WO2016158358A1 - 白色ポリエステルフィルム及びその製造方法、太陽電池用バックシート並びに太陽電池モジュール - Google Patents
白色ポリエステルフィルム及びその製造方法、太陽電池用バックシート並びに太陽電池モジュール Download PDFInfo
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- WO2016158358A1 WO2016158358A1 PCT/JP2016/058021 JP2016058021W WO2016158358A1 WO 2016158358 A1 WO2016158358 A1 WO 2016158358A1 JP 2016058021 W JP2016058021 W JP 2016058021W WO 2016158358 A1 WO2016158358 A1 WO 2016158358A1
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- polyester film
- film
- white
- solar cell
- white polyester
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- PTLZMJYQEBOHHM-UHFFFAOYSA-N oxiran-2-ylmethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC1CO1 PTLZMJYQEBOHHM-UHFFFAOYSA-N 0.000 description 1
- KYVUJPJYTYQNGJ-UHFFFAOYSA-N oxiran-2-ylmethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC1CO1 KYVUJPJYTYQNGJ-UHFFFAOYSA-N 0.000 description 1
- DJTYNOVDSWHTJM-UHFFFAOYSA-N oxiran-2-ylmethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC1CO1 DJTYNOVDSWHTJM-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- KFDKNTQGTAEZGC-UHFFFAOYSA-N phenanthrene-1-carboxylic acid Chemical compound C1=CC2=CC=CC=C2C2=C1C(C(=O)O)=CC=C2 KFDKNTQGTAEZGC-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004448 titration Methods 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- 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
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- 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
Definitions
- the present disclosure relates to a white polyester film and a manufacturing method thereof, a back sheet for a solar cell, and a solar cell module.
- the solar cell module includes a solar cell element, a sealing material surrounding (sealing) the solar cell element, a transparent front substrate disposed on the light receiving surface side of the solar cell element, and a side opposite to the light receiving surface side It is comprised from members, such as the back surface protection sheet for solar cells (it is also called a "back sheet for solar cells” or a “back sheet”) which protects (back side). Since the solar cell module is used outdoors for a long period of time, these components are required to have weather resistance, that is, durability against the natural environment.
- Japanese Patent Application Laid-Open No. 2013-49791 contains two or more types of polyester resin and end-capping agents having a number average molecular weight of 4000 or more, and maintains the tear strength after 60 hours of thermostat at 120 ° C. and 100% relative humidity.
- a polyester film having a rate of 50% or more is disclosed.
- Japanese Patent Application Laid-Open No. 2011-192790 discloses a polyester film for a solar cell comprising a biaxially oriented film of polyethylene terephthalate, wherein the polyethylene terephthalate has a weight average molecular weight of 44,000 to 61,000 and a terminal carboxyl. Film having a base concentration of 6 to 29 equivalents / ton, an elongation retention when the film is aged for 3000 hours at a temperature of 85 ° C. and a humidity of 85% RH for 50% or more, and heat-treated at 150 ° C.
- the heat shrinkage rate in the longitudinal direction and the width direction is both ⁇ 0.1% to 1.5%
- the light transmittance of the film at a wavelength of 550 nm is 80% or more
- the tear load is 0.4N or more.
- a battery polyester film is disclosed.
- the polyester films disclosed in JP 2012-214726 A, JP 2013-47991 A, or JP 2011-192790 A are all for the purpose of improving the weather resistance and the like of a transparent film.
- the surface layer of a polyester film may cleave and adhesiveness may become inadequate.
- sufficient adhesion can be obtained mainly by devising the formulation of the coating layer, but in the white polyester film including white particles, only the coating layer is improved. It is difficult to obtain sufficient adhesion.
- the present disclosure provides a white polyester film excellent in weather resistance and adhesion to other resin layers, a method for producing the same, and a solar cell backsheet and solar that contribute to achieving high power generation efficiency over a long period of time.
- An object is to provide a battery module.
- ⁇ 1> including polyester and white particles, Thick 250 ⁇ m corresponding, the longitudinal stretching direction tear strength F MD is 2.5 ⁇ 6.0 N, the transverse stretching direction of the tear strength F TD is 2.0 ⁇ 5.0 N, and, in the transverse stretching direction tear strength F TD the ratio of longitudinal stretching direction tear strength F MD is from 1.05 to 4.00 with respect to,
- the terminal carboxyl group concentration is 5 to 25 equivalents / ton, White polyester film.
- ⁇ 2> The white polyester film according to ⁇ 1>, wherein the peak temperature of tan ⁇ measured with a dynamic viscoelasticity measuring device is 122 to 133 ° C.
- ⁇ 3> The white polyester film according to ⁇ 1> or ⁇ 2>, wherein the content of white particles is 2 to 10% by mass relative to the total mass of the film.
- ⁇ 4> The white polyester film according to any one of ⁇ 1> to ⁇ 3>, which has an intrinsic viscosity of 0.65 to 0.90 dL / g.
- the white polyester film according to ⁇ 5> thickness transverse stretching direction of the tear strength F TD at 250 ⁇ m equivalent is, any one of which is 2.0 ⁇ 4.0N ⁇ 1> ⁇ ⁇ 4>.
- ⁇ 6> The white polyester film according to any one of ⁇ 1> to ⁇ 5>, which is a film roll wound in a roll shape.
- ⁇ 7> A method for producing the white polyester film according to any one of ⁇ 1> to ⁇ 6>, When a melt obtained by melting a mixture containing raw material polyester and white particles is discharged from a die and landed on a cooling roll to form an unstretched film, the discharge temperature of the melt discharged from the die and the cooling roll An unstretched film forming step in which the difference from the landing point temperature is 20 ° C.
- the manufacturing method of the white polyester film which has NO. ⁇ 8>
- a solar cell backsheet comprising the white polyester film according to any one of ⁇ 1> to ⁇ 6>.
- a solar cell element ⁇ 9> a solar cell element; A sealing material for sealing the solar cell element; A front substrate disposed outside the sealing material on the light-receiving surface side of the solar cell element; A solar cell backsheet comprising the white polyester film according to any one of ⁇ 1> to ⁇ 5> disposed on the side opposite to the light receiving surface side of the solar cell element and outside the sealing material; Including solar cell module.
- a white polyester film excellent in weather resistance and adhesion to other resin layers, a method for producing the same, and a solar cell backsheet and a solar cell module that contribute to achieving high power generation efficiency over a long period of time are provided.
