WO2011040398A1 - 太陽電池用ポリエステルフィルム - Google Patents
太陽電池用ポリエステルフィルム Download PDFInfo
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- WO2011040398A1 WO2011040398A1 PCT/JP2010/066805 JP2010066805W WO2011040398A1 WO 2011040398 A1 WO2011040398 A1 WO 2011040398A1 JP 2010066805 W JP2010066805 W JP 2010066805W WO 2011040398 A1 WO2011040398 A1 WO 2011040398A1
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- film
- polyester
- polyester film
- resin
- solar cell
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- 239000000088 plastic resin Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- NUBZKXFFIDEZKG-UHFFFAOYSA-K trisodium;5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=CC(C([O-])=O)=CC(S([O-])(=O)=O)=C1 NUBZKXFFIDEZKG-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/9122—Mirror
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a polyester film for solar cells. More specifically, the present invention relates to a solar cell polyester film suitable for a solar cell backsheet that provides a high reflectance in the reflectance, particularly in the infrared region, when used in a solar cell backsheet.
- a solar cell is a solar power generation system that directly converts solar energy into electricity, and the heart of the solar cell is made of a semiconductor.
- solar cell elements are not used as they are, and generally several to several tens of solar cell elements are wired in series and in parallel, for a long time (about 20 years or more).
- various packaging is performed and unitized. The unit incorporated in this package is called a solar cell module.
- the surface that is exposed to sunlight is covered with glass, the gap is filled with a filler made of a thermoplastic resin, and the back surface is backed with a heat-resistant or weather-resistant plastic material. It is the structure protected by the protective sheet which has a some layer structure called a sheet
- the back sheet is a moisture-proof layer / adhesive / polyvinyl fluoride film such as a film having a polyester film / adhesive / metal foil or metal thin film layer from the solar cell element side.
- a laminated structure such as a polyester-based highly durable moisture-proof film (outermost layer) is common.
- solar cell elements and solar cell backsheets have been improved. For example, even when light incident from the front side of the solar cell module is transmitted through the solar cell element, the light is re-incident on the solar cell element by reflecting the light, and the photovoltaic power is effectively utilized by using the light effectively. improves.
- the solar cell backsheet is required to have a high reflectance and a small reflection directivity in order to reflect uniformly to nearby elements.
- crystalline silicon used as a solar cell element has sensitivity in the wavelength range of 400 to 1200 nm, and has high sensitivity in the near-infrared light region rather than the visible light region. Therefore, the reflection characteristics of the solar cell backsheet are important not only in the visible light region but also in the near infrared light region (wavelength 700 to 1200 nm). Then, the following are proposed as a polyester film used for the solar cell backsheet, for example.
- Patent Document 1 proposes a solar cell back surface sealing film in which an incompatible resin is mixed with polyethylene terephthalate resin and the reflection efficiency is improved by using bubbles generated during film formation, and reflection at a wavelength of 560 nm is proposed.
- the film for solar cell backside sealing whose rate is 84 to 87% is illustrated.
- Patent Document 2 proposes a plastic film for a solar cell back surface protective film in which a plastic that constitutes a plastic film is mixed with a white colorant, and has an average reflectance of 82 to 93% in the wavelength range of 600 to 1400 nm. A protective film plastic film is illustrated.
- Patent Document 3 proposes a white polyester film for protecting a back surface of a solar cell in which barium sulfate particles are contained in a polyester resin, and the back surface of the solar cell having an average reflectance of 86 to 97% in the visible light region having a wavelength of 400 to 700 nm.
- the white polyester film for protective films is illustrated.
- Patent Document 4 proposes a solar cell module using a biaxially stretched polyethylene terephthalate film kneaded with a white pigment, a polyethylene terephthalate film containing fine bubbles, or a resin film provided with a light-reflective coating layer. A back cover film having total light reflectance of 95% and 97% is illustrated.
- the solar cell backsheet is required to have a high reflectance not only in the visible light region but also in the near infrared region in order to obtain high conversion efficiency of the solar cell module. It is expected that.
- a method of adding a foaming agent or a white pigment to a film is used to impart light reflectivity to a film, and the reflectance is improved by increasing the amount of these additives.
- the reflectance is improved by increasing the amount of these additives.
- the improvement in the reflectance in the visible light region and the near infrared region is small, but by adding a large amount of a foaming agent or a white pigment, mechanical strength such as tensile strength decreases, There is a limit in maintaining strength because creases tend to occur.
- an object of the present invention is to provide a solar cell polyester film suitable for a solar cell backsheet that is required not only in the visible light region but also in the near infrared region and having a high reflectance and a small reflection directivity. Is to provide.
- the inventors of the present invention have made extensive studies on the reflectance of the polyester film for solar cells, particularly the reflectance in the near infrared region.
- a large amount of a foaming agent or white pigment was added, and the light reflecting film alone
- a white film having a predetermined near-infrared transmittance by using a white film having a predetermined near-infrared transmittance, a light-reflective layer such as a metal moisture-proof layer such as an aluminum foil disposed on the back surface is provided.
- a first invention of the present application is a void-containing polyester film having an average reflectance in a wavelength range of 400 to 1200 nm of 70% or more and 95% or less, and an average transmittance of 5% in a wavelength range of 700 to 1200 nm.
- the above is a polyester film for solar cells that is 30% or less.
- 2nd invention of this application is the said polyester film for solar cells whose cyclic trimer content in a polyester film is 5000 ppm or less.
- 3rd invention of this application is the said polyester film for solar cells containing aluminum and / or its compound, and a phenol type compound.
- the solar cell backsheet using the polyester film for solar cells of the present invention has a high reflectivity not only in the visible light region but also in the near infrared region, and has a small reflection directivity.
- the constituent of the polyester film for solar cells of the present invention is a void-containing polyester film.
- the average reflectance in the wavelength range of 400 to 1200 nm is 70% or more and 95% or less, and the average transmittance in the wavelength range of 700 to 1200 nm is 5%.
- the polyester film for solar cells which is 30% or less is obtained.
- a light reflective layer such as a metal layer
- a back sheet for solar cell having high light reflectivity and small reflection directivity can be obtained.
- the void-containing polyester film of the present invention can be obtained, for example, by appropriately dispersing a thermoplastic resin incompatible with the resin in a polyester resin and stretching the resin.
- the above polyester-based resin is mainly composed of an ester unit formed from dicarboxylic acid (or an ester derivative thereof) and glycol.
- dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, or esters thereof (alkyl esters such as methyl ester) derivatives, and other known aliphatic dicarboxylic acids.
- the glycol include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and the like.
- polyester-based resins are subjected to a transesterification reaction between an alkyl ester of a dicarboxylic acid and a glycol and then polycondensed, or the diglycol ester of a dicarboxylic acid is polymerized. It can be produced by a method such as condensation.
- the polyester polycondensation catalyst used in the polycondensation of the polyester resin used in the present invention can be selected from antimony compounds, aluminum compounds, titanium compounds, and germanium compounds. Further, the polycondensation catalyst may be one kind or a combination of two or more kinds of catalysts.
- the polyester composition used for the polyester film of the present invention is produced by adding a magnesium compound, a potassium compound and a phosphorus compound to the same reaction vessel in addition to the polycondensation catalyst. Details thereof will be described later.
