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WO2010079798A1 - Film polyester pour couche de protection de surface arrière de cellule solaire - Google Patents

Film polyester pour couche de protection de surface arrière de cellule solaire Download PDF

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Publication number
WO2010079798A1
WO2010079798A1 PCT/JP2010/050084 JP2010050084W WO2010079798A1 WO 2010079798 A1 WO2010079798 A1 WO 2010079798A1 JP 2010050084 W JP2010050084 W JP 2010050084W WO 2010079798 A1 WO2010079798 A1 WO 2010079798A1
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WO
WIPO (PCT)
Prior art keywords
film
polyester
solar cell
back surface
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/050084
Other languages
English (en)
Japanese (ja)
Inventor
勝也 伊藤
潤 稲垣
睦夫 西
史朗 濱本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009001489A external-priority patent/JP5114681B2/ja
Priority claimed from JP2009002369A external-priority patent/JP5572949B2/ja
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Publication of WO2010079798A1 publication Critical patent/WO2010079798A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/488—Reflecting light-concentrating means, e.g. parabolic mirrors or concentrators using total internal reflection
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • Y02E10/52—PV systems with concentrators

Definitions

  • This invention relates to the polyester film for solar cell back surface protective films.
  • a solar cell module generally has a plurality of plate-like solar cell elements sandwiched between a glass substrate on a light receiving side and a back surface protective film, It takes a structure in which the internal gap is filled with sealing resin.
  • a plastic film having excellent mechanical properties, heat resistance and moisture resistance is used for the back surface protective film.
  • Japanese Patent Laid-Open Nos. 2002-26354 and 2003-60218 propose a back surface protective film using a polyethylene terephthalate film.
  • a white back surface protective film may be used for the purpose of improving the power generation efficiency of a solar cell.
  • JP 2002-26354 A Japanese Patent Laid-Open No. 2003-60218 JP-A-60-250946 JP 2004-247390 A JP 2002-134771 A JP 2007-208179 A JP 2008-85270 A
  • a white polyester film By using a white polyester film, it is possible to reflect sunlight and increase power generation efficiency.
  • a white polyester film needs to add a large amount of particles to a polyester substrate. Therefore, in order to improve their dispersibility and mixing state, the raw material is preliminarily mixed with two or more kinds of materials, and the resin is deteriorated because the melting time is increased even in a normal extrusion process. Easy to do. Therefore, when used as a solar cell under high temperature and high humidity, it has been a problem that durability is poor.
  • the present invention relates to the above-mentioned problem, that is, a polyester film for a solar cell back surface protective film having good durability under high temperature and high humidity.
  • the present invention relates to a polyester film for a solar cell back surface protective film having good adhesion to EVA resin.
  • the present invention relates to a polyester film for a solar cell back surface protective film having good durability under light irradiation.
  • the first invention contains 3 to 50% by mass of fine particles having a whiteness of 50 or more and an average particle size of 0.1 to 3 ⁇ m, and the acid value of the film is 1 (eq / ton) to 30 (eq / ton)
  • It is a polyester film for solar cell back surface protective film characterized by the following.
  • 2nd invention is the said polyester film for solar cell back surface protective films which has a coating layer which has at least 1 sort (s) of a polyester resin, a polyurethane resin, or a polyacryl resin as a main component at least on one side.
  • a third invention is the above-mentioned polyester film for a solar cell backside protective film, characterized by having a thermal adhesive layer having a thickness of 1.0 to 40 ⁇ m mainly composed of an amorphous polyester resin on at least one side.
  • a fourth invention is the polyester film for a solar cell back surface protective film, wherein the fine particles are titanium dioxide fine particles mainly composed of a rutile type and contain 3 to 50% by mass of the fine particles.
  • 5th invention is the said polyester film for solar cell back surface protective films characterized by having an apparent specific gravity of 0.7 or more and 1.3 or less by having many fine cavities inside a film.
  • the sixth invention contains a polyester layer (skin layer) containing many cavities derived from fine particles having an average particle size of 0.1 to 3 ⁇ m, and contains many cavities derived from a thermoplastic resin incompatible with polyester.
  • 7th invention is the polyester film for solar cell back surface protective films characterized by the acid value of polyester used as a film raw material being 1 (eq / ton) or more and 30 (eq / ton) or less.
  • the present invention has light reflection efficiency and excellent durability under high temperature and high humidity. Furthermore, the preferable aspect of this invention has favorable adhesiveness with EVA resin in addition to the said effect. Furthermore, the preferable aspect of this invention has the outstanding durability under light irradiation in addition to the said effect. Therefore, it is useful in solar cells, particularly thin film silicon solar cells.
  • the polyester in the present invention is a polycondensation of an aromatic dicarboxylic acid or its ester such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid with a glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol or neopentyl glycol.
  • Polyester produced In addition to the method of directly reacting aromatic dicarboxylic acid and glycol, these polyesters can be polycondensed by transesterification of alkyl ester of aromatic dicarboxylic acid and glycol, or diglycol ester of aromatic dicarboxylic acid. Can be produced by a method such as polycondensation.
  • polyesters include polyethylene terephthalate, polyethylene butylene terephthalate, polyethylene-2,6-naphthalate and the like.
  • This polyester may be a homopolymer or a copolymer of a third component.
  • a polyester having an ethylene terephthalate unit, a butylene terephthalate unit or an ethylene-2,6-naphthalate unit of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more is preferable. .
  • the polyester used as the film raw material preferably has an acid value of 1 (eq / ton) to 30 (eq / ton), more preferably 2 (eq / ton) to 20 (eq / ton), Preferably they are 2 (eq / ton) or more and 16 (eq / ton) or less. If it exceeds 30 (eq / ton), a film having good hydrolysis resistance cannot be obtained. Polyesters of less than 1 (eq / ton) are difficult to produce industrially.
  • the white polyester film substrate used in the present invention is preferably a white polyester film having a whiteness of 50 or more.