- White polyester film of the present disclosure (hereinafter, may be referred to as "polyester film” or “film”.), And a polyester and white particles, with a thickness of 250 ⁇ m corresponding, the longitudinal stretching direction tear strength F MD is 2.5 to 6.0 N, tear strength F TD in the transverse stretching direction is 2.0 to 5.0 N, and ratio of tear strength F MD in the longitudinal stretching direction to tear strength F TD in the transverse stretching direction (F MD / F TD ) is 1.05 to 4.00, and the terminal carboxyl group concentration is 5 to 25 equivalents / ton.
- the present inventors have found that the tear strength in the stretching direction of a biaxially stretched white polyester film is closely related to adhesion and weather resistance.
- the peeling between the white polyester film and the resin layer is likely to occur in the longitudinally stretched direction when the white polyester film is produced by biaxial stretching.
- the unstretched film is drawn in the longitudinal direction (conveying direction) after the melt (melt) obtained by kneading and melting the raw material containing polyester and white particles is discharged from the die and landed on the cooling roll.
- the presence of white particles in the stage promotes the formation of spherulite and longitudinal orientation of the polyester. It is considered that the longitudinally oriented spherulites are partly present after stretching, so that peeling in the longitudinal direction is relatively likely to occur.
- the white polyester film of the present disclosure tear strength in the longitudinal stretching direction F MD and in the transverse stretching direction tear strength F TD are in each within a predetermined range, the longitudinal stretching direction tear strength F MD is the transverse stretching direction tear greater than the strength F TD, that the ratio of their tear strength (F MD / F TD) is within the range between 1.05 and 4.00 is considered that the balance of the adhesion and weather resistance can be taken.
- the polyester contained in the white polyester film of the present disclosure is not particularly limited, and examples thereof include a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
- Specific examples include polyethylene terephthalate (PET), polyethylene isophthalate, polybutylene terephthalate (PBT), poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate (PEN), and the like.
- PET polyethylene terephthalate
- PBT polyethylene isophthalate
- PBT polybutylene terephthalate
- PEN poly (1,4-cyclohexylenedimethylene terephthalate
- PEN polyethylene-2,6-naphthalate
- polyethylene terephthalate and polyethylene-2,6-naphthalate are preferred, and polyethylene terephthalate is particularly preferred from the viewpoint of the balance between mechanical properties and cost.
- the polyester contained in the white polyester film of the present disclosure may be a homopolymer or a copolymer.
- the white polyester film of the present disclosure may be a film obtained by blending a small amount of other types of resins such as polyimide in addition to polyester as a resin component.
- polyester The kind in particular of polyester contained in the stretched white polyester film of this indication is not restrict
- combined from an aromatic dibasic acid or its ester-forming derivative, and diol or its ester-forming derivative is mentioned.
- Specific examples of the linear saturated polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate, and the like. Of these, polyethylene terephthalate, polyethylene-2,6-naphthalate, poly (1,4-cyclohexylenedimethylene terephthalate) and the like are particularly preferable from the viewpoint of the balance between mechanical properties and cost.
- polyester is not limited to the above-mentioned polyester, and other polyesters may be used.
- a polyester synthesized using a dicarboxylic acid component and a diol component may be used, or a commercially available polyester may be used.
- a dicarboxylic acid component and (b) a diol component can be obtained by performing at least one of an esterification reaction and a transesterification reaction by a known method.
- the dicarboxylic acid component for example, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid
- Aliphatic dicarboxylic acids such as ethylmalonic acid
- alicyclic dicarboxylic acids such as adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid
- terephthalic acid isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic
- diol component examples include fats such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol.
- group diols cycloaliphatic diols such as cyclohexanedimethanol, spiroglycol and isosorbide; bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl)
- Aromatic diols such as fluorene;
- the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component.
- the “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more.
- a dicarboxylic acid component other than the aromatic dicarboxylic acid may be included. Examples of such a dicarboxylic acid component include ester derivatives such as aromatic dicarboxylic acids.
- (B) It is preferable to use at least one aliphatic diol as the diol component.
- the aliphatic diol for example, ethylene glycol can be included, and ethylene glycol is preferably contained as a main component.
- the main component means that the proportion of ethylene glycol in the diol component is 80% by mass or more.
- the amount of the aliphatic diol (for example, ethylene glycol) to be used is in the range of 1.015 to 1.50 mol with respect to 1 mol of the aromatic dicarboxylic acid (for example, terephthalic acid) and, if necessary, its ester derivative. preferable.
- the amount of the aliphatic diol used is more preferably in the range of 1.02 to 1.30 mol, and still more preferably in the range of 1.025 to 1.10 mol.
- the esterification reaction proceeds well, and in the range of 1.50 mol or less, for example, a by-product of diethylene glycol by dimerization of ethylene glycol. It is possible to keep a large number of properties such as melting point, glass transition temperature, crystallinity, heat resistance, hydrolysis resistance, weather resistance and the like.
- a known reaction catalyst can be used for the esterification reaction or transesterification reaction.
- the reaction catalyst include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds.
- an antimony compound, a germanium compound, a titanium compound or the like as a polymerization catalyst at an arbitrary stage before the production of the polyester is completed.
- a germanium compound is taken as an example, it is preferable to add the germanium compound powder as it is.
- an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound.
- an organic chelate titanium complex having an organic acid as a ligand is used as a catalyst titanium compound, and at least an organic chelate titanium complex, a magnesium compound, and an aromatic ring as a substituent are used in the process. It is preferable to provide a process of adding a pentavalent phosphate ester which is not included in this order.
- an aromatic dicarboxylic acid and an aliphatic diol are mixed with a catalyst containing an organic chelate titanium complex, which is a titanium compound, prior to the addition of the magnesium compound and the phosphorus compound.
- a catalyst containing an organic chelate titanium complex which is a titanium compound
- Titanium compounds such as organic chelate titanium complexes have high catalytic activity for esterification reactions, so that esterification reactions can be performed satisfactorily.
- the titanium compound may be added to the mixture of the aromatic dicarboxylic acid component and the aliphatic diol component, or the aliphatic diol after mixing the aromatic dicarboxylic acid component (or aliphatic diol component) and the titanium compound.
- the pentavalent phosphorus compound at least one pentavalent phosphate having no aromatic ring as a substituent is used.
- pentavalent phosphate having no aromatic ring as a substituent
- an amount in which the P element conversion value is in the range of 50 ppm to 90 ppm is preferable.
- the amount of the phosphorus compound is such that the P element conversion value is more preferably 60 ppm to 80 ppm, and still more preferably 60 ppm to 75 ppm.
- the electrostatic applicability of the polyester is improved.
- the magnesium compound include magnesium salts such as magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate.
- magnesium acetate is most preferable from the viewpoint of solubility in aliphatic diols such as ethylene glycol.