- the polyester polycondensation catalyst used at the time of polyester polycondensation is not particularly limited, but antimony trioxide is suitable because it is inexpensive and has excellent catalytic activity.
- a known method can be used to obtain a polyester resin using antimony trioxide as a catalyst.
- the polyester resin mentioned in patent 4023220 gazette can be illustrated.
- a germanium compound or a titanium compound as the polycondensation catalyst.
- More preferable polycondensation catalysts include a catalyst containing aluminum and / or its compound and a phenol compound, a catalyst containing aluminum and / or its compound and a phosphorus compound, and a catalyst containing an aluminum salt of a phosphorus compound.
- a catalyst containing aluminum and / or a compound thereof and a phosphorus compound By using a catalyst containing aluminum and / or a compound thereof and a phosphorus compound, a polyester resin polymerized using an antimony trioxide catalyst is used. In the extruder during the film forming process, in the stretching process, and heat setting. It is because the production
- known aluminum compounds can be used without limitation in addition to metal aluminum.
- the aluminum compound examples include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate.
- Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, etc.
- Aluminum chelate compounds such as aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysates thereof And aluminum oxide.
- carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.
- the amount of the aluminum and / or aluminum compound added is preferably 0.001 to 0.05 mol% with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. More preferably, it is 0.005 to 0.02 mol%. If the addition amount is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited. If the addition amount is 0.05 mol% or more, the thermal stability or thermal oxidation stability is deteriorated, resulting from the catalyst. Occurrence of foreign matters or increased coloring may be a problem.
- the polymerization catalyst of the present invention has a great feature in that it exhibits a sufficient catalytic activity even when the addition amount of the aluminum component is small. As a result, the thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by the catalyst can be reduced.
- the phenol compound constituting the polycondensation catalyst is not particularly limited as long as it is a compound having a phenol structure.
- the amount of the phenolic compound added is preferably 5 ⁇ 10 ⁇ 7 to 0.01 mol with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polyvalent carboxylic acid of the polyester obtained.
- the amount is preferably 1 ⁇ 10 ⁇ 6 to 0.005 mol.
- a phosphorus compound may be used together with the phenol compound.
- a phosphorus compound which comprises the said polycondensation catalyst The group which consists of a phosphonic acid type compound, a phosphinic acid type compound, a phosphine oxide type compound, a phosphonous acid type compound, a phosphinic acid type compound, a phosphine type compound
- the use of one or two or more selected compounds is preferable because the effect of improving the catalytic activity is great. Among these, when one or two or more phosphonic acid compounds are used, the effect of improving the catalytic activity is particularly large and preferable.
- the phosphorus compound constituting the polycondensation catalyst is particularly preferably a compound that is a group having an aromatic ring structure.
- Examples of the phosphorus compound constituting the polycondensation catalyst include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl phosphophosphonate, diethyl benzylphosphonate, and diphenylphosphine.
- the amount of the phosphorus compound added is preferably 5 ⁇ 10 ⁇ 7 to 0.01 mol with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polyvalent carboxylic acid of the polyester obtained.
- the amount is preferably 1 ⁇ 10 ⁇ 6 to 0.005 mol.
- the phosphorus compound having a phenol part constituting the polycondensation catalyst in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound having a phenol part in the same molecule,
- Use of one or two or more compounds selected from the group consisting of phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds is preferable because the effect of improving catalytic activity is great.
- a phosphonic acid compound having one or two or more phenol moieties in the same molecule is used, the effect of improving the catalytic activity is particularly large and preferable.
- the polyester catalyst used in the present invention has catalytic activity not only in the polymerization reaction but also in the esterification reaction and transesterification reaction.
- polymerization by an ester exchange reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually carried out in the presence of an ester exchange catalyst such as a titanium compound or a zinc compound.
- an ester exchange catalyst such as a titanium compound or a zinc compound.
- the catalyst described in the claims of the present invention can be used together with these catalysts.
- the catalyst has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization, and any method can produce a polyester resin suitable for production of a polyester film for solar cells. Is possible.
- polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene butylene terephthalate, polyethylene − 2,6 − naphthalate and the like.
- This polyester may be a homopolymer or a copolymer of the third component.
- the ethylene terephthalate unit, the propylene terephthalate unit, the butylene terephthalate unit or the ethylene − 2,6 − naphthalate unit is 70 mol% or more, preferably 80 mol% or more, in 100 mol% of the constituent unit. It is recommended to use a polyester that is more preferably 90 mol% or more.
- the above-mentioned polyester resin incompatible thermoplastic resin acts as a cavity developing agent and contributes to the formation of cavities in the film. .
- the incompatible thermoplastic resin is uniformly mixed in the polyester resin in a dispersed state, and peels off at the interface with the base resin at the time of stretching to become a cavity forming source.
- the incompatible thermoplastic resin that can be used in the present invention is not particularly limited as long as it is phase-separated when melt-mixed with the polyester resin by a general method.
- a polymer having a copolymer component may be used.
- a polyolefin-based resin is preferable from the viewpoint of expressing a cavity having a suitable shape.
- polystyrene-based resin examples include resins such as polyethylene, polypropylene, polybutene, and polymethylpentene.
- polymethylpentene resin is preferable because it is difficult to soften even at high temperatures and can exhibit excellent cavities.
- These polyolefin resin may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the amount of the incompatible thermoplastic resin used is 3 parts by mass or more, more preferably 4 parts by mass or more, and 20 parts by mass or less, based on 100 parts by mass of the polyester resin. It is recommended that the amount be 10 parts by mass or less, more preferably 4 parts by mass or more and 8 parts by mass or less. If the amount of the incompatible thermoplastic resin used is less than the above range, the formation of cavities may be insufficient and the reflection directivity may increase. On the other hand, if the amount of the incompatible thermoplastic resin exceeds the above range, the reflection effect of the light reflecting layer disposed on the back surface cannot be fully utilized, and particularly the reflectance in the near infrared region cannot be obtained sufficiently. During film production, film breaks and creases are likely to occur, and productivity is significantly reduced.
- the incompatible thermoplastic resin is further blended with another incompatible thermoplastic resin as a dispersible resin.
- the dispersible resin is a thermoplastic resin that is incompatible with both the polyester resin and the incompatible thermoplastic resin added as a cavity developing agent, and has a surface tension (surface energy) higher than that of the cavity developing agent. ) Is a large resin.
- a dispersible resin By blending a dispersible resin, it exerts a "dispersing action" that finely disperses a thermoplastic resin that is incompatible with polyester in the raw material resin, thereby more favorably dissociating the cavity developer and the polyester resin. This has the effect of forming and thus forming fine cavities uniformly.
- the dispersible resin having such a function include a polystyrene-based resin.
- the polystyrene resin may be a copolymer having various copolymer components in addition to a homopolymer. However, in the latter case, it is required that the copolymer component does not impair the effects of the present invention.
- the lower limit of the content of the dispersible resin is 10 parts by mass, preferably 15 parts by mass, and more preferably 20 parts by mass with respect to 100 parts by mass of the incompatible thermoplastic resin.
- the upper limit is 50 parts by mass, preferably 40 parts by mass, particularly preferably 30 parts by mass.
