
22:接着性樹脂層1
23:接着性樹脂層2
24:太陽電池モジュール用表面保護シート
25:光起電力素子
32、42:EVAシート1
33、43:EVAシート2
35:インターコネクター
34、44:ガラス板
45:離型フィルム
Claims (7)
- A層/B層/C層の3層構成からなるポリオレフィン系樹脂多層フィルムとプラスチックフィルムと紫外線吸収層とがこの順に積層された太陽電池モジュール用裏面保護シートフィルムであって、A層がポリエチレン系樹脂とポリプロピレン系樹脂を混合した樹脂組成物からなり、B層が白色微粒子を含有するポリプロピレン系樹脂組成物からなり、C層がポリプロピレン系樹脂組成物からなることを特徴とする太陽電池モジュール用裏面保護シート。
- プラスチックフィルムがポリエチレンテレフタレートフィルム、耐加水分解性ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルムのいずれかを含むことを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- プラスチックフィルムがフッ素系樹脂フィルムを含むことを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- プラスチックフィルムがポリエチレンテレフタレートフィルムまたは耐加水分解性ポリエチレンテレフタレートフィルム、およびフッ素系樹脂フィルムを積層したフィルムであり、紫外線吸収層がフッ素系樹脂フィルム側に積層されることを特徴とする請求項2または3に記載の太陽電池モジュール用裏面保護シート。
- 太陽電池モジュール用裏面保護シートの厚さが250~350μmであり、ポリオレフィン樹脂系多層フィルムの厚さが130~200μmであることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- 太陽電池モジュール用裏面保護シートの厚さが250~350μmであり、プラスチックフィルムの厚さが200~250μmであることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- 請求項1~6のいずれかに記載の太陽電池モジュール用裏面保護シートを用いた太陽電池モジュール。
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- 2012-09-21 KR KR1020147011961A patent/KR20140074376A/ko not_active Application Discontinuation
- 2012-09-21 EP EP12837703.3A patent/EP2765616A4/en not_active Withdrawn
- 2012-09-21 JP JP2012544992A patent/JP6015449B2/ja not_active Expired - Fee Related
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JP2015168151A (ja) * | 2014-03-07 | 2015-09-28 | 東レフィルム加工株式会社 | ポリプロピレン系複合フィルムおよびそれを用いた積層体 |
JP2015168150A (ja) * | 2014-03-07 | 2015-09-28 | 東レフィルム加工株式会社 | ポリプロピレン系複合フィルムおよびそれを用いた積層体 |
JP2015171778A (ja) * | 2014-03-12 | 2015-10-01 | 東レフィルム加工株式会社 | ポリプロピレン系複合フィルムおよびそれを用いた積層体 |
JP2015191944A (ja) * | 2014-03-27 | 2015-11-02 | 大日本印刷株式会社 | 裏面保護シート及びそれを用いた太陽電池モジュール |
JP2015192107A (ja) * | 2014-03-28 | 2015-11-02 | 富士フイルム株式会社 | 太陽電池用裏面保護シート及びその製造方法、並びに太陽電池モジュール |
WO2015168174A1 (en) * | 2014-04-28 | 2015-11-05 | Madico, Inc. | Protective sheet for a photovoltaic module |
WO2015182282A1 (ja) * | 2014-05-28 | 2015-12-03 | 東レ株式会社 | 太陽電池バックシート用ポリエステルフィルム |
CN106463558A (zh) * | 2014-05-28 | 2017-02-22 | 东丽株式会社 | 太阳能电池背板用聚酯膜 |
WO2017122713A1 (ja) * | 2016-01-13 | 2017-07-20 | 三井化学株式会社 | 積層シートおよびこれを用いてなる太陽電池バックシート |
JPWO2017122713A1 (ja) * | 2016-01-13 | 2018-11-01 | 三井化学株式会社 | 積層シートおよびこれを用いてなる太陽電池バックシート |
US10896988B2 (en) | 2016-01-13 | 2021-01-19 | Mitsui Chemicals, Inc. | Laminated sheet and solar cell backsheet using same |
JP2019050346A (ja) * | 2017-09-07 | 2019-03-28 | ダイヤプラスフィルム株式会社 | 太陽電池裏面保護シート用多層フィルム、太陽電池裏面保護シート及び太陽電池モジュール |
Also Published As
Publication number | Publication date |
---|---|
CN103958192A (zh) | 2014-07-30 |
EP2765616A1 (en) | 2014-08-13 |
JP6015449B2 (ja) | 2016-10-26 |
KR20140074376A (ko) | 2014-06-17 |
EP2765616A4 (en) | 2015-05-27 |
JPWO2013051403A1 (ja) | 2015-03-30 |
CN103958192B (zh) | 2016-06-29 |
TW201321187A (zh) | 2013-06-01 |
US20140318616A1 (en) | 2014-10-30 |
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