- the amount of magnesium compound added is preferably such that the Mg element conversion value is 50 ppm or more, more preferably in the range of 50 ppm to 100 ppm, in order to impart high electrostatic applicability.
- the addition amount of the magnesium compound is an amount such that the Mg element conversion value is preferably in the range of 60 ppm to 90 ppm, more preferably in the range of 70 ppm to 80 ppm, in terms of imparting electrostatic applicability.
- the titanium compound as the catalyst component and the magnesium compound and phosphorus compound as the additive are so calculated that the value Z calculated from the following formula (i) satisfies the following relational expression (ii). It is particularly preferred to add and melt polymerize.
- the P content is the amount of phosphorus derived from the entire phosphorus compound including the pentavalent phosphate ester having no aromatic ring
- the Ti content is the amount of titanium derived from the entire Ti compound including the organic chelate titanium complex. It is.
- Formula (i) expresses the amount of phosphorus that can act on titanium by excluding the phosphorus content that acts on magnesium from the total amount of phosphorus that can be reacted.
- Z When the value Z is positive, it can be said that there is an excess of phosphorus that inhibits titanium, and conversely, when it is negative, there is a shortage of phosphorus necessary to inhibit titanium.
- each mole number in the formula is weighted by multiplying by a valence.
- Polyester synthesis does not require special synthesis, etc., and has the reaction activity required for the reaction using inexpensive and easily available titanium compounds, such phosphorus compounds, and magnesium compounds. However, it is possible to obtain a polyester excellent in color tone and heat resistance against heat.
- a chelated titanium complex having 1 ppm to 30 ppm of citric acid or citrate as a ligand is added to the aromatic dicarboxylic acid and the aliphatic diol before the esterification reaction is completed. It is good to add. Thereafter, 60 ppm to 90 ppm (more preferably 70 ppm to 80 ppm) of a weak acid magnesium salt is added in the presence of the chelate titanium complex, and after the addition, an aromatic ring of 60 ppm to 80 ppm (more preferably 65 ppm to 75 ppm) is further added. It is preferable to add a pentavalent phosphate that does not have a substituent.
- the esterification reaction step should be carried out using a multistage apparatus in which at least two reactors are connected in series under conditions where ethylene glycol is refluxed while removing water or alcohol produced by the reaction out of the system. Can do.
- the esterification reaction process may be performed in one stage or may be performed in multiple stages.
- the esterification reaction temperature is preferably 230 ° C to 260 ° C, more preferably 240 ° C to 250 ° C.
- the temperature of the esterification reaction in the first reaction tank is preferably 230 ° C. to 260 ° C., more preferably 240 ° C. to 250 ° C.
- the pressure is 1.0 kg / cm. It is preferably 2 to 5.0 kg / cm 2 , more preferably 2.0 kg / cm 2 to 3.0 kg / cm 2 .
- the temperature of the esterification reaction in the second reaction tank is preferably 230 ° C. to 260 ° C., more preferably 245 ° C. to 255 ° C., and the pressure is 0.5 kg / cm 2 to 5.0 kg / cm 2 , more preferably 1 0.0 kg / cm 2 to 3.0 kg / cm 2 . Furthermore, when carrying out by dividing into three or more stages, it is preferable to set the conditions for the esterification reaction in the intermediate stage to the conditions between the first reaction tank and the final reaction tank.
- esterification reaction product produced by the esterification reaction is subjected to a polycondensation reaction to produce a polycondensate.
- the polycondensation reaction may be performed in one stage or may be performed in multiple stages.
- the esterification reaction product such as an oligomer generated by the esterification reaction is subsequently subjected to a polycondensation reaction.
- This polycondensation reaction can be suitably performed by supplying the esterification reaction product to a multistage polycondensation reaction tank.
- the polycondensation reaction conditions in the case of performing in a three-stage reaction tank are as follows: the first reaction tank has a reaction temperature of 255 ° C. to 280 ° C., more preferably 265 ° C. to 275 ° C., and a pressure of 100 to 10 torr (13 3 ⁇ 10 ⁇ 3 MPa to 1.3 ⁇ 10 ⁇ 3 MPa), more preferably 50 to 20 torr (6.67 ⁇ 10 ⁇ 3 MPa to 2.67 ⁇ 10 ⁇ 3 MPa), and the second reaction The tank has a reaction temperature of 265 ° C. to 285 ° C., more preferably 270 ° C.
- a 10tor ⁇ 3torr is (1.33 ⁇ 10 -3 MPa ⁇ 4.0 ⁇ 10 -4 MPa)
- a third reaction vessel in the final reaction tank the reaction temperature is 270 ° C. ⁇ 290 ° C.
- pressure 10torr ⁇ 0.1torr (1.33 ⁇ 10 -3 MPa ⁇ 1.33 ⁇ 10 -5 MPa), and more preferably 5 torr ⁇ 0.5 torr (6.67
- An embodiment of ⁇ 10 ⁇ 4 MPa to 6.67 ⁇ 10 ⁇ 5 MPa) is preferable.
- Additives such as light stabilizers, antioxidants, UV absorbers, flame retardants, lubricants (fine particles), nucleating agents (crystallization agents), crystallization inhibitors, etc. to the polyester synthesized as described above May further be included.
- the ethylene glycol (EG) gas concentration at the start of solid phase polymerization is preferably higher in the range of 200 ppm to 1000 ppm than the EG gas concentration at the end of solid phase polymerization, more preferably 250 ppm to 800 ppm, and even more preferably 300 ppm. It is preferable to carry out solid phase polymerization at a high level in the range of ⁇ 700 ppm.
- the terminal COOH concentration can be controlled by adding an average EG gas concentration (average gas concentration at the start and end of solid-phase polymerization). That is, the terminal COOH concentration can be reduced by reacting with the terminal COOH by adding EG.
- the EG is preferably 100 ppm to 500 ppm, more preferably 150 ppm to 450 ppm, and still more preferably 200 ppm to 400 ppm.
- the temperature of the solid phase polymerization is preferably 180 ° C. to 230 ° C., more preferably 190 ° C. to 215 ° C., and further preferably 195 ° C. to 209 ° C.
- the solid phase polymerization time is preferably 10 hours to 40 hours, more preferably 14 hours to 35 hours, and further preferably 18 hours to 30 hours.
- the polyester preferably has high hydrolysis resistance. Therefore, the carboxyl group content in the polyester is preferably 50 equivalent / t or less (where t means ton, where ton means 1000 kg), and more preferably 35 equivalent / t or less, More preferably, it is 20 equivalent / t or less.
- the lower limit of the carboxyl group content is preferably 2 equivalents / t, more preferably 3 equivalents / t, and even more preferably 3 equivalents in terms of maintaining adhesion between the layer formed on the polyester (for example, a resin layer). / T.