  • the white polyester film substrate used in the present invention is preferably a white polyester film having a thickness of 38 to 1000 ⁇ m, more preferably 50 to 250 ⁇ m, and further preferably 75 to 188 ⁇ m.
  • the thickness of the substrate is less than 38 ⁇ m, the rigidity as a support becomes insufficient, and when it exceeds 1000 ⁇ m, it is not preferable because processing such as cutting becomes difficult.
  • the film of the present invention contains fine particles having an average particle diameter of 0.1 to 3 ⁇ m in an amount of 3 to 50% by mass, preferably 4 to 25% by mass, based on the total mass of the film. If it is 0.1 ⁇ m or less or exceeds 3 ⁇ m, it is difficult to make the whiteness of the film 50 or more even if the addition amount is increased. Moreover, if it is less than 3 mass%, it will become difficult to make whiteness into 50 or more. If it exceeds 50% by mass, the film weight increases, making it difficult to handle it during processing.
  • the average particle diameter of this invention is calculated
  • inorganic or organic particles can be used as the fine particles of the present invention.
  • these fine particles include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, acid value zinc, titanium oxide, zinc sulfide, and organic white pigment, but are not particularly limited. Absent. From the viewpoint of improving whiteness and productivity, titanium oxide or barium sulfate is preferable, and titanium oxide is more preferable. The titanium oxide may be either anatase type or rutile type. Further, the surface of the fine particles may be subjected to an inorganic treatment such as alumina or silica, or may be subjected to an organic treatment such as silicon or alcohol.
  • the addition of fine particles into the film is possible by using a known method, but a master batch method (MB method) in which a polyester resin and fine particles are mixed in an extruder in advance is preferable. Further, it is possible to adopt a method in which a polyester resin and fine particles which have not been dried in advance are put into an extruder and MB is produced while moisture and air are deaerated. Furthermore, it is preferable to prepare an MB using a polyester resin that has been slightly dried in advance to suppress an increase in the acid value of the polyester. In this case, a method of extruding while degassing, a method of extruding without deaeration with a sufficiently dried polyester resin, and the like can be mentioned.
  • the UV irradiation when excellent durability is required even under light irradiation, specifically, when the UV irradiation is performed at 63 ° C., 50% Rh, irradiation intensity of 100 mW / cm 2 for 100 hours, the elongation at break is maintained.
  • the rate is preferably 35% or more, more preferably 40% or more.
  • titanium dioxide mainly composed of rutile type As fine particles to the film of the present invention.
  • Titanium oxide is mainly known in two crystalline forms, rutile and anatase.
  • the anatase has a very high spectral reflectance of ultraviolet rays
  • the rutile type has a high absorption rate of ultraviolet rays (spectral spectroscopy). (Reflectance is small).
  • the present inventor paid attention to such a difference in spectral characteristics in the crystal form of titanium dioxide, and by using the rutile-type ultraviolet absorption performance, in the polyester film for protecting the back surface of the solar cell, the light resistance was improved. is there.
  • the present invention is excellent in film durability under light irradiation even when other ultraviolet absorbers are not substantially added. For this reason, problems such as contamination due to bleeding out of the ultraviolet absorber and a decrease in adhesion are unlikely to occur.
  • the titanium dioxide particle in the preferable aspect of this invention has a rutile type as a main body.
  • “main body” means that the amount of rutile titanium dioxide in all titanium dioxide particles exceeds 50% by mass.
  • the amount of anatase type titanium dioxide in all the titanium dioxide particles is 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 0 mass% or less. If the content of anatase type titanium dioxide exceeds the above upper limit, the amount of rutile type titanium dioxide in the total titanium dioxide particles may be reduced, resulting in insufficient ultraviolet absorption performance. Since the photocatalytic action is strong, the light resistance tends to be lowered by this action.
  • Rutile titanium dioxide and anatase titanium dioxide can be distinguished by X-ray structure diffraction and spectral absorption characteristics.
  • titanium dioxide fine particles having an average particle diameter of 0.1 to 3 ⁇ m are contained in the film of the present invention in an amount of 3 to 50% by mass, preferably 4 to 4% by mass. 25% by mass is contained. If it is 0.1 ⁇ m or less or exceeds 3 ⁇ m, it is difficult to make the whiteness of the film 50 or more even if the addition amount is increased. Moreover, if it is less than 3 mass%, durability under light irradiation may fall. If it exceeds 50% by mass, the film weight increases, making it difficult to handle it during processing.
  • fine particles other than titanium dioxide when fine particles other than titanium dioxide are contained, even when the average particle size and the added amount of the fine particles are within the above ranges, durability under light irradiation is lowered.
  • fine particles other than rutile type titanium oxide fine particles such as silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, acid value zinc, zinc sulfide, organic white pigment, etc. in addition to anatase type titanium dioxide Is exemplified.
  • the rutile titanium dioxide fine particles described above may be subjected to inorganic treatment such as alumina or silica on the fine particle surface, or may be subjected to organic treatment such as silicon or alcohol.
  • Rutile titanium dioxide may be subjected to particle size adjustment and coarse particle removal using a purification process before blending with the polyester composition.
  • a purification process for example, a jet mill or a ball mill can be applied as a pulverizing means, and as a classification means, for example, dry or wet centrifugation can be applied.
  • the film of the present invention may contain many fine cavities inside.
  • the apparent specific gravity is 0.7 or more and 1.3 or less, preferably 0.9 or more and 1.3 or less, more preferably 1.05 or more and 1.2 or less. If it is less than 0.7, the film is not elastic and processing at the time of producing the solar cell module becomes difficult. Even if the film exceeds 1.3, it is within the range of the film of the present invention. However, if the film exceeds 1.3, the film weight is so large that it may become an obstacle when considering the reduction in weight of solar cells. There is.
  • the fine cavities can be formed from a thermoplastic resin that is incompatible with the fine particles and / or polyester described below.