- the shape of the cavity is important for reflection of near infrared light. That is, in the case of a flat cavity that extends in the plane direction with respect to the thickness direction of the cavity, reflection of near-infrared light and transmission of light can be well balanced.
- the cavity-expressing agent and the dispersible resin are controlled within a suitable range so that the cavity is expressed more uniformly, and a flat cavity is formed with respect to the thickness of the cavity. Furthermore, interfacial peeling with a cavity developing agent can be made larger by making the intrinsic viscosity of the polyester resin forming the film relatively high by solid phase polymerization. Thereby, it becomes possible to express a cavity more suitably.
- the average reflectance in the wavelength range of 400 to 1200 nm is 70 to 95%, and the wavelength is 700 to 1200 nm.
- a polyester film for solar cells having an average transmittance in the range of 5% or more and 30% or less can be obtained.
- the average reflectance in the wavelength range of 400 to 1200 nm is less than 70%, and the reflection directivity may increase.
- the void content is large, not only the mechanical strength decreases, but the average reflectance in the wavelength range of 400 to 1200 nm exceeds 95%, and the reflective layer such as a metal layer disposed on the back surface of the film.
- the lower limit of the average reflectance in the wavelength range of 400 to 1200 nm is more preferably 72%, and even more preferably 75%.
- the upper limit of the average reflectance in the wavelength range of 400 to 1200 nm is preferably 93%, and more preferably 90%.
- the average transmittance in the near-infrared wavelength range of 700 to 1200 nm is less than 5%, the reflection characteristics of a reflective layer such as a metal layer disposed on the back surface cannot be fully utilized. If the average transmittance in the wavelength range of 700 to 1200 nm exceeds 30%, the reflection directivity may increase.
- the lower limit of the average transmittance in the wavelength range of 700 to 1200 nm is preferably 6% or more, and more preferably 8% or more.
- the upper limit of the average transmittance in the wavelength range of 700 to 1200 nm is preferably 28% or less, and more preferably 25% or less.
- the cavity shape is preferably achieved by appropriately adjusting the intrinsic viscosity of the polyester resin, the type of the incompatible thermoplastic resin to be added, the combination (particularly, the combination with the dispersant), and the concentration thereof. Can do.
- the film of the present invention preferably has a 60 ° gloss value of 70 or less, more preferably 60 or less.
- the 60 ° gloss value is 70 or less, the light reflection directivity is small, and the light irradiated to the solar cell can be used more efficiently.
- particles may be contained in the film to impart handling properties.
- the type and content of the particles may be inorganic particles or organic particles, and are not particularly limited, but include metal oxides such as silica, titanium dioxide, talc, and kaolinite, calcium carbonate, Examples thereof include inorganic particles inert to polyester such as calcium phosphate and barium sulfate. Among these, titanium dioxide which is easily available industrially is preferable.
- Titanium oxide is mainly known in two crystalline forms, rutile type and anatase type, whereas anatase type has a very high spectral reflectance of ultraviolet rays, whereas rutile type has a high absorption rate of ultraviolet rays ( The spectral reflectance is small). These can be selected as needed.
- These inert inorganic particles may be used alone or in combination of two or more.
- the content of the titanium oxide particles in the film of the present invention is 0.1% by mass or more, preferably 0.5% by mass or more, and 30% by mass or less, preferably 20% by mass or less, based on the total amount of the film. It is recommended that there be. When the content of titanium oxide particles is below the above range, sufficient handling properties may not be ensured. On the other hand, when the content of the titanium oxide particles exceeds the above range, an operation such as stretching becomes difficult during production of the film, and productivity may be lowered.
- the average particle diameter of the titanium oxide particles is 0.02 ⁇ m, preferably 0.05 ⁇ m, more preferably 0.1 ⁇ m, and the upper limit is 3 ⁇ m, preferably 2 ⁇ m, more preferably 1 ⁇ m. Recommended. When the average particle size of the titanium oxide particles is below the above range, sufficient handling properties may not be obtained. When the average particle size exceeds the above range, coarse surface protrusions may be generated, and a moisture-proof layer such as a laminated metal foil May be adversely affected.
- the average particle diameter of the particles can be measured by the following method. Take a photograph of the particles with an electron microscope or an optical microscope and at a magnification such that the size of one smallest particle is 2 to 5 mm, the maximum diameter of 300 to 500 particles (in the case of porous silica, Particle diameter) is measured, and the average value is taken as the average particle diameter.
- a known method can be adopted.
- it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or after the end of the ester exchange reaction and before the start of the polycondensation reaction.
- the polycondensation reaction may proceed.
- a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material or a method of blending dried particles and a polyester raw material using a kneading extruder It can be carried out.
- the filtered material is the polyester raw material before the esterification reaction, during the esterification reaction, or after the esterification reaction.
- the method of adding to the remainder of is preferable. According to this method, since the monomer liquid has a low viscosity, homogeneous dispersion of particles and high-accuracy filtration of the slurry can be easily performed, and when added to the remainder of the raw material, the dispersibility of the particles is good and new aggregation is achieved. Aggregation is unlikely to occur.
- the aggregate of the lubricant can be further reduced by a method (master batch method) in which the pellet and the pellet not containing the particle are kneaded and extruded. Since the number can be reduced, it is preferable.
- the polyester film of the present invention preferably has a cyclic trimer content of 5000 ppm or less. More preferably, it is 4000 ppm or less, and particularly preferably 3500 ppm or less.
- a cyclic trimer content is 5000 ppm or less, hydrolysis of the film is suppressed, and an effect of retaining an important characteristic as a solar cell member called durability is easily obtained.
- the durability can be evaluated by the elongation at break after 192 hours at 105 ° C., 100% RH, 0.03 MPa.
- This breaking elongation retention is preferably 65% or more, more preferably 70% or more.
- the polyester film for solar cells of the present invention can exhibit high hydrolysis resistance that can withstand long-term use outdoors.
- the solid phase polymerization method referred to in the present invention is a method in which a polyester resin is heated in a solid phase under reduced pressure or in an inert gas stream as described above to further proceed polycondensation. You may combine the method of heating under reduced pressure in a solid-phase state, and the method of heat-processing in inert gas stream.
- the solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus, similarly to the melt polycondensation reaction. Melt polycondensation and solid phase polycondensation may be carried out continuously or separately.
- there is no restriction on taking measures such as removing oligomers such as cyclic trimers and by-products such as acetaldehyde contained in the polyester resin.
- the solid phase polymerization is desirably carried out at a temperature of 180 ° C. or higher and lower than the melting point, and particularly preferably 195 to 235 ° C. Above the melting point, the polyester resin melts and is not practical, and below 180 ° C., the rate of reduction of the cyclic trimer is extremely slow, which is not preferable. Furthermore, the solid phase polymerization needs to be performed under an inert gas flow or under reduced pressure. This inert gas means a gas that does not cause deterioration of the polyester resin obtained after solid-phase polymerization, and it is generally preferable to use inexpensive nitrogen.
- the amount of water in the inert gas may be in a range where the intrinsic viscosity of the polyester resin does not decrease during solid phase polymerization, and is usually 500 ppm or less.
- the degree of vacuum is usually 0.1 KPa or less, more preferably 0.05 KPa or less.