- the carboxyl group content in the polyester can be adjusted by polymerization catalyst species, film forming conditions (film forming temperature and time), solid phase polymerization, additives (end-capping agent, etc.) and the like.
- the white polyester film of the present disclosure can be further improved in hydrolysis resistance (weather resistance) by adding an end-capping agent.
- the white polyester film of the present disclosure can contain 0.1 to 10% by mass of a terminal blocking agent based on the total mass of the polyester.
- the added amount of the end-capping agent with respect to the total mass of the polyester contained in the polyester film is more preferably 0.2 to 5% by mass, still more preferably 0.3 to 2% by mass.
- an end-capping agent that reacts with the terminal carboxyl group is used to improve hydrolysis resistance (weather resistance). It is effective to add. If the added amount of the end-capping agent is 0.1% by mass or more with respect to the total mass of the polyester, the effect of improving the weather resistance is easily exhibited, and if it is 10% by mass or less, it acts as a plasticizer for the polyester. Is suppressed, and the decrease in mechanical strength and heat resistance is suppressed.
- end capping agent examples include epoxy compounds, carbodiimide compounds, oxazoline compounds, carbonate compounds, and the like, but carbodiimide compounds (hereinafter referred to as “carbodiimide” or “carbodiimide” having a high affinity with polyethylene terephthalate (PET) and high end capping ability. It may be referred to as “carbodiimide end-capping agent”).
- terminal blocker (especially carbodiimide terminal blocker) is high molecular weight. Volatilization during melt film formation can be reduced by using a high molecular weight end-capping agent.
- the molecular weight of the end-capping agent is preferably 200 to 100,000, more preferably 2000 to 80,000, still more preferably 10,000 to 50,000. If the molecular weight of the end-capping agent (particularly carbodiimide end-capping agent) is in the range of 200 to 100,000, the end-capping agent tends to be uniformly dispersed in the polyester, and the effect of improving weather resistance can be sufficiently exhibited. Moreover, it is difficult for the end-capping agent to be volatilized during extrusion and film formation, and the effect of improving weather resistance is easily exhibited.
- the molecular weight of terminal blocker means a weight average molecular weight.
- the carbodiimide compound having a carbodiimide group includes a monofunctional carbodiimide and a polyfunctional carbodiimide.
- the monofunctional carbodiimide include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, and diphenylcarbodiimide. , Di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide and the like. Particularly preferred are dicyclohexylcarbodiimide and diisopropylcarbodiimide.
- carbodiimide having a polymerization degree of 3 to 15 is preferably used.
- the carbodiimide compound is preferably a carbodiimide compound having high heat resistance because an isocyanate gas is generated by thermal decomposition.
- the molecular weight degree of polymerization
- the terminal of the carbodiimide compound has a structure with high heat resistance.
- the terminal blocker carbodiimide is also preferably a carbodiimide having a cyclic structure (for example, a carbodiimide having a cyclic structure described in JP 2011-153209 A). Even if the carbodiimide having a cyclic structure has a low molecular weight, the same effect as that of the above high molecular weight carbodiimide is exhibited. This is because the terminal carboxyl group of the polyester and the cyclic carbodiimide undergo a ring-opening reaction, one reacts with this polyester, and the other with the ring-opening reacts with another polyester to increase the molecular weight, thus generating an isocyanate gas. This is because it is suppressed.
- a carbodiimide having a cyclic structure for example, a carbodiimide having a cyclic structure described in JP 2011-153209 A.
- the end-capping agent is a carbodiimide compound having a carbodiimide group and a cyclic structure in which the first nitrogen and the second nitrogen are bonded by a bonding group.
- the end capping agent has a cyclic structure in which at least one carbodiimide group adjacent to the aromatic ring is present, and the first nitrogen and the second nitrogen of the carbodiimide group adjacent to the aromatic ring are bonded by a bonding group.
- carbodiimide also referred to as aromatic cyclic carbodiimide.
- the aromatic cyclic carbodiimide may have a plurality of cyclic structures.
- An aromatic cyclic carbodiimide is an aromatic carbodiimide having no ring structure in which the first nitrogen and the second nitrogen of two or more carbodiimide groups are bonded by a linking group in the molecule, that is, an aromatic carbodiimide having a single ring. Can also be preferably used.
- the cyclic structure has one carbodiimide group (—N ⁇ C ⁇ N—), and the first nitrogen and the second nitrogen are bonded by a bonding group.
- One cyclic structure has only one carbodiimide group.
- the compound may have a plurality of carbodiimide groups.
- the number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
- the number of atoms in the cyclic structure means the number of atoms directly constituting the cyclic structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. If the number of atoms in the cyclic structure is 8 or more, the stability of the cyclic carbodiimide compound increases, and storage and use become easy. From the standpoint of reactivity, there is no particular limitation on the upper limit of the number of ring members, but cyclic carbodiimide compounds having 50 or less atoms are less difficult to synthesize and the cost can be kept low. From this viewpoint, the number of atoms in the cyclic structure is preferably in the range of 10 to 30, more preferably 10 to 20, and particularly preferably 10 to 15.
- carbodiimide end-capping agent having a cyclic structure examples include the following compounds. However, the present disclosure is not limited by the following specific examples.
- Epoxy end sealant Preferable examples of the epoxy compound include glycidyl ester compounds and glycidyl ether compounds.
- glycidyl ester compounds include benzoic acid glycidyl ester, t-Bu-benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, and lauric acid glycidyl ester.
- glycidyl ether compound examples include phenyl glycidyl ether, O-phenyl glycidyl ether, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) butane, 1,6-bis ( ⁇ , ⁇ -epoxypropoxy).
- Oxazoline-based end-capping agent As the oxazoline compound, a bisoxazoline compound is preferable, and specifically, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4-dimethyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-2-oxazoline), 2,2 '-Bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'- Bis (4-phenyl-2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p- Phenylenebis (2-oxazoline), 2,2'-m- Enylene
- 2,2′-bis (2-oxazoline) is most preferably used from the viewpoint of reactivity with polyester.
- the bisoxazoline compound mentioned above may be used individually by 1 type, or may use 2 or more types together.
- the white polyester film of the present disclosure contains white particles. By containing white particles, light reflectivity or design can be imparted to the film.
- the white particles contained in the white polyester film of the present disclosure may be either inorganic particles or organic particles, or both may be used in combination.