  • the term “cavity derived from a thermoplastic resin that is incompatible with fine particles or polyester” means that there are voids around the fine particles or the thermoplastic resin. For example, confirm with a cross-sectional photograph of the film by an electron microscope. Can do.
  • the polyester used in the present invention can be optionally added with an incompatible thermoplastic resin, and is not particularly limited as long as it is incompatible with the polyester.
  • an incompatible thermoplastic resin includes polystyrene resins, polyolefin resins, polyacrylic resins, polycarbonate resins, polysulfone resins, and cellulose resins.
  • polystyrene resins or polyolefin resins such as polymethylpentene and polypropylene are preferably used.
  • the mixing amount of these void forming agents that is, the thermoplastic resin incompatible with the polyester, with respect to the polyester varies depending on the amount of the target void, but may be in the range of 3 to 20% by mass with respect to the entire film. More preferably, it is 5 to 18% by mass. And if it is less than 3 mass%, there exists a limit in increasing the production amount of a cavity. On the other hand, if it is 20% by mass or more, the stretchability of the film is remarkably impaired, and the heat resistance, strength, and waist strength are impaired.
  • the polyester film for a solar cell back surface protective film of the present invention can be a void-containing polyester film.
  • the polyester film of the present invention may have a single layer or a laminated structure composed of two or more layers.
  • the laminated structure includes a skin layer composed of a polyester layer containing many cavities derived from fine particles having an average particle diameter of 0.1 to 3 ⁇ m, and a polyester containing many cavities derived from a thermoplastic resin incompatible with polyester. It is also a preferred embodiment of the present invention to have a core layer composed of layers.
  • the manufacturing method is arbitrary and is not particularly limited, for example, it can be manufactured as follows.
  • Each raw material is mixed, put into an extruder, melted, extruded from a T-die, and adhered to a cooling roll to obtain an unstretched sheet.
  • the unstretched sheet is further expanded by stretching between rolls having a speed difference (roll stretching), stretching by gripping and expanding by a clip (tenter stretching), stretching by expanding with air pressure (inflation stretching), and the like.
  • Axial orientation treatment By performing the orientation treatment, interfacial peeling occurs between the polyester / incompatible thermoplastic resin and between the polyester / fine particles, and many fine cavities appear. Therefore, the conditions for stretching / orienting the unstretched sheet are closely related to the formation of cavities.
  • the first-stage longitudinal stretching process is the most important process for forming many fine cavities inside the film.
  • stretching is performed between two or many rolls having different peripheral speeds.
  • a heating means at this time a method using a heating roll or a method using a non-contact heating method may be used, or they may be used in combination.
  • the most preferable stretching method is a method using both roll heating and non-contact heating.
  • the film is first preheated to a temperature of 50 ° C. to the glass transition point of polyester using a heating roll, and then heated with an infrared heater.
  • the uniaxially stretched film thus obtained is introduced into a tenter and stretched 2.5 to 5 times in the width direction.
  • a preferred stretching temperature at this time is 100 ° C. to 200 ° C.
  • the biaxially stretched film thus obtained is subjected to heat treatment as necessary.
  • the heat treatment is preferably carried out in a tenter, preferably in the range of the melting point Tm-50 ° C. to Tm of the polyester.
  • the coating solution used for forming the coating layer of the present invention is preferably an aqueous coating solution containing at least one of water-soluble or water-dispersible copolymerized polyester resin, acrylic resin and polyurethane resin.
  • these coating liquids include water-soluble or water-dispersible copolyester resin solutions, acrylic resin solutions, polyurethane resin solutions disclosed in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, and the like. Etc.
  • the coating layer can be obtained by applying the coating liquid on one or both sides of a uniaxially stretched film in the longitudinal direction, drying at 100 to 150 ° C., and stretching in the transverse direction.
  • the final coating amount of the coating layer is preferably controlled to 0.05 to 0.20 g / m 2 . If the coating amount is less than 0.05 g / m 2 , adhesion with the resulting EVA resin may be insufficient. On the other hand, when the coating amount exceeds 0.20 g / m 2 , blocking resistance may be lowered.
  • the coating amounts of the coating layers on both sides may be the same or different, and can be independently set within the above range.
  • the particles to be included in the coating layer include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide, barium sulfate, calcium fluoride, and fluoride.
  • Inorganic particles such as lithium, zeolite, molybdenum sulfide and mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate resin particles, benzoguanamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, polytetrafluoroethylene particles And heat resistant polymer particles.
  • silica particles having a relatively close refractive index to the resin component of the coating layer are preferable.
  • a known method can be used as a method for applying the coating solution.
  • reverse roll coating method gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, etc.
  • spray coating method air knife coating method, wire bar coating method, pipe doctor method, etc.
  • wire bar coating method wire bar coating method
  • pipe doctor method etc.
  • thermo adhesive layer in order to improve the adhesiveness with the EVA resin, it is also preferable to laminate a thermal adhesive layer mainly composed of an amorphous polyester resin on at least one surface of the white polyester film substrate.
  • main component as used herein means that the amorphous polyester resin is 50% by mass or more based on the mass of the entire thermal bonding layer.
  • the thermal adhesive layer here is a layer that can be thermally bonded to the EVA resin under heating conditions. By laminating this thermal adhesive layer on the white polyester film substrate, it is possible to adhere to the EVA resin without providing an adhesive layer. It is important that the thickness of the thermal adhesive layer is 1 to 40 ⁇ m per layer.
  • the thickness of the thermal adhesive layer is preferably 3 to 30 ⁇ m, more preferably 5 to 25 ⁇ m, and particularly preferably 10 to 20 ⁇ m for the above reasons.
  • the means for providing the thermal adhesive layer on the surface of the white polyester film substrate is not particularly limited, but an unstretched sheet is produced using a method in which two kinds of resins are coextruded and laminated in a melt extrusion process, a so-called coextrusion method. It is preferable. Moreover, it is preferable to laminate
  • the thermal adhesive layer in the present invention is mainly composed of an amorphous polyester resin, and has a thermal expansion coefficient greatly different from that of a base material layer mainly composed of a crystalline polyester resin. For this reason, when a thermal adhesive layer is provided only on one side of the substrate, it may curl like a bimetal depending on processing conditions and use conditions, and there is a concern about poor flatness and handling properties.