- the solid-phase polymerization apparatus uniformly heats pellet resins such as a rotary solid-phase polymerization apparatus, a tower-type stationary solid-state polymerization apparatus, a fluidized-bed solid-phase polymerization apparatus, and a solid-phase polymerization apparatus having various stirring blades. What can be done is preferred.
- polyester having a high molecular weight by solid phase polymerization or low acid value polyester is also preferable to use.
- the hydrolysis resistance of the polyester film can be further improved.
- the polyester is made to have a high molecular weight by solid phase polymerization
- the intrinsic viscosity is preferably 0.65 to 0.80 dl / g in order to obtain high heat resistance and hydrolysis resistance, and more preferably 0.70. ⁇ 0.75 dl / g.
- the intrinsic viscosity of the polyester can be measured by dissolving the polyester in a mixed solvent of parachlorophenol (6 parts by mass) and 1,1,2,2-tetrachloroethane (4 parts by mass) at 30 ° C. it can.
- polyester used in the present invention other arbitrary polycondensates, antistatic agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other An additive may be contained.
- antioxidants aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.
- the polyester film of the present invention may be a single-layer polyester film or a laminated polyester film having at least three layers having an outermost layer and a center layer.
- the outermost layers on the front and back may be the same composition or different compositions, but the two types and three layers (A layer / B layer / A layer) are flat. To preferred.
- particles are contained in the outermost layer (A layer in the case of the above-mentioned two types and three layers), and the incompatible heat is contained in the central layer (B layer in the case of the above two types and three layers).
- a layer containing a plastic resin is preferred.
- the reason why particles are included in the A layer is to provide the handling layer and increase the surface area in a post-processing step such as laminating a moisture-proof functional layer such as a metal or metal oxide thin film layer or a coating layer. This is for improving the adhesion.
- a post-processing step such as laminating a moisture-proof functional layer such as a metal or metal oxide thin film layer or a coating layer. This is for improving the adhesion.
- a moisture-proof functional layer such as a metal or metal oxide thin film layer or a coating layer. This is for improving the adhesion.
- the handling property of the laminated film of the present invention can be evaluated by the coefficient of dynamic friction ( ⁇ d) between the laminated film surfaces.
- the dynamic friction coefficient ( ⁇ d) is preferably 0.7 or less from the viewpoint of workability.
- the thickness of the film used in the present invention is not particularly limited, but can be arbitrarily determined in the range of 30 to 350 ⁇ m according to the standard to be used.
- the upper limit of the thickness of the base film is preferably 250 ⁇ m, particularly preferably 200 ⁇ m.
- the lower limit of the film thickness is preferably 50 ⁇ m, more preferably 75 ⁇ m, and particularly preferably 100 ⁇ m.
- the film thickness is less than 30 ⁇ m, rigidity and mechanical strength tend to be insufficient.
- the film thickness exceeds 300 ⁇ m, the cost increases.
- the film comprises a mixture of the desired film composition (for example, including a polyester resin, an incompatible thermoplastic resin, a dispersible resin, and inorganic particles).
- the desired film composition for example, including a polyester resin, an incompatible thermoplastic resin, a dispersible resin, and inorganic particles.
- the mixture is melted and extruded into a film to obtain an unstretched film, it is stretched in the uniaxial direction in the longitudinal direction or the width direction as necessary, or sequentially biaxially or simultaneously biaxially stretched in the biaxial direction.
- a biaxially oriented polyester film subjected to heat setting treatment is preferable.
- Pellets made of a mixture containing a polyester resin, an incompatible thermoplastic resin, and inorganic particles are sufficiently vacuum-dried, then melt-extruded into a sheet at 270 to 295 ° C., and cooled and solidified to obtain an unoriented cast film. .
- the obtained cast film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented polyester film.
- the both ends of the film are gripped with clips, guided to a hot air zone heated to 80 to 180 ° C., and stretched 2.5 to 5.0 times in the width direction after drying. Subsequently, it is led to a heat treatment zone of 220 to 240 ° C., heat setting treatment and cooling are performed to complete crystal orientation. In this heat treatment step, a relaxation treatment of 1 to 12% may be performed in the width direction or the longitudinal direction as necessary.
- the film of the present invention when the film of the present invention is produced, it is preferable to remove foreign matters contained in the raw material polyester that cause projections.
- high-precision filtration is performed at an arbitrary place where the molten resin is maintained at about 280 ° C. during melt extrusion.
- the filter medium used for high-precision filtration of molten resin is not particularly limited, but in the case of a stainless steel sintered filter medium, aggregates mainly composed of Si, Ti, Sb, Ge, Cu, and Al, and high melting point organic substances Is excellent in removal performance and is suitable.
- the filter particle size (initial filtration efficiency: 95%) of the filter medium used for high-precision filtration of molten resin is preferably 25 ⁇ m or less.
- the filter particle size of the filter medium exceeds 25 ⁇ m, removal of foreign matters of 20 ⁇ m or more tends to be insufficient.
- Productivity may be reduced by performing high-precision filtration of molten resin using a filter medium with a filtration particle size (initial filtration efficiency: 95%) of 25 ⁇ m or less, but it is important to obtain a film with few protrusions. is there.
- the residence time of the molten resin in the extruder is preferably as short as possible from the viewpoint of cyclic trimer formation.
- the polyester film of the present invention may be subjected to a surface modification treatment on the film surface in order to impart adhesion to other materials.
- a surface modification treatment include corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and ozone treatment.
- an easy-adhesion layer can be provided on one side of the polyester film for solar cell for the purpose of improving the adhesiveness with a sealing resin for solar cell such as ethylene-vinyl acetate copolymer.
- the easy-adhesion layer is not particularly limited as long as it has good adhesion to the sealing resin, but an easy-adhesion layer containing at least one of a copolyester resin, an acrylic resin and a polyurethane resin is suitable. is there.
- Examples of the coating solution for forming these easy-adhesion layers include water-soluble or water-dispersible copolyester solutions, acrylic solutions, polyurethane solutions and the like exemplified in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, etc. Is mentioned.
- the easy-adhesion layer can be obtained by applying these coating solutions to one or both sides of a uniaxially stretched polyester film in the longitudinal direction, drying at 100 to 150 ° C., and further stretching in the transverse direction.
- the final coating amount of the easy adhesion 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 , the adhesion with the sealing resin may be insufficient. On the other hand, when the coating amount exceeds 0.20 g / m 2 , blocking resistance may be lowered.
- the particles to be included in the easy-adhesion layer include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide, barium sulfate, calcium fluoride, fluoride.
- Inorganic particles such as lithium fluoride, zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate resin particles, benzoguanamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, polytetrafluoroethylene
- heat-resistant polymer particles such as particles.
- silica particles are preferable because they can be obtained relatively inexpensively.
- 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. can be mentioned. Or it can carry out in combination.
- the solar cell backsheet of the present invention has a solar cell polyester film and a light reflective layer disposed on one side of the solar cell polyester film.
- the light-reflective layer may be directly laminated on the solar cell polyester film, or may be disposed via an adhesive layer or other transparent film layer.
- the light reflective layer may be a metal foil film layer such as an aluminum foil, or may be a transparent film layer in which metal thin film layers are laminated.
- a configuration of polyester film / adhesive / metal foil or film having a metal-based thin film layer / adhesive / polyvinyl fluoride film or polyester-based highly durable moisture-proof film is exemplified. Is done.