- inorganic particles include wet silica, dry silica, colloidal silica, calcium carbonate, aluminum silicate, calcium phosphate, alumina, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide (also called zinc white), antimony oxide, cerium oxide, Zirconium oxide, tin oxide, lanthanum oxide, magnesium oxide, barium carbonate, zinc carbonate, basic lead carbonate (also called lead white), barium sulfate, calcium sulfate, lead sulfate, zinc sulfide, mica, titanium mica, talc, clay, Kaolin, lithium fluoride, calcium fluoride or the like can be used.
- the surface of the white particles may be subjected to a surface treatment with an inorganic material such as alumina or silica, or may be subjected to a surface treatment with an organic material such as silicone or alcohol.
- the white polyester film of the present disclosure can exhibit excellent durability even under light irradiation.
- Titanium dioxide includes rutile type and anatase type
- the white polyester film of the present disclosure preferably includes titanium dioxide particles mainly composed of rutile type.
- the term “main body” as used herein means that the amount of rutile titanium dioxide in all titanium dioxide particles exceeds 50% by mass. Since the light in the ultraviolet region hardly contributes to the power generation of the solar cell, it is desirable that the spectral reflectance of the white particles is high from the viewpoint of preventing the polyester from being deteriorated by ultraviolet rays.
- the rutile type of titanium dioxide has a very high spectral reflectance of ultraviolet rays, whereas the anatase type has a characteristic of high absorption rate of ultraviolet rays (small spectral reflectance).
- the titanium dioxide crystal form From the difference in the spectral characteristics of the titanium dioxide crystal form, it is possible to improve the light resistance in, for example, a solar cell back surface protection polyester film (solar cell back sheet) by utilizing the rutile ultraviolet absorption performance. it can. Further, by utilizing the ultraviolet absorbing performance of rutile titanium dioxide, the film durability under light irradiation is excellent even when no other ultraviolet absorber is substantially added. For this reason, contamination due to bleeding out of the ultraviolet absorber and reduction in adhesion are unlikely to occur.
- the content of anatase-type titanium dioxide in the titanium dioxide particles contained in the white polyester film of the present disclosure is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass. If the content of anatase-type titanium dioxide in the titanium dioxide particles contained in the white polyester film of the present disclosure is 10% by mass or less, the amount of rutile-type titanium dioxide in the total titanium dioxide particles is relatively high. In addition to sufficient UV absorption performance, anatase-type titanium dioxide has a strong photocatalytic action, so that it is possible to suppress a decrease in light resistance due to the photocatalytic action. Rutile titanium dioxide and anatase titanium dioxide can be distinguished by X-ray structural diffraction or spectral absorption characteristics.
- the rutile titanium dioxide particles may be subjected to a surface treatment with an inorganic material such as alumina or silica on the particle surface, or may be subjected to a surface treatment with an organic material such as a silicone or alcohol.
- Rutile titanium dioxide may be adjusted in particle diameter and removed coarse particles using a purification process before blending with polyester.
- 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 white polyester film of the present disclosure may contain organic particles as white particles.
- the organic particles are preferably particles that can withstand heat during the formation of the polyester film.
- white particles made of a cross-linked resin are used. Specifically, polystyrene cross-linked with divinylbenzene is used.
- the content of white particles contained in the white polyester film of the present disclosure is preferably 2 to 10% by mass with respect to the total mass of the film.
- the content of the white particles contained in the white polyester film of the present disclosure is 2% by mass or more, high light reflectance is obtained, and when it is 10% by mass or less, high weather resistance and adhesion can be obtained.
- the content of the white particles contained in the white polyester film of the present disclosure is more preferably 2 to 8% by mass, and further preferably 3 to 6% by mass.
- the white polyester film of the present disclosure may contain one type or two or more types of white particles.
- the total content of the white particles is preferably 2 to 10% by mass.
- the content of white particles contained in the white polyester film can be measured by the following method. 3 g of a film is taken as a measurement sample in a crucible and heated at 900 ° C. for 120 minutes in an electric oven. Then, after the electric oven has cooled, the crucible is taken out and the mass of ash remaining in the crucible is measured. This ash is white particle content, and the mass obtained by dividing the mass of the ash by the mass of the measurement sample and multiplying by 100 is defined as the content (mass%) of the white particles. In addition, if it is before manufacture of a film, you may obtain
- the average particle size of the white particles is preferably 0.03 to 0.25 ⁇ m, more preferably 0.07 to 0.25 ⁇ m, and still more preferably 0.1 to 0.2 ⁇ m. If the average particle diameter of the particles is 0.03 to 0.25 ⁇ m, light can be effectively reflected from the visible light region to the near infrared light region, which is particularly effective for power generation.
- the average particle diameter of the white particles contained in the white polyester film in the present disclosure is determined by a method using an electron microscope. Specifically, the following method is used.
- the white particles in the cross section in the thickness direction of the film are observed with a scanning electron microscope, the magnification is appropriately changed according to the size of the particles, a photograph is taken, and an enlarged copy is made.
- the circumference of each particle is traced for at least 200 randomly selected particles.
- the equivalent circle diameter of the particles is measured from these trace images with an image analysis apparatus, and the average value of these is taken as the average particle diameter.
- the rutile-type titanium oxide particles may be subjected to a surface treatment with an inorganic material such as alumina or silica on the particle surface, or a surface treatment with an organic material such as silicone or alcohol.
- Rutile titanium oxide may be subjected to particle size adjustment and coarse particle removal using a purification process before blending with polyester.
- 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.
- a thickness of 250 ⁇ m corresponding, longitudinally stretched direction tear strength F MD is 2.5 ⁇ 6.0 N
- the transverse stretching direction of the tear strength F TD is 2.0 ⁇ 5.0 N
- the ratio of longitudinal stretching direction tear strength F MD in the transverse stretching direction relative to the tear strength F TD is from 1.05 to 4.00.
- tear strength F MD in the longitudinal stretching direction per 250 ⁇ m thickness is preferably 2.5 to a 5.5 N, is preferably 3.0 - 5.0 N.
- the transverse stretching direction of the tear strength F TD per 250 ⁇ m thickness is more than 2.0 N, high adhesion, cracks during cutting of the film by at most 5.0N Occurrence is suppressed.
- the tear strength F TD in the transverse stretching direction per 250 ⁇ m thickness is preferably 2.0 to 4.5 N, and more preferably 2.0 to 4.0 N. It may also be particularly improved weatherability by the tear strength F TD in the transverse stretching direction within a range of 2.0 ⁇ 4.0 N.
- the white polyester film of the present disclosure the lateral thickness of 250 ⁇ m corresponding, tear strength F MD in the longitudinal stretching direction is 2.5 ⁇ 6.0 N, and the transverse stretching direction tear strength F TD 2.0 Even if it is ⁇ 5.0 N, the weather resistance is insufficient if the tear strength ratio is less than 1.05, and if it exceeds 4.00, the adhesion is insufficient.