  • the thermal adhesive layers are provided on both surfaces of the substrate, the thickness ratio of the front and back thermal adhesive layers is preferably 0.5 to 2.0. When it is out of this range, curling may occur due to the above reason.
  • the curl value after heating at 110 ° C. for 30 minutes in a no-load state is 5 mm or less, there will be no substantial hindrance to handling properties. It is preferably 3 mm or less, and more preferably 1 mm or less.
  • the thermal adhesive layer in the present invention is important for the thermal adhesive layer in the present invention to use an amorphous polyester resin as a main component occupying 50% by mass or more of the layer.
  • the amorphous polyester resin here is a polyester resin having a heat of fusion of 20 J / g or less.
  • the heat of fusion is measured by heating at a rate of 10 ° C./min in a nitrogen atmosphere using a DSC apparatus according to “Method for measuring the heat of transition of plastic” described in JIS − K7122.
  • the heat of fusion is preferably 10 J / g or less, and more preferably 5 J / g or less. When the amount of heat of fusion exceeds 20 J / g, sufficient heat adhesion cannot be obtained.
  • the amorphous polyester resin preferably has a glass transition temperature of 50 ° C. or higher and 100 ° C. or lower.
  • This glass transition temperature is a DSC curve obtained by heating at a rate of 10 ° C./min in a nitrogen atmosphere using a DSC apparatus according to “Method for measuring plastic transition temperature” described in JIS − K7121. Is the midpoint glass transition temperature (Tmg) determined based on
  • the glass transition temperature of the amorphous polyester resin A is preferably 60 to 90 ° C, more preferably 70 to 85 ° C.
  • the glass transition temperature is less than 50 ° C., the heat adhesion is insufficient and deforms, or the thermal adhesive layer peels off again due to the temperature rise during use.
  • the glass transition temperature exceeds 100 ° C., it is necessary to heat the solar cell panel at a higher temperature, which increases the burden on the electric circuit and the like.
  • the kind of the amorphous polyester resin is not particularly limited, but from the viewpoint of versatility, cost, durability, or thermal adhesiveness, those in which various copolymerization components are introduced into the molecular skeleton of the aromatic polyester resin are preferable.
  • the copolymer components to be introduced include ethylene glycol, diethylene glycol, neopentyl glycol (NPG), cyclohexanedimethanol (CHDM), propanediol, butanediol, and the acid components include terephthalic acid, isophthalic acid, and naphthalene. Dicarboxylic acid and the like are preferably used.
  • a copolymer polyester resin in which isophthalic acid, CHDM, and / or NPG is introduced into the molecular skeleton of a polyethylene terephthalate resin is preferable from the viewpoint of processability, and one in which NPG is introduced is more preferable.
  • the thermal adhesive layer in the present invention preferably contains a thermoplastic resin that is incompatible with the amorphous polyester resin.
  • a thermoplastic resin that is incompatible with the amorphous polyester resin.
  • thermoplastic resin that is incompatible with the amorphous polyester resin is not particularly limited, but as a highly versatile resin, polystyrene, polycarbonate, acrylic, cyclic polyolefin and copolymers thereof, crystalline polyolefin such as polypropylene and polyethylene, etc. And copolymers thereof.
  • polystyrene, polyolefin, or a copolymer thereof is preferable, and polystyrene, polypropylene, or polyethylene is more preferable.
  • the amount of the thermoplastic resin contained in the thermal adhesive layer is 1 to 30% by mass with respect to the material constituting the thermal adhesive layer. 3 to 25% by mass is preferable, and 5 to 20% by mass is more preferable.
  • the content of the thermoplastic resin is less than 1% by mass, the necessary slip properties cannot be obtained.
  • it exceeds 30% by mass the thermal adhesiveness is inhibited.
  • the above-mentioned fine particles are contained in the heat-adhesive layer as long as the heat-adhesive property is not impaired.
  • the fine particles white pigments, that is, titanium oxide or barium sulfate and composite particles thereof are preferable, and titanium oxide is more preferably used from the viewpoint of concealment effect.
  • These white pigments are preferably contained in the heat bonding layer in an amount of 30% by mass or less, and more preferably 15% by mass or less. If added beyond the above range, the thermal adhesiveness may be inhibited.
  • the film of the present invention has an acid value of 1 (eq / ton) to 30 (eq / ton), preferably 2 (eq / ton) to 20 (eq / ton), more preferably 2 (eq / ton). ton) to 16 (eq / ton). If it exceeds 30 (eq / ton), a film having good hydrolysis resistance cannot be obtained. A film of less than 1 (eq / ton) is difficult to produce industrially.
  • the film of the present invention has a breaking elongation retention ratio of 60% or more, preferably 70% or more, more preferably 80% or more, which is an evaluation of hydrolysis resistance. If it is less than 60%, the durability as a solar cell back surface protective film is low and cannot be used.
  • sample A film or a raw material polyester resin is pulverized and vacuum-dried at 70 ° C. for 24 hours, and then weighed in a range of 0.20 ⁇ 0.0005 g using a balance. The mass at that time is defined as W (g).
  • a sample weighed with 10 ml of benzyl alcohol is added to a test tube, the test tube is immersed in a benzyl alcohol bath heated to 205 ° C., and the sample is dissolved while stirring with a glass rod. Samples with dissolution times of 3 minutes, 5 minutes, and 7 minutes are designated as A, B, and C, respectively.
  • the titration amounts of samples a, b, and c are Xa, Xb, and Xc (ml).