- a metal or metal thin film laminated film having a water vapor barrier property and a relatively high reflectance in a wavelength range of 400 to 1200 nm is preferable. Can be used.
- the metal examples include aluminum, tin, magnesium, silver, and stainless steel. Among them, aluminum and silver are preferable because they have a relatively high reflectance and are easily available industrially.
- the metal layer may be used as a metal foil, or may be laminated as a thin film on a polyester film or the like. As a method of laminating these metals as a thin film, a vacuum deposition method, a sputtering method, an ion plating method, a plasma vapor deposition method (CVD), or the like can be used.
- each layer of a light diffusing layer such as a polyester film, a metal foil or a film having a metal-based thin film layer, a polyvinyl fluoride film or a polyester-based high durability moisture-proof film is integrated by vacuum suction or the like, and is thermocompression bonded.
- a solar cell backsheet can be produced by thermocompression-molding each of the above-mentioned layers as an integral molded body using a normal molding method such as a lamination method.
- the adhesive include (meth) acrylic resins, olefinic resins, vinyl resins, and other heat melting adhesives, solvent-based adhesives, photo-curing adhesives, etc. whose main component is a vehicle. It is done.
- the high durability moisture-proof film is laminated for the purpose of improving the weather resistance.
- the high durability moisture-proof film include polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer.
- Polymer (PFA) 4-Fluoroethylene-6-Fluoropropylene Copolymer (FEP), 2-Ethylene-4 Fluoroethylene Copolymer (ETFE), Poly-3-Fluoroethylene (PCTFE), Polyfluoride Fluorine resin film such as vinylidene (PVDF) or polyfuca vinyl (PVF), or UV absorber for resin such as polycarbonate, polymethyl methacrylate, polyacrylate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic A film made of a kneaded resin composition It is.
- PVDF vinylidene
- PEN polyfuca vinyl
- a spectrophotometer (Shimadzu Corporation self-recording spectrophotometer "UV-3150") is equipped with an integrating sphere and a standard white plate (SpereOptics white standard plate “ZRS-99-010-W”) The reflectance was 100%, and the spectral reflectance was measured. The measurement was performed in 1 nm increments in the wavelength range of 400 to 1200 nm, and the average value was obtained.
- measurement was performed by placing a non-reflective black mount on the back of the sample film.
- Average particle diameter The inert particles were observed with a scanning electron microscope (S-51O type, manufactured by Hitachi, Ltd.), and the magnification was appropriately changed according to the size of the particles. Next, the outer circumference of each particle was traced for at least 300 particles selected at random, the equivalent circle diameter of the particles was measured from these trace images with an image analyzer, and the average of these was taken as the average particle diameter.
- Elongation at break As the hydrolysis resistance evaluation, HAST (Highly Accelerated Temperature and Humidity Stress Test) standardized in JIS-60068-2-66 was performed. The equipment was EHS-221 manufactured by ESPEC CORP. Under the conditions of 105 ° C., 100% RH and 0.03 MPa. The film was cut into 70 mm ⁇ 190 mm, and the film was placed using a jig. Each film was placed at a distance where it did not touch. The treatment was performed for 192 hours under the conditions of 105 ° C., 100% RH, and 0.03 MPa.
- Breaking elongation retention ratio (%) [(breaking elongation after treatment (MPa)) / (breaking elongation before treatment (MPa))] ⁇ 100
- Reflection directivity 60 ° gloss value
- a surface gloss meter Nippon Denshoku Kogyo Co., Ltd. gloss meter: VG-SENSOR
- Photoelectric conversion efficiency A solar cell using a microcrystalline silicon thin film prepared by PE-CVD is prepared as a solar cell, a sample film with a glass plate on the front and an aluminum foil on the back is placed, and EVA is used as a filler As described above, a solar cell module was manufactured by stacking and integrating by a vacuum laminating method. The photoelectric conversion efficiency (%) of the obtained solar cell module was measured and evaluated according to the following criteria. ⁇ : Conversion efficiency 10.5% or more ⁇ : Conversion efficiency less than 10.5%
- polyester resins (A-1 and A-2)
- 86.4 parts by mass of high-purity terephthalic acid and 64.4 parts of ethylene glycol were used.
- the slurry which consists of a mass part was prepared, and 0.03 mass part of antimony trioxide and 0.16 mass part of triethylamine were added as a catalyst, stirring.
- the pressure esterification reaction was carried out under the conditions of a pressure increase in temperature and a gauge pressure of 3.5 kg / cm 2 and 240 ° C. Thereafter, the inside of the esterification reaction can was returned to normal pressure.
- polyester (A-1) is subjected to solid phase polymerization at 220 ° C. under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus to obtain polyester resin (A-2) having an intrinsic viscosity of 0.75 dl / g. It was.
- polyester resins B-1 and B-2
- Aluminum chloride as a polycondensation catalyst for a mixture of bis (2-hydroxyethyl) terephthalate and oligomer produced from high-purity terephthalic acid and ethylene glycol according to a conventional method
- Polyester (A-1) was subjected to solid phase polymerization at 220 ° C. under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus, to obtain a polyester resin (B-2) having an intrinsic viscosity of 0.75 dl / g. .
- polyester resin (C) When the temperature of the esterification reaction can reached 200 ° C, a slurry composed of 86.4 parts by mass of high-purity terephthalic acid and 64.4 parts by mass of ethylene glycol was prepared. Add ethylene glycol slurry of 0.03 parts by weight of antimony trioxide, 0.16 parts by weight of triethylamine and silica particles with an average particle diameter of 2.5 ⁇ m as a catalyst while charging and stirring to 2000 ppm with respect to the generated PET. did. Next, the pressure esterification reaction was carried out under the conditions of a pressure increase in temperature and a gauge pressure of 3.5 kg / cm 2 and 240 ° C. Thereafter, the inside of the esterification reaction can was returned to normal pressure.
- the resulting esterification reaction product was transferred to a polycondensation reaction can and subjected to a polycondensation reaction under reduced pressure at 280 ° C. until the intrinsic viscosity reached 0.65 dl / g.
- Polyethylene terephthalate obtained by polycondensation was chipped according to a conventional method to obtain polyester (C). At this time, the molten resin was maintained at about 275 ° C., and the filtration particle size (initial filtration efficiency: 95%) was filtered with a 20 ⁇ m stainless sintered body filter to remove foreign substances contained in the resin.
- master pellet (A) 70% by mass of a polymethylpentene resin having a melt flow rate of 180 and 30% by mass of a polystyrene resin having a melt flow rate of 2.0 are charged into a twin screw extruder and melt mixed at 260 ° C. Thus, an incompatible thermoplastic resin master batch pellet was obtained and dried with hot air at 70 ° C. for 4 hours to obtain a master pellet (A).
- Example 1 After 94 parts by weight of polyester resin (A-2) was vacuum-dried at 180 ° C. for 3 hours in a vacuum dryer, 6 parts of master pellets (A) were mixed and put into a twin screw extruder, and from T-die An unstretched sheet was obtained by melting and extruding at 290 ° C. and electrostatically adhering to a cooling rotating roll. Next, the unstretched sheet was longitudinally stretched 3.1 times at 80 ° C. by a roll stretching machine, then transversely stretched 3.6 times at 125 ° C. by a tenter, and further at 220 ° C. by a tenter. A heat setting treatment for 10 seconds and a relaxation heat treatment of 4% at 170 ° C. were performed to obtain a polyester film having a thickness of 50 ⁇ m.