- the tear strength ratio F MD / F TD of MD and TD is preferably 1.05 to 3.00, and more preferably 1.05 to 2.50.
- Tear strength of each direction it tends to increase tear strength F MD in the longitudinal stretching direction by reducing the difference between the temperature of the landing point of the discharge temperature from the die to the cooling roll is in the unstretched film forming step, tear strength F TD in the transverse stretching direction by increasing the heat setting temperature tends to increase. Details of the manufacturing method will be described later.
- the tear strength of the white polyester film of the present disclosure is measured by the following method.
- ⁇ Measurement method> Cut out the sample film in the MD and TD directions to 2 cm width (short side) ⁇ 10 cm length (long side), respectively.
- -A notch with a length of 5 cm is placed in the center of the short side in parallel with the long side direction, and the stress is measured by the following method using a tensile tester. The measurement is performed at 25 ° C. and 50% relative humidity.
- (1-1) One end of the cut portion is held by one chuck of the tensile tester, and the other end is held by the other chuck.
- (1-2) Measure the tensile stress of the chuck at 30 mm / min.
- the film manufactured through processes such as biaxial stretching
- the circumferential direction (conveying direction) of the roll is MD
- the width direction is TD.
- MD and TD can be specified by setting MD as a direction with a large heat shrinkage rate.
- the white polyester film of the present disclosure preferably has a terminal carboxyl group concentration of 5 to 25 equivalents / ton.
- the terminal carboxyl group concentration is also referred to as an acid value (Acid value) and may be described as “AV”.
- acid value acid value
- AV acid value
- “equivalent / ton” represents a molar equivalent per ton and may be described as “eq / t”.
- the terminal carboxyl group concentration in the polyester film is 5 equivalents / ton or more, the surface carboxyl groups (COOH groups) do not become too small (that is, the polarity does not become too low), and other materials such as other resin layers It can have high adhesiveness.
- hydrolysis of the polyester molecule terminal CO + group is promoted using a catalyst. If the terminal carboxyl group density
- the terminal carboxyl group concentration in the white polyester film of the present disclosure is more preferably 10 to 25 equivalents / ton, and even more preferably Is 15 to 25 equivalents / ton.
- the terminal carboxyl group concentration is a value measured by the following method. That is, after dissolving 0.1 g of a resin measurement sample in 10 mL of benzyl alcohol, chloroform is further added to obtain a mixed solution, and phenol red indicator is dropped into this mixed solution. This solution is titrated with a standard solution (0.01 mol / L KOH-benzyl alcohol mixed solution), and the terminal carboxyl group concentration is determined from the amount added.
- the white polyester film of the present disclosure preferably has a tan ⁇ peak temperature of 122 to 135 ° C. measured with a dynamic viscoelasticity measuring apparatus. If the peak temperature of tan ⁇ measured by a dynamic viscoelasticity measuring apparatus is 122 ° C. or higher, the weather resistance can be improved, and if it is 135 ° C. or lower, the adhesion can be improved. From this viewpoint, the white polyester film of the present disclosure has a tan ⁇ peak temperature of more preferably 122 to 130 ° C., and particularly preferably 122 to 128 ° C.
- the tan ⁇ peak temperature of the white polyester film is adjusted by the polymerization catalyst type before film formation, the solid-state polymerization conditions after normal polymerization, and the film formation conditions (film formation temperature, time, stretching conditions and thermal relaxation conditions), etc. Is possible. In particular, it is particularly preferable to control by stretching conditions (stretching ratio and heat setting temperature) that can be adjusted online.
- the peak temperature of tan ⁇ was adjusted at 25 ° C.
- Vibron Dynamic Viscoelasticity measuring device
- the white polyester film of the present disclosure preferably has an intrinsic viscosity (IV) of 0.65 to 0.90 dL / g. If the IV of the film is 0.65 dL / g or more, sufficient weather resistance can be obtained. On the other hand, if the IV of the film is 0.90 dL / g or less, it is easy to extrude the melt (melt) in the unstretched film forming step when manufacturing the film, and the shear heat generation is suppressed, and the water resistance is reduced. The degradation of the decomposition performance is suppressed.
- IV intrinsic viscosity
- the IV of the film is more preferably 0.65 to 0.85 dL / g, and further preferably 0.67 to 0.77 dL / g.
- the method described in Examples is used as a method for measuring IV of the white polyester film of the present disclosure.
- the thickness of the white polyester film of the present disclosure is preferably 220 to 450 ⁇ m.
- the thickness of the film is 250 ⁇ m or more, high voltage resistance can be obtained.
- the thickness of the film is 500 ⁇ m or less, a decrease in hydrolysis resistance due to a decrease in the heating / cooling ability of the film during film formation is suppressed, and the film is stretched without placing a high load on the stretching machine. It can be carried out. From this viewpoint, the thickness of the film is more preferably 250 to 350 ⁇ m.
- the method described in Examples is used.
- the white polyester film of the present disclosure may be subjected to surface treatment such as corona treatment, flame treatment, glow discharge treatment and the like, as necessary, in order to further improve the adhesion with different materials.
- Corona discharge treatment is usually performed by applying high frequency and high voltage between a metal roll (dielectric roll) coated with a derivative and an insulated electrode to cause dielectric breakdown of the air between the electrodes. Is ionized to generate a corona discharge between the electrodes. And a surface treatment is performed by letting a polyester film pass between this corona discharge.
- the treatment conditions used in the present disclosure are preferably a gap clearance of 1 to 3 mm between the electrode and the dielectric roll, a frequency of 1 to 100 kHz, and an applied energy of about 0.2 to 5 kV ⁇ A ⁇ min / m 2 .
- Glow discharge treatment is a method called vacuum plasma treatment or low-pressure plasma treatment, and is a method of treating the surface of a film by generating plasma by discharge in a gas (plasma gas) in a low-pressure atmosphere.
- the low-pressure plasma used in the glow discharge treatment of the present disclosure is non-equilibrium plasma generated under a condition where the pressure of the plasma gas is low.
- the glow discharge treatment of the polyester film is performed by placing a film to be treated (polyester film) in this low-pressure plasma atmosphere.
- the power source used for discharging may be direct current or alternating current.
- alternating current a range of about 30 Hz to 20 MHz is preferable.
- alternating current a commercial frequency of 50 or 60 Hz may be used, or a high frequency of about 10 to 50 kHz may be used.
- a method using a high frequency of 13.56 MHz is also preferable.
- an inorganic gas such as oxygen gas, nitrogen gas, water vapor gas, argon gas, and helium gas can be used.