  • Carboxyl terminal concentration (eq / ton) [(V ⁇ V0) ⁇ 0.04 ⁇ NF ⁇ 1000] / W NF: factor W of 0.04 mol / l potassium hydroxide solution: sample mass (g)
  • thermocompression-bonded sample at 23 ° C and 50% RH in accordance with JIS-Z0237 with the unattached film sandwiched between the upper and lower clips at a peel angle of 180 ° and a pulling speed of 100 mm / min. did.
  • EVA is an abbreviation for ethylene-vinyl acetate copolymer.
  • Example 1 (Preparation of fine particle-containing masterbatch) The average particle size was 50% by mass of polyethylene terephthalate resin (PET-I) having an intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton), which was dried at 120 ° C. under 10 ⁇ 3 torr for about 8 hours in advance.
  • PET-I polyethylene terephthalate resin
  • a mixture of 50% by mass of rutile titanium dioxide with a diameter of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder, kneaded and extruded at 275 ° C while degassing to produce fine particles (titanium oxide) Containing masterbatch (MB-I) pellets were prepared.
  • the acid value of this pellet was 8.6 (eq / ton).
  • the raw material of the layer (A) in which 50% by mass of polyethylene terephthalate resin (PET-I) and 50% by mass of the previously prepared MB-I were mixed, 90% by mass of PET-I and MB-I were 10% by mass is used as a raw material for the layer (B), put into separate extruders, mixed and melted at 280 ° C., and then, using a feed block, the layer B is joined to one side of the layer A in a molten state. .
  • the discharge rate ratio of the A layer and the B layer was controlled using a gear pump.
  • the sheet was extruded onto a cooling drum adjusted to 30 ° C. using a T-die to prepare an unstretched sheet so as to be an A / B / A layer.
  • the obtained unstretched sheet was uniformly heated to 70 ° C. using a heating roll, and 3.3-fold roll stretching was performed at 90 ° C.
  • the obtained uniaxially stretched film was led to a tenter, heated to 140 ° C. and transversely stretched 3.7 times, fixed in width and subjected to heat treatment at 220 ° C. for 5 seconds, and further at 220 ° C. in the width direction of 4%.
  • a plastic film for a solar cell back surface protective film having a thickness of 188 ⁇ m (19/150/19) was obtained.
  • Example 2 Preparation of cavity forming agent
  • 20% by mass of polystyrene with a melt flow rate of 1.5 manufactured by Nippon Polystyrene Co., Ltd., G797N
  • 20% by mass of vapor phase polymerization polypropylene with a melt flow rate of 3.0 melt flow rate of 3.0
  • melt flow 60% by mass pellet of polymethylpentene having a rate of 180 Mitsubishi Chemicals Co., Ltd .: TPX DX-820 was supplied to a twin screw extruder and kneaded sufficiently to prepare a cavity forming agent (MB-II).
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 1 except that PET-I: MB-I: MB-II was changed to 82: 10: 8 (mass%) as a raw material for the B layer. It was.
  • Example 3 Example 4, Comparative Example 1 Except that the acid value of polyethylene terephthalate resin as a film raw material was 10.1, 19.5, 30.2 (PET-II, PET-III, PET-IV, respectively) A plastic film for the battery back surface protective film was obtained.
  • Comparative Example 2 In the preparation of a master batch containing fine particles, a polyethylene terephthalate resin having an undried intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton) stored in a paper bag as a raw material in a place where temperature and humidity are not controlled (PET-I) 50 mass% mixed with 50 mass% rutile type titanium dioxide having an average particle size of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder and kneaded to 305 ° C. A masterbatch (MB-III) pellet containing fine particles (titanium oxide) was prepared while degassing with a. The acid value of this pellet was 38.4 (eq / ton). Other than that obtained the plastic film for solar cell back surface protective films by the method similar to Example 2.
  • Example 5 In the production of the master batch containing fine particles, barium sulfate having an average particle size of 0.6 ⁇ m was used instead of rutile titanium dioxide (MB-IV), and it was used instead of MB-I as a raw material for the A layer.
  • MB-IV rutile titanium dioxide
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 2.
  • Example 6 (Preparation of fine particle-containing masterbatch) The average particle size was 50% by mass of polyethylene terephthalate resin (PET-I) having an intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton), which was dried at 120 ° C. under 10 ⁇ 3 torr for about 8 hours in advance.
  • PET-I polyethylene terephthalate resin
  • a mixture of 50% by mass of rutile titanium dioxide with a diameter of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder, kneaded and extruded at 275 ° C while degassing to produce fine particles (titanium oxide) Containing masterbatch (MB-I) pellets were prepared.
  • the acid value of this pellet was 8.6 (eq / ton).
  • a transesterification reaction and a polycondensation reaction were carried out by a conventional method, and as a dicarboxylic acid component (based on the total dicarboxylic acid component) 46 mol% terephthalic acid, 46 mol% isophthalic acid and 8 mol% sodium 5-sulfonatoisophthalate, A water-dispersible sulfonic acid metal base-containing copolymer polyester resin having a composition of 50 mol% ethylene glycol and 50 mol% neopentyl glycol as a glycol component (based on the entire glycol component) was prepared.
  • the raw material of the layer (A) in which 50% by mass of polyethylene terephthalate resin (PET-I) and 50% by mass of the previously prepared MB-I were mixed, 90% by mass of PET-I and MB-I were 10% by mass is used as a raw material for the layer (B), put into separate extruders, mixed and melted at 280 ° C., and then, using a feed block, the layer B is joined to one side of the layer A in a molten state. .
  • the discharge rate ratio of the A layer and the B layer was controlled using a gear pump.
  • the sheet was extruded onto a cooling drum adjusted to 30 ° C. using a T-die to prepare an unstretched sheet so as to be an A / B / A layer.
  • the obtained unstretched sheet was uniformly heated to 70 ° C. using a heating roll, and 3.3-fold roll stretching was performed at 90 ° C. to obtain a uniaxially stretched polyester film.
  • the coating solution was applied to one side of the obtained uniaxially stretched polyester film so that the final coating layer thickness was 0.08 g / m 2, and then dried at 135 ° C.