- Example 2 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that 93 parts by mass of the polyester resin (A-2) and 7 parts by mass of the master pellet (A) were used.
- Example 3 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that 92 parts by mass of the polyester resin (A-2) and 8 parts by mass of the master pellet (A) were used.
- Example 4 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 2 except that the polyester resin (A-2) was replaced with the polyester resin (A-1).
- Example 6 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 5 except that the master pellet (B) was replaced with the master pellet (C).
- Example 7 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 2 except that the polyester resin (A-2) was replaced with the polyester resin (B-2).
- Example 8 Polyester having a thickness of 50 ⁇ m in the same manner as in Example 6 except that the raw material for the intermediate layer (B layer) and the raw material for the outer layer (A layer) were both changed from the polyester resin (A-2) to the polyester resin (B-2). A film was obtained.
- Example 9 A polyester film was obtained in the same manner as in Example 8 except that the final thickness was changed from 50 ⁇ m to 100 ⁇ m.
- Example 10 A polyester film was obtained in the same manner as in Example 8 except that the final thickness was changed from 50 ⁇ m to 188 ⁇ m.
- Example 11 (Coating solution adjustment) 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.
- Example 12 A silver laminated film was bonded to one side of the polyester film obtained in Example 1 as follows.
- a pressure-sensitive adhesive (X395-270S-1: manufactured by Seiden Chemical Co., Ltd.) was applied by a die coating method so as to have a wet weight of 30 g / m 2 and dried at 100 ° C. for 1 minute to form a pressure-sensitive adhesive layer.
- Example 1 A polyester resin (A-1) and a polyester resin (C) were mixed so as to have a silica particle concentration of 300 ppm, and a polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that the raw material for the polyester film was used.
- Example 2 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that the polyester resin (A-2) was 97 parts by mass and the master pellet (A) was 3 parts by mass.
- Example 3 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that 90 parts by mass of the polyester resin (A-2) and 10 parts by mass of the master pellet (A) were used.
- Example 4 A polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that 90 parts by mass of the polyester resin (A-2) and 10 parts by mass of the polymethylpentene resin having a melt flow rate of 180 were used.
- Example 5 A polyester film having a thickness of 50 ⁇ m was prepared in the same manner as in Example 1 except that the polyester resin (A-2) and the master pellet (C) were mixed so as to have a titanium oxide particle concentration of 35% and used as a raw material for the polyester film. Obtained.
- Example 6 A polyester film having a thickness of 50 ⁇ m was prepared in the same manner as in Example 1 except that the polyester resin (A-2) and the master pellet (D) were mixed so as to have a barium sulfate particle concentration of 35% and used as a raw material for the polyester film. Obtained.
- the polyester film for solar cell of the present invention is a back for solar cell in a solar cell having a thin film solar cell element that is required not only in the visible light region but also in the near infrared region and having high reflectance and small reflection directivity. It is useful as a structural member of a sheet.
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Abstract
Description
本願の第1の発明は、空洞含有ポリエステルフィルムであって、波長400~1200nmの範囲における平均反射率が70%以上、95%以下であり、波長700~1200nmの範囲における平均透過率が5%以上、30%以下である太陽電池用ポリエステルフィルムである。
本願の第2の発明は、ポリエステルフィルム中の環状三量体含有量が5000ppm以下である前記太陽電池用ポリエステルフィルムである。
本願の第3の発明は、アルミニウム及び/又はその化合物とフェノール系化合物を含有する前記太陽電池用ポリエステルフィルムである。
本願の第4の発明は、前記太陽電池用ポリエステルフィルムと、当該太陽電池用ポリエステルフィルムの片面に配する光反射性層とを有する太陽電池用バックシートである。
本願の第5の発明は、前記光反射層がアルミニウムおよび銀のいずれか少なくとも1種を含む金属箔または金属系薄膜層である前記太陽電池用バックシートである。
粒子を電子顕微鏡または光学顕微鏡で写真を撮り、最も小さい粒子1個の大きさが2~5mmとなるような倍率で、300~500個の粒子の最大径(多孔質シリカの場合は凝集体の粒径)を測定し、その平均値を平均粒子径とする。