- oxygen gas or a mixed gas of oxygen gas and argon gas can be used. Is preferred.
- a method in which a gas such as water entering the processing container due to a leak and water vapor coming out of the object to be processed is used as the plasma gas without introducing a gas into the processing container.
- the plasma gas pressure needs to be low enough to achieve non-equilibrium plasma conditions.
- the specific plasma gas pressure is preferably in the range of about 0.005 to 10 Torr (0.666 to 1333 Pa), more preferably about 0.008 to 3 Torr (1.067 to 400 Pa). If the pressure of the plasma gas is 0.666 Pa or more, the effect of improving the adhesiveness is sufficient, and if it is 1333 Pa or less, the current is increased and the discharge is suppressed from becoming unstable.
- the plasma output cannot be generally specified depending on the shape and size of the processing vessel and the shape of the electrode, but is preferably about 100 to 2500 W, more preferably about 500 to 1500 W.
- the treatment time of the glow discharge treatment is preferably about 0.05 to 100 seconds, more preferably about 0.5 to 30 seconds. If the treatment time is 0.05 seconds or longer, the effect of improving adhesiveness is sufficiently obtained, and if it is 100 seconds or less, deformation, coloring, etc. of the film to be treated can be prevented.
- the discharge treatment intensity of the glow discharge treatment depends on the plasma output and the treatment time, but is preferably in the range of 0.01 to 10 kV ⁇ A ⁇ min / m 2 , more preferably 0.1 to 7 kV ⁇ A ⁇ min / m 2 . Discharge treatment intensity that is sufficient adhesion improving effect of the 0.01 kV ⁇ A ⁇ min / m 2 or more is obtained and deformation of the processed film by a 10 kV ⁇ A ⁇ min / m 2 or less, coloration Can be avoided.
- the heating temperature is preferably in the range of 40 ° C. to the softening temperature of the film to be treated + 20 ° C., more preferably in the range of 70 ° C. to the softening temperature of the film to be processed.
- the heating temperature is preferably in the range of 40 ° C. or higher, a sufficient adhesive improvement effect can be obtained.
- the handleability of a favorable film can be ensured during a process by making heating temperature below into the softening temperature of a to-be-processed film.
- Specific methods for raising the temperature of the film to be treated in vacuum include heating with an infrared heater, heating by contacting with a hot roll, and the like.
- Examples of the flame treatment include flame treatment using a flame introduced with a silane compound.
- the method for producing the stretched white polyester film of the present disclosure is not particularly limited.
- the stretched white polyester film of the present disclosure can be suitably produced by the following method.
- the method for producing a white polyester film of the present disclosure is such that a melt obtained by melting a mixture containing a raw material polyester and white particles is discharged from a die and landed on a cooling roll to form an unstretched film.
- the manufacturing method of the white polyester film of this indication performs a heat relaxation process after a heat setting process.
- in-line coating for forming an undercoat layer may be performed. Good.
- the manufacturing method of the white polyester film of this indication is not limited to the following method.
- the raw material containing white particles such as polyester and titanium oxide is dried, the raw material is melted, and the obtained melt (melt) is passed through a gear pump and a filter. Then, an unstretched film is obtained by discharging a molten material from die
- A A method in which white particles are added before the end of the ester exchange reaction or esterification reaction during polyester synthesis, or white particles are added before the start of the polycondensation reaction.
- B A method in which white particles are added to polyester and melt-kneaded.
- C A master batch (also referred to as master pellet) in which a large amount of white particles is added by the method of (A) or (B) above is produced, and the master batch and white particles are contained or a small amount of white pigment is contained.
- D A method of melt-kneading using the master pellet of (C) as it is.
- the method (C) that is, a master batch (hereinafter sometimes referred to as “MB”) in which a large amount of white particles is added is produced, and the master batch and the white particles are not contained or a small amount.
- a method of kneading with a polyester containing a white pigment to contain a predetermined amount of white particles (hereinafter sometimes referred to as “masterbatch method”) is preferred.
- masterbatch method it is possible to adopt a method in which polyester and white particles that have not been dried in advance are put into an extruder and a master batch is produced while degassing moisture and air.
- the moisture content of the polyester resin when producing a masterbatch (MB), it is preferable to reduce the moisture content of the polyester resin to be charged in advance by drying.
- the drying conditions are preferably 100 to 200 ° C., more preferably 120 to 180 ° C., for 1 hour or longer, more preferably 3 hours or longer, and even more preferably 6 hours or longer. Thereby, it is sufficiently dried so that the moisture content of the polyester resin is preferably 50 ppm or less, more preferably 30 ppm or less.
- the method for performing the preliminary mixing is not particularly limited, and a batch method may be used, or the preliminary mixing may be performed by a single-screw or biaxial or more kneading extruder.
- the polyester resin When producing a masterbatch while deaeration, the polyester resin is melted at a temperature of 250 ° C. to 300 ° C., preferably 270 ° C. to 280 ° C., and one, preferably two or more deaeration ports are provided in the pre-kneader. It is preferable to employ a method of performing continuous suction deaeration of 0.05 MPa or more, more preferably 0.1 MPa or more, and maintaining the reduced pressure in the mixer.
- the extrusion of the molten resin (melt) is preferably performed in an evacuated or inert gas atmosphere.
- the melting temperature in the extruder is preferably from the melting point of the raw material polyester used to the melting point + 80 ° C. or less, more preferably the melting point + 10 ° C. or more, the melting point + 70 ° C. or less, more preferably the melting point + 20 ° C. or more, the melting point + 60 ° C. or less. .
- the melting temperature in the extruder is a melting point + 10 ° C. or higher, the resin is sufficiently melted.
- the melting temperature is 70 ° C. or lower, decomposition of polyester or the like is preferably suppressed.
- the raw material polyester is preferably dried before the raw material is put into the extruder, and the preferred moisture content is 10 ppm to 300 ppm, more preferably 20 ppm to 150 ppm.
- an end-capping agent may be added when the raw material resin is melted.
- the end-capping agent may be added directly to the extruder together with the polyester or the like, but it is preferable from the viewpoint of extrusion stability that a polyester and a master batch are formed in advance and charged into the extruder.
- Extruded melt (melt) is poured on a cooling roll (cast drum) through a gear pump, a filter and a die.
- the shape of the die may be a T-die, a hanger coat die, or a fish tail.
- the molten resin (melt) can be brought into close contact with the cooling roll using an electrostatic application method.
- the discharge temperature of the melt discharged from the die is preferably 270 to 310 ° C, more preferably 275 to 300 ° C, and further preferably 280 to 295 ° C.