  • Example 7 Preparation of cavity forming agent
  • 20% by mass of polystyrene with a melt flow rate of 1.5 manufactured by Nippon Polystyrene Co., Ltd., G797N
  • 20% by mass of vapor phase polymerization polypropylene with a melt flow rate of 3.0 melt flow rate of 3.0
  • melt flow 60% by mass pellet of polymethylpentene having a rate of 180 Mitsubishi Chemicals Co., Ltd .: TPX DX-820 was supplied to a twin screw extruder and kneaded sufficiently to prepare a cavity forming agent (MB-II).
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 6 except that PET-I: MB-I: MB-II was changed to 82: 10: 8 (mass%) as a raw material for the B layer. It was.
  • Example 8 Example 9, Comparative Example 3 Except that the acid value of polyethylene terephthalate resin as a film raw material was 10.1, 19.5, 30.2 (PET-II, PET-III, PET-IV, respectively) A plastic film for the battery back surface protective film was obtained.
  • Comparative Example 4 In the preparation of a master batch containing fine particles, a polyethylene terephthalate resin having an undried intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton) stored in a paper bag as a raw material in a place where temperature and humidity are not controlled (PET-I) 50 mass% mixed with 50 mass% rutile type titanium dioxide having an average particle size of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder and kneaded to 305 ° C. A masterbatch (MB-III) pellet containing fine particles (titanium oxide) was prepared while degassing with a. The acid value of this pellet was 38.4 (eq / ton). Other than that obtained the plastic film for solar cell back surface protective films by the method similar to Example 7. FIG.
  • Example 10 In the production of the master batch containing fine particles, barium sulfate having an average particle size of 0.6 ⁇ m was used instead of rutile titanium dioxide (MB-IV), and it was used instead of MB-I as a raw material for the A layer.
  • MB-IV rutile titanium dioxide
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 7.
  • Example 11 A polyester film for a solar cell back surface protective film was obtained in the same manner as in Example 7 except that the coating layer was not provided.
  • Example 12 (Preparation of fine particle-containing masterbatch)
  • a polyethylene terephthalate resin (PET-A) having an intrinsic viscosity of 0.69 and an acid value of 8 (eq / ton) dried at 120 ° C. under a vacuum of 10 Pa for about 8 hours in advance has an average particle size of 0.1%.
  • PET-A polyethylene terephthalate resin
  • rutile titanium oxide to a vent type twin screw extruder, kneading and extruding at 275 ° C while degassing, preparing fine particle-containing master batch pellets did.
  • this master batch pellet was subjected to solid phase polymerization under a vacuum of 10 Pa until the intrinsic viscosity became 0.79, to prepare a fine particle-containing master batch (MB-A).
  • the acid value of MB-A was 23 (eq / ton).
  • amorphous polyester resin (Preparation of amorphous polyester resin) Transesterification and polycondensation reactions are carried out by conventional methods, and an amorphous polyester resin (Co-PET) comprising 100 mol% terephthalic acid as the dicarboxylic acid component, 70 mol% ethylene glycol and 30 mol% neopentyl glycol as the glycol component was prepared. This resin had an intrinsic viscosity of 0.72 and an acid value of 19 eq / ton.
  • the discharge rate ratio of the A layer and the B layer was controlled using a gear pump.
  • the sheet was extruded onto a cooling drum adjusted to 30 ° C. using a T-die to produce an unstretched sheet having an A / B / A layer structure.
  • the obtained unstretched sheet was uniformly heated to 70 ° C. using a heating roll, and 3.3-fold roll stretching was performed at 90 ° C. to obtain a uniaxially stretched polyester film. This was led to a tenter, heated to 140 ° C. and stretched to 3.7 times, fixed in width, subjected to heat treatment at 230 ° C. for 5 seconds, and further relaxed by 4% in the width direction at 220 ° C.
  • stacked the thermal adhesive layer of 188 micrometers (19/150/19) was obtained.
  • Example 13 Preparation of coating solution
  • a water / isopropyl alcohol-based coating solution containing 1% by mass with respect to the solid content was prepared.
  • Example 14 Preparation of cavity forming agent master batch
  • 20% by mass of polystyrene having a melt flow rate of 1.5 (manufactured by Nippon Polystyrene Co., Ltd., G797N)
  • 20% by mass of vapor phase polymerization polypropylene having a melt flow rate of 3.0 (manufactured by Idemitsu Kosan Co., Ltd., F300SP)
  • 60% by mass of polymethylpentene having a melt flow rate of 180 manufactured by Mitsui Chemicals: TPX DX-820
  • TPX DX-820 60% by mass of polymethylpentene having a melt flow rate of 180
  • Example 15 The polyethylene terephthalate resin used as a raw material was changed to one having an intrinsic viscosity of 0.69 and an acid value of 19 (eq / ton) (PET-B). Further, solid phase polymerization treatment was not performed in the production of the fine particle-containing master batch, and the master batch (MB-A2) having an acid value of 39 eq / ton was used. Except this, the polyester film for solar cell back surface protective films which laminated
  • Comparative Example 5 In the preparation of the master batch containing fine particles, PET-A (water content 3500 ppm) which was not subjected to drying treatment was used, and solid phase polymerization treatment was not conducted. The acid value of the pellet (MB-A3) was 57 (eq / ton). In place of PET-A, a polyethylene terephthalate resin (PET-C) having an acid value of 31 (eq / ton) was used. Except this, the polyester film for solar cell back surface protective films which laminated
  • PET-C polyethylene terephthalate resin
  • Example 16 A master batch (MB-A4) containing fine particles was prepared using anatase-type titanium oxide having an average particle size of 0.2 ⁇ m instead of rutile-type titanium oxide.
  • a polyester film for a solar cell back surface protective film in which a thermal adhesive layer was laminated was obtained in the same manner as in Example 14 except that this was used in place of MB-A1 as a raw material for the B layer.