分光光度計(島津製作所社製自記分光光度計「UV-3150」)に積分球を装着し、標準白色板(SpereOptics社製白色標準板「ZRS-99-010-W」)の反射率を100%として校正し、分光反射率を測定した。測定は波長400~1200nmの領域で1nm刻みに行い平均値を求めた。尚、フィルム単体の測定時は試料フィルム背面に無反射の黒台紙を背面に配し測定した。光反射性層を配したときの測定は試料フィルム背面にアルミニウム箔(厚さ11μm、算術的表面粗さ(Ra=0.11μm)を背面に配し測定した。
分光光度計(島津製作所社製自記分光光度計「UV-3150」)に積分球を装着し、無試料の透過率を100%として校正し、分光透過率を測定した。測定は波長700~1200nmの領域で1nm刻みに行い平均値を求めた。
ポリエステルフィルム中の環状三量体の含有量は以下の方法で測定した。細砕したフィルム試料100mgを精秤し、ヘキサフルオロイソプロパノ-ル/クロロホルム混合液(容量比=2/3)3mlに溶解し、さらにクロロホルム20mlを加えて希釈する。これにメタノ-ル10mlを加えてポリマ-を沈殿させた後、濾過する。濾液を蒸発乾固し、ジメチルフォルムアミド10mlで定容とした。次いで下記の高速液体クロマトグラフ法で環状三量体を定量した。
装置:L-7000(日立製作所製)
カラム:μ-Bondasphere C18 5μ 100オングストローム 3.9mm×15cm(Waters製)
溶媒:溶離液A:2%酢酸/水(v/v)
溶離液B:アセトニトリル
グラジエントB%:10→100%(0→55分)
流速:0.8ml/分
温度:30℃
検出器:UV-259nm
不活性粒子を走査型電子顕微鏡(日立製作所製、S-51O型)で観察し、粒子の大きさに応じて適宜倍率を変え、写真撮影したものを拡大コピーした。次いで、ランダムに選んだ少なくとも300個の粒子について各粒子の外周をトレースし、画像解析装置にてこれらのトレース像から粒子の円相当径を測定し、これらの平均を平均粒子径とした。
ポリエステルをパラクロロフェノール/1,1,2,2-テトラクロロエタンの6/4(重量比)混合溶媒を使用して溶解し、温度30℃にて測定した。
耐加水分解性評価として、JIS-60068-2-66で規格化されているHAST(Highly Accelerated temperature and humidity Stress Test)を行った。機器はエスペック社製EHS-221を用い、105℃、100%RH、0.03MPa下の条件で行った。
フィルムを70mm×190mmにカットし、治具を用いてフィルムを設置した。各フィルムは各々が接触しない距離を保ち設置した。105℃、100%RH、0.03MPaの条件下で192時間処理を行った。処理前、処理後の破断伸度をJIS-C-2318-1997 5.3.31(引張強さ及び伸び率)に準拠して測定し、下記式に従い破断伸度保持率を算出した。
破断伸度保持率(%)=[(処理後の破断伸度(MPa))/(処理前の破断伸度(MPa))]×100
表面光沢度計(日本電色工業社製グロスメーター:VG-SENSOR)使用し、光の入射方向の角度(入射角)を60度、受光側の角度(受光角)60度の条件で測定した。
太陽電池としてPE-CVD法により作製した微結晶シリコン薄膜を用いた太陽電池を用意し、前面にガラス板、背面にアルミニウム箔を背面に配した試料フィルムを配置し、EVAを充填剤として、真空ラミネート法で積層、一体化して太陽電池モジュールを作製した。得られた太陽電池モジュールの光電変換効率(%)を測定し、下記基準により評価した。
○:変換効率 10.5%以上
×: 変換効率 10.5%未満
エステル化反応缶を昇温し、200℃に到達した時点で、高純度テレフタル酸を86.4質量部及びエチレングリコールを64.4質量部からなるスラリーを仕込み、攪拌しながら触媒として三酸化アンチモンを0.03質量部、トリエチルアミンを0.16質量部添加した。次いで、加圧昇温を行いゲージ圧3.5kg/cm2 、240℃の条件で、加圧エステル化反応を行った。その後、エステル化反応缶内を常圧に戻した。
15分後、得られたエステル化反応生成物を重縮合反応缶に移送し、280℃の減圧下で固有粘度が0.65dl/gに到達するまで重縮合反応を行った。
重縮合にて得られたポリエチレンテレフタレートを常法に従ってチップ化しポリエステル(A-1)を得た。この際、溶融樹脂が約275℃に保たれ状態で濾過粒子サイズ(初期濾過効率95%)は5μmステンレス焼結体フィルターで樹脂中に含まれる異物を除去するために高精度濾過を行った。
ポリエステル樹脂(A-1)を回転型真空重合装置を用いて、0.5mmHgの減圧下、220℃で固相重合を行い、固有粘度0.75dl/gのポリエステル樹脂(A-2)を得た。
高純度テレフタル酸とエチレングリコールから常法に従って製造したビス(2-ヒドロキシエチル)テレフタレート及びオリゴマーの混合物に対し、重縮合触媒として塩化アルミニウムの13g/lのエチレングリコール溶液をポリエステル中の酸成分に対してアルミニウム原子として0.015mol%とIrganox
1425(チバ・スペシャルティーケミカルズ社製)の10g/lエチレングリコール溶液を酸成分に対してIrganox 1425として0.02mol%を加えて、窒素雰囲気下、常圧にて245℃で10分間撹拌した。次いで50分間を要して275℃まで昇温しつつ反応系の圧力を徐々に下げて13.3Pa(1Torr)としてさらに275℃、13.3Paで固有粘度が0.65dl/gに到達するまで重縮合反応を行った。重縮合にて得られたポリエチレンテレフタレートを常法に従ってチップ化しポリエステル(B-1)を得た。 この際溶融樹脂が約275℃に保たれ状態で濾過粒子サイズ(初期濾過効率95%)は20μmステンレス焼結体フィルターで樹脂中に含まれる異物を除去するために高精度濾過を行った。
ポリエステル(A-1)を回転型真空重合装置を用いて、0.5mmHgの減圧下、220℃で固相重合を行い、固有粘度0.75dl/gのポリエステル樹脂(B-2)を得た。
エステル化反応缶を昇温し、200℃に到達した時点で、高純度テレフタル酸を86.4質量部及びエチレングリコールを64.4質量部からなるスラリーを仕込み、攪拌しながら触媒として三酸化アンチモンを0.03質量部、トリエチルアミンを0.16質量部と平均粒径2.5μmのシリカ粒子のエチレングリコールスラリーを、生成PETに対し、2000ppmとなるよう添加した。次いで、加圧昇温を行いゲージ圧3.5kg/cm2 、240℃の条件で、加圧エステル化反応を行った。その後、エステル化反応缶内を常圧に戻した。
15分後、得られたエステル化反応生成物を重縮合反応缶に移送し、280℃の減圧下で固有粘度が0.65dl/gに到達するまで重縮合反応を行った。
重縮合にて得られたポリエチレンテレフタレートを常法に従ってチップ化しポリエステル(C)を得た。この際、溶融樹脂が約275℃に保たれ状態で濾過粒子サイズ(初期濾過効率95%)は20μmステンレス焼結体フィルターで樹脂中に含まれる異物を除去するために高精度濾過を行った。
メルトフローレート180のポリメチルペンテン樹脂70質量%とメルトフローレート2.0のポリスチレン樹脂30質量%を二軸押出機に投入し、260℃で溶融混合して非相溶性熱可塑性樹脂マスターバッチペレットを得、70℃の熱風で4時間乾燥させマスターペレット(A)を得た。
真空オーブンを用い、平均粒径:0.2μmのアナターゼ型酸化チタン粒子(ルチル型混入率3%)を170℃、10Paの条件で乾燥した。また、上記のポリエステル樹脂(A-1)を140℃、10Paの条件で6時間乾燥した。乾燥後の上記酸化チタン粒子50質量%と上記ポリエステル樹脂(A-1)50質量%を、ベント式二軸押出機に供給して270℃で予備混練した。予備混練後の溶融樹脂を連続的にベント式単軸混練機に供給し、275℃で混練して押出し、得られたストランドを冷却、切断してアナターゼ型酸化チタン粒子含有マスターバッチペレット(B)を得た。
アナターゼ型酸化チタン粒子に代えて、平均粒径:0.3μmのルチル型酸化チタン粒子(アナターゼ型混入率5%)を用い、上記マスターペレット(B)と同様にして、ルチル型酸化チタン粒子含有マスターバッチペレット(C)を得た。
真空オーブンを用い、平均粒径:0.7μmの硫酸バリウム粒子を170℃、10Paの条件で乾燥した。また、上記のポリエステル樹脂(A-1)を140℃、10Paの条件で6時間乾燥した。乾燥後の上記硫酸バリウム粒子50質量%と上記ポリエステル樹脂(A-1)50質量%を、ベント式二軸押出機に供給して270℃で予備混練した。予備混練後の溶融樹脂を連続的にベント式単軸混練機に供給し、275℃で混練して押出し、得られたストランドを冷却、切断してマスターバッチペレット(D)を得た。
ポリエステル樹脂(A-2)94質量部を、真空乾燥機で180℃3時間真空乾燥した後、マスターペレット(A)を6質量と混合し、2軸スクリュー押し出し機に投入し、T-ダイスより290℃で溶融押し出して、静電気的に冷却回転ロールに密着固化することにより未延伸シートを得た。次に、該未延伸シートをロール延伸機により80℃で3.1倍に縦延伸を行った後、テンターにて125℃で3.6倍に横延伸するとともに、さらにテンターにて220℃で10秒間熱固定処理、170℃で4%の緩和熱処理を行い、厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)93質量部、マスターペレット(A)を7質量とした以外は実施例1と同様にして、厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)92質量部、マスターペレット(A)を8質量とした以外は実施例1と同様にして、厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)をポリエステル樹脂(A-1)に替えた以外は実施例2と同様にして、厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)94.0質量部を、真空乾燥機で180℃3時間真空乾燥した後、マスターペレット(A)を6.0質量と混合して中間層(B層)用原料とし、ポリエステル樹脂(A-2)99.6質量部、マスターペレット(B)0.4質量部を混合して外層(A層)用原料として2台の2軸スクリュー押し出し機に別々に投入し、T-ダイス内で積層した後、T-ダイスより290℃で溶融押し出し、静電気的に冷却回転ロールに密着固化することにより未延伸シートを得た。次いで、実施例1と同様にして厚さ50μm、層厚比A層/B層/A層=10/80/10のポリエステルフィルムを得た。
マスターペレット(B)をマスターペレット(C)に替えた以外は実施例5と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)をポリエステル樹脂(B-2)に替えた以外は実施例2と同様にして厚さ50μmのポリエステルフィルムを得た。
中間層(B層)用原料、外層(A層)用原料、ともにポリエステル樹脂(A-2)からポリエステル樹脂(B-2)に替えた以外は実施例6と同様にして厚さ50μmのポリエステルフィルムを得た。
最終厚さ50μmから100μmに変更した以外は実施例8と同様にしてポリエステルフィルムを得た。
最終厚さ50μmから188μmに変更した以外は実施例8と同様にしてポリエステルフィルムを得た。
(塗布液の調整)
常法によりエステル交換反応および重縮合反応を行って、ジカルボン酸成分として(ジカルボン酸成分全体に対して)テレフタル酸46モル%、イソフタル酸46モル%および5-スルホナトイソフタル酸ナトリウム8モル%、グリコール成分として(グリコール成分全体に対して)エチレングリコール50モル%およびネオペンチルグリコール50モル%の組成の水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂を調製した。次いで、水51.4質量部、イソプロピルアルコール38質量部、n-ブチルセルソルブ5質量部、ノニオン系界面活性剤0.06質量部を混合した後、加熱撹拌し、77℃に達したら、上記水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂5質量部を加え、樹脂の固まりが無くなるまで撹拌し続けた後、樹脂水分散液を常温まで冷却して、固形分濃度5.0質量%の均一な水分散性共重合ポリエステル樹脂液を得た。さらに、凝集体シリカ粒子(平均粒径1.4μm)3質量部を水50質量部に分散させた後、上記水分散性共重合ポリエステル樹脂液99.46質量部に前記凝集体シリカ粒子の水分散液0.54質量部を加えて、撹拌しながら水20質量部を加えて、塗布液を得た。
実施例8と同様にして未延伸シートを得た。次いで、前記未延伸シートの片面に前記塗布液を最終塗布量が0.08g/m2となるように塗布した後、135℃で乾燥させた。
その後、実施例8と同様にして厚さ50μmのポリエステルフィルムを得た。
実施例1で得たポリエステルフィルムの片面に以下のようにして銀積層フィルムを貼り合わせた。ダイコート方式により粘着剤(X395-270S-1:サイデン化学社製)をWETで30g/m2となるよう塗布し、100℃で1分乾燥させ粘着剤層を形成した。50nmの厚さの金属銀層を蒸着法で積層された12μm厚さのポリエチレンテレフタレートフィルムを前記粘着面に重ねて、二本のゴムロール間に導き、圧着して接着させ、積層ポリエステルフィルムを得た。
ポリエステル樹脂(A-1)とポリエステル樹脂(C)をシリカ粒子濃度300ppmになるように混合し、ポリエステルフィルムの原料とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)を97質量部、マスターペレット(A)を3質量部とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)を90質量部、マスターペレット(A)を10質量部とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)を90質量部、メルトフローレート180のポリメチルペンテン樹脂を10質量部とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)と、マスターペレット(C)を酸化チタン粒子濃度35%になるように混合し、ポリエステルフィルムの原料とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
ポリエステル樹脂(A-2)と、マスターペレット(D)を硫酸バリウム粒子濃度35%になるように混合し、ポリエステルフィルムの原料とした以外は実施例1と同様にして厚さ50μmのポリエステルフィルムを得た。
Claims (5)
- 空洞含有ポリエステルフィルムであって、
波長400~1200nmの範囲における平均反射率が70%以上、95%以下であり、
波長700~1200nmの範囲における平均透過率が5%以上、30%以下である太陽電池用ポリエステルフィルム。 - ポリエステルフィルム中の環状三量体含有量が5000ppm以下である請求項1に記載の太陽電池用ポリエステルフィルム。
- アルミニウム及び/又はその化合物とフェノール系化合物を含有する請求項1又は2の太陽電池用ポリエステルフィルム。
- 請求項1~3のいずれかに記載の太陽電池用ポリエステルフィルムと、当該太陽電池用ポリエステルフィルムの片面に配する光反射性層とを有する太陽電池用バックシート。
- 前記光反射層がアルミニウムおよび銀のいずれか少なくとも1種を含む金属箔または金属系薄膜層である請求項4の太陽電池用バックシート。
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JP2013021273A (ja) * | 2011-07-14 | 2013-01-31 | Fujifilm Corp | 太陽電池用バックシート及び太陽電池モジュール |
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US20140137935A1 (en) * | 2011-07-07 | 2014-05-22 | Yupo Corporation | Back sheet for solar cells, and solar cell using same |
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CN104170098A (zh) * | 2012-03-14 | 2014-11-26 | 东洋纺株式会社 | 太阳能电池背面密封片材及太阳能电池组件 |
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 |
CN104512081A (zh) * | 2014-11-27 | 2015-04-15 | 苏州赛伍应用技术有限公司 | 一种二层结构pet薄膜及由其组成的太阳能电池背板 |
WO2016152638A1 (ja) * | 2015-03-20 | 2016-09-29 | 東洋紡株式会社 | 太陽電池用白色ポリエステルフィルム、これを用いた太陽電池裏面封止シートおよび太陽電池モジュール |
CN107408595A (zh) * | 2015-03-20 | 2017-11-28 | 东洋纺株式会社 | 太阳能电池用白色聚酯薄膜、使用其的太阳能电池背面密封片材及太阳能电池组件 |
US10475943B2 (en) | 2015-03-20 | 2019-11-12 | Toyobo Co., Ltd. | White polyester film for a solar cell, sealing sheet for back surface of solar cell using same, and solar cell module |
CN107408595B (zh) * | 2015-03-20 | 2020-03-10 | 东洋纺株式会社 | 太阳能电池用白色聚酯薄膜、使用其的太阳能电池背面密封片材及太阳能电池组件 |
WO2017150072A1 (ja) * | 2016-03-04 | 2017-09-08 | 東レ株式会社 | 太陽電池モジュール用シート、および太陽電池モジュール |
Also Published As
Publication number | Publication date |
---|---|
EP2484716A4 (en) | 2014-11-19 |
KR101662872B1 (ko) | 2016-10-05 |
JP2011097039A (ja) | 2011-05-12 |
CN102549053B (zh) | 2013-11-06 |
JP4766192B2 (ja) | 2011-09-07 |
CN102549053A (zh) | 2012-07-04 |
EP2484716B1 (en) | 2018-02-21 |
US8916264B2 (en) | 2014-12-23 |
KR20120083887A (ko) | 2012-07-26 |
US20120183792A1 (en) | 2012-07-19 |
EP2484716A1 (en) | 2012-08-08 |
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