  • Example 17 For the raw material supplied to the extruder A, PET-A was used instead of Co-PET. Except this, a polyester film for solar cell back surface protective film having no thermal adhesive layer was obtained in the same manner as in Example 14.
  • Example 18 In Example 12, instead of the polystyrene resin supplied to the extruder A, a polyethylene resin (manufactured by Ube Industries, Umerit 2040F, melting point 116 ° C., density 0.918 g / cm 3 ) was used. The raw material ratio was changed to that shown in Table 5. This obtained the polyester film for solar cell back surface protective films which laminated
  • a polyethylene resin manufactured by Ube Industries, Umerit 2040F, melting point 116 ° C., density 0.918 g / cm 3
  • Example 19 A transesterification reaction and a polycondensation reaction were carried out by a conventional method to prepare an amorphous polyester resin composed of 80 mol% terephthalic acid and 20 mol% isophthalic acid as the dicarboxylic acid component and 100 mol% ethylene glycol as the glycol component.
  • This resin had an intrinsic viscosity of 0.67 and an acid value of 22 eq / ton. 95% by mass of this amorphous polyester resin and 5% by mass of polyethylene wax (manufactured by Mitsui Chemicals, NL500) were mixed and supplied to a twin screw extruder, and kneaded thoroughly to prepare a wax agent master batch (MB- C) was adjusted.
  • MB- C wax agent master batch
  • Example 20 The raw material supplied to the extruder A was a mixture of Co-PET, PET-A and polystyrene at the ratio shown in Table 3. Except this, a polyester film for a solar cell back surface protective film having no thermal adhesive layer was obtained in the same manner as in Example 12.
  • the polyester film for the solar cell back surface protective film of the examples within the scope of the present invention exhibited excellent durability and EVA resin adhesion.
  • the films of Comparative Examples 1 and 2 that are outside the scope of the present invention have poor durability, and the films of Examples 17, 20, and 21 have poor adhesion to the EVA resin.
  • Example 22 (Preparation of fine particle-containing masterbatch) The average particle size was 50% by mass of polyethylene terephthalate resin (PET-I) having an intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton), which was dried at 120 ° C. under 10 ⁇ 3 torr for about 8 hours in advance.
  • PET-I polyethylene terephthalate resin
  • a mixture of 50% by mass of rutile type titanium dioxide having a diameter of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder, kneaded and extruded at 275 ° C. while degassing, and rutile type titanium dioxide fine particles.
  • Containing masterbatch (MB-I) pellets were prepared. The acid value of this pellet was 8.6 (eq / ton).
  • the discharge rate ratio of the A layer and the B layer was controlled using a gear pump.
  • the sheet was extruded onto a cooling drum adjusted to 30 ° C. using a T-die to prepare an unstretched sheet so as to be an A / B / A layer.
  • the obtained unstretched sheet was uniformly heated to 70 ° C. using a heating roll, and 3.3-fold roll stretching was performed at 90 ° C.
  • the obtained uniaxially stretched film was led to a tenter, heated to 140 ° C. and transversely stretched 3.7 times, fixed in width and subjected to heat treatment at 220 ° C. for 5 seconds, and further at 220 ° C. in the width direction of 4%.
  • a plastic film for a solar cell back surface protective film having a thickness of 188 ⁇ m (19/150/19) was obtained.
  • Example 23 Preparation of cavity forming agent
  • 20% by mass of polystyrene with a melt flow rate of 1.5 manufactured by Nippon Polystyrene Co., Ltd., G797N
  • 20% by mass of vapor phase polymerization polypropylene with a melt flow rate of 3.0 melt flow rate of 3.0
  • melt flow 60% by mass pellet of polymethylpentene having a rate of 180 Mitsubishi Chemicals Co., Ltd .: TPX DX-820
  • a twin screw extruder and kneaded sufficiently to prepare a cavity forming agent (MB-II).
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 22 except that PET-I: MB-I: MB-II was changed to 80: 12: 8 (mass%) as a raw material for the B layer. It was.
  • Example 24, Example 25, Comparative Example 7 A solar cell was produced in the same manner as in Example 23 except that the acid value of polyethylene terephthalate resin as a film raw material was 10.1, 19.5, 30.2 (PET-II, PET-III, and PET-IV, respectively). A plastic film for the battery back surface protective film was obtained.
  • Example 26 A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 24 except that the amount of MB-I added in Example 24 was changed as shown in the table.
  • Example 27 In the preparation of the fine particle-containing masterbatch, as a raw material, 50% by mass of polyethylene terephthalate resin (PET-I) and 50% by mass of anatase-type titanium dioxide having an average particle size of 0.3 ⁇ m (electron microscopic method) are bent. The mixture was supplied to a shaft extruder, kneaded and extruded at 275 ° C. while degassing to prepare fine particle-containing master batch (MB-III) pellets. The acid value of this pellet was 8.1 (eq / ton). A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 23 except that MB-III was used instead of the fine particle-containing master batch MB-I.
  • PET-I polyethylene terephthalate resin
  • anatase-type titanium dioxide having an average particle size of 0.3 ⁇ m electrostatic method
  • Comparative Example 8 In the preparation of a master batch containing fine particles, a polyethylene terephthalate resin having an undried intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton) stored in a paper bag as a raw material in a place where temperature and humidity are not controlled (PET-I) 50 mass% mixed with 50 mass% rutile type titanium dioxide having an average particle size of 0.3 ⁇ m (electron microscopic method) is supplied to a vent type twin screw extruder and kneaded to 305 ° C. A masterbatch (MB-IV) pellet containing fine particles (titanium oxide) was prepared while degassing with a vacuum. The acid value of this pellet was 38.4 (eq / ton). A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 23 except that MB-IV was used instead of the fine particle-containing master batch MB-I.
  • PET-I polyethylene terephthalate resin having an undried intrinsic
  • Example 28 A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 22 except that MB-III was used instead of the fine particle-containing master batch MB-I.
  • Example 29 In the preparation of the master batch containing fine particles, barium sulfate having an average particle diameter of 0.6 ⁇ m was used instead of rutile titanium dioxide (MB-V), and it was used instead of MB-I as a raw material for the A layer.
  • MB-V rutile titanium dioxide
  • a plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 23.
  • the polyester film for solar cell back surface protective film of the present invention is excellent in durability and light reflection efficiency under high temperature and high humidity, and is useful as a material constituting the solar cell back surface protective film.

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Abstract

L'invention concerne un film polyester pour couche de protection de surface arrière de cellule solaire présentant, pour une cellule solaire à silicium à couche mince, des propriétés excellentes de durée de vie dans des conditions de température et d'humidité élevées. Le film polyester pour couche de protection de surface arrière de cellule solaire se caractérise par le fait que son degré de blancheur est supérieur ou égal à 50; par le fait qu'il possède de 3 à 50% en masse de microparticules dont le diamètre de particule moyen est compris entre 0,1 et 3µm; et par le fait que son indice d'acidité est supérieur ou égal à 1 (eq/ton) et inférieur ou égal à 30 (eq/ton).
PCT/JP2010/050084 2009-01-07 2010-01-07 Film polyester pour couche de protection de surface arrière de cellule solaire Ceased WO2010079798A1 (fr)

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JP2009001489A JP5114681B2 (ja) 2009-01-07 2009-01-07 太陽電池裏面保護膜用ポリエステルフィルム
JP2009-001489 2009-01-07
JP2009-002369 2009-01-08
JP2009002369A JP5572949B2 (ja) 2009-01-08 2009-01-08 太陽電池裏面保護膜用ポリエステルフィルムの製造方法
JP2009224198 2009-09-29
JP2009-224198 2009-09-29
JP2009-226778 2009-09-30
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WO2012132922A1 (fr) * 2011-03-30 2012-10-04 リンテック株式会社 Feuille de protection pour cellules solaires, son procédé de fabrication, et module de cellules solaires
WO2012132921A1 (fr) * 2011-03-30 2012-10-04 リンテック株式会社 Feuille de protection pour cellule solaire, procédé de fabrication associé, et module cellule solaire
JP2013058748A (ja) * 2011-08-17 2013-03-28 Fujifilm Corp 太陽電池用バックシート及びその製造方法並びに太陽電池モジュール
WO2013137167A1 (fr) * 2012-03-12 2013-09-19 富士フイルム株式会社 Film polyester et son procédé de production, feuille arrière pour module solaire photovoltaïque, et module solaire photovoltaïque
US20150068601A1 (en) * 2012-03-14 2015-03-12 Toyobo Co., Ltd. Sealing sheet for back surface of solar cell, and solar cell module
TWI499064B (zh) * 2011-10-07 2015-09-01 Toyo Boseki 太陽能電池用白色聚酯薄膜、使用其之太陽能電池背面封裝片及太陽能電池模組
WO2019072108A1 (fr) * 2017-10-11 2019-04-18 珠海奔图电子有限公司 Puce et son procédé de détection d'installation, unité remplaçable et dispositif de formation d'image
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CN110845694A (zh) * 2019-11-08 2020-02-28 浙江华峰热塑性聚氨酯有限公司 一种可进行光传输的热塑性聚氨酯及其制备方法

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WO2012005034A1 (fr) * 2010-07-06 2012-01-12 帝人デュポンフィルム株式会社 Film polyester pour membrane protectrice de surface arrière d'une cellule photovoltaïque
JP2012018971A (ja) * 2010-07-06 2012-01-26 Teijin Dupont Films Japan Ltd 太陽電池裏面保護膜用ポリエステルフィルム
WO2012132922A1 (fr) * 2011-03-30 2012-10-04 リンテック株式会社 Feuille de protection pour cellules solaires, son procédé de fabrication, et module de cellules solaires
WO2012132921A1 (fr) * 2011-03-30 2012-10-04 リンテック株式会社 Feuille de protection pour cellule solaire, procédé de fabrication associé, et module cellule solaire
JP2012209461A (ja) * 2011-03-30 2012-10-25 Lintec Corp 太陽電池用保護シートおよびその製造方法、ならびに太陽電池モジュール
JP2012209462A (ja) * 2011-03-30 2012-10-25 Lintec Corp 太陽電池用保護シートおよびその製造方法、ならびに太陽電池モジュール
JP2013058748A (ja) * 2011-08-17 2013-03-28 Fujifilm Corp 太陽電池用バックシート及びその製造方法並びに太陽電池モジュール
TWI499064B (zh) * 2011-10-07 2015-09-01 Toyo Boseki 太陽能電池用白色聚酯薄膜、使用其之太陽能電池背面封裝片及太陽能電池模組
WO2013137167A1 (fr) * 2012-03-12 2013-09-19 富士フイルム株式会社 Film polyester et son procédé de production, feuille arrière pour module solaire photovoltaïque, et module solaire photovoltaïque
US20150068601A1 (en) * 2012-03-14 2015-03-12 Toyobo Co., Ltd. Sealing sheet for back surface of solar cell, and solar cell module
US10896987B2 (en) * 2012-03-14 2021-01-19 Toyobo Co., Ltd. Sealing sheet for back surface of solar cell, and solar cell module
US10439086B2 (en) 2014-07-08 2019-10-08 Dupont Teijin Films U.S. Limited Partnership Polyester film comprising amorphous polyester
WO2019072108A1 (fr) * 2017-10-11 2019-04-18 珠海奔图电子有限公司 Puce et son procédé de détection d'installation, unité remplaçable et dispositif de formation d'image
US10996611B2 (en) 2017-10-11 2021-05-04 Zhuhai Pantum Electronics Co., Ltd. Chip and replaceable unit of image forming apparatus
CN110845694A (zh) * 2019-11-08 2020-02-28 浙江华峰热塑性聚氨酯有限公司 一种可进行光传输的热塑性聚氨酯及其制备方法

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