- the discharge temperature from the die can be controlled by the temperature of the melt extruded from the extruder, the temperature of the piping and the die, and the like.
- the surface temperature of the cooling roll can be approximately 10 ° C to 40 ° C.
- the diameter of the cooling roll is preferably 0.5 m or more and 5 m or less, more preferably 1 m or more and 4 m or less.
- the driving speed of the cooling roll (the outermost linear velocity) is preferably 1 m / min or more and 50 m / min or less, more preferably 3 m / min or more and 30 m / min or less.
- ⁇ T is preferably 12 ° C. or less, and more preferably 7 ° C. or less.
- the melt discharged from the die is rapidly cooled by air blow and / or convection of the outside air for cooling the unstretched film after landing on the cooling roll before landing on the cooling roll.
- the means for suppressing ⁇ T to 20 ° C. or lower is not particularly limited.
- a cover 74 is provided around the discharge portion of the die 70, and wind is applied to the melt 72 discharged from the die 70.
- ⁇ T may be suppressed to 20 ° C. or less by setting the distance D between the discharge portion of the die 70 and the cooling rolls 76 and 78 (the landing point of the melt 72) to 10 to 100 mm. Further, ⁇ T may be suppressed to 20 ° C. or less by reducing the difference between the set temperature at the discharge portion of the die 70 and the set temperature at the surface of the cooling rolls 76 and 78.
- the discharge temperature T1 of the melt 72 discharged from the die 70 and the landing temperature T2 of the melt 72 discharged from the die 70 on the cooling rolls 76 and 78 can be measured by a radiation thermometer, respectively.
- the measurement field of the radiation thermometer is desirably small, and the measurement field is desirably 30 mm or less.
- a biaxially stretched film is formed by stretching an unstretched film cooled by a cooling roll in a machine direction (MD) and a transverse direction (TD).
- MD machine direction
- TD transverse direction
- FIG. 1 schematically shows an example of a biaxial stretching machine used for production of a stretched white polyester film of the present disclosure.
- FIG. 1 shows a biaxial stretching machine 100 and a polyester film 200 attached to the biaxial stretching machine 100.
- the biaxial stretching machine 100 includes a pair of annular rails 60a and 60b, and is arranged symmetrically with the polyester film 200 in between.
- the biaxial stretching machine 100 includes a preheating unit 10 that preheats the polyester film 200, a stretching unit 20 that stretches the polyester film 200 in an arrow TD direction that is a direction orthogonal to the arrow MD direction, and applies tension to the polyester film, The heat fixing part 30 that heats the polyester film to which the tension is applied is heated, the heat relaxation part 40 that relaxes the tension of the polyester film that is heat-fixed by heating the heat-fixed polyester film, and the heat relaxation part. And a cooling unit 50 for cooling the polyester film.
- the annular rail 60a includes at least gripping members 2a, 2b, 2e, 2f, 2i, and 2j that can move the edge of the annular rail 60a.
- the annular rail 60b is a gripping member 2c that can move the edge of the annular rail 60b. 2d, 2g, 2h, 2k, and 2l.
- the gripping members 2a, 2b, 2e, 2f, 2i, and 2j grip one end of the polyester film 200 in the TD direction, and the gripping members 2c, 2d, 2g, 2h, 2k, and 2l are polyesters The other end of the film 200 in the TD direction is gripped.
- the gripping members 2a to 2l are generally called chucks, clips, and the like. In FIG.
- the gripping members 2a, 2b, 2e, 2f, 2i, and 2j move counterclockwise along the edge of the annular rail 60a, and the gripping members 2c, 2d, 2g, 2h, 2k, and 2l moves clockwise along the edge of the annular rail 60b.
- the gripping members 2a to 2d grip the end portion of the polyester film 200 in the preheating unit 10, and move the edge of the annular rail 60a or 60b as it is, so that the extending portion 20 and the gripping members 2e to 2h are shown.
- the process proceeds to the cooling section 50 where the gripping members 2i to 2l are shown.
- the gripping members 2a, 2b and the gripping members 2c, 2d are separated from the end of the polyester film 200 at the downstream end in the MD direction of the cooling unit 50 in the transport direction, and the annular rail 60a or 60b is left as it is. It advances along an edge and returns to the preheating part 10. As a result, the polyester film 200 moves in the direction of the arrow MD in FIG.
- the moving speed of the gripping members 2a to 2l becomes the transport speed at the gripping portion of the polyester film 200.
- the gripping members 2a to 2l can change the moving speed independently of each other. Therefore, the biaxial stretching machine 100 allows the stretching portion 20 to perform lateral stretching in which the polyester film 200 is stretched in the TD direction, but the polyester film 200 is changed to MD by changing the moving speed of the gripping members 2a to 2l. It can also be stretched in the direction. That is, simultaneous biaxial stretching can be performed using the biaxial stretching machine 100.
- the biaxial stretching machine 100 In addition to 2l, it has a gripping member (not shown).
- the gripping members 2a to 2l may be collectively referred to as “grip member 2”.
- the polyester film 200 is preheated. Before the polyester film 200 is stretched, it is preheated to facilitate the lateral stretching of the polyester film 200.
- the film surface temperature at the end point of the preheating part (hereinafter also referred to as “preheating temperature”) is preferably Tg ⁇ 10 ° C. to Tg + 60 ° C., where Tg is the glass transition temperature of the polyester film 200, and Tg ° C. to Tg + 50. More preferably, it is ° C.
- the end point of the preheating portion refers to the time when the preheating of the polyester film 200 is finished, that is, the position where the polyester film 200 is separated from the region of the preheating portion 10.
- the preheated polyester film 200 is laterally stretched at least in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 to give tension to the polyester film 200.
- Stretching (transverse stretching) in the direction (TD) orthogonal to the longitudinal direction (conveying direction, MD) of the polyester film 200 is an angle direction perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 (90 °). It is intended to be stretched.
- the stretching stress is 5 MPa or more and 15 MPa or less and the stretching ratio is 2.5 times or more and 4.5 times in the machine direction of the polyester film with respect to the unstretched film formed in the unstretched film formation step. Longitudinal stretching of less than double is performed.
- the polyester film is led to a group of rolls heated to a temperature of 70 ° C. or more and 120 ° C. or less, and the stretching stress is 5 MPa or more and 15 MPa or less in the longitudinal direction (longitudinal direction, that is, the film traveling direction), and
- the longitudinal stretching is performed at a stretching ratio of 2.5 to 4.5 times, more preferably at a stretching stress of 8 to 14 MPa and a stretching ratio of 3.0 to 4.0 times. It is preferable to cool with the roll group of the temperature of 20 to 50 degreeC after longitudinal stretching.
- the transverse stretching is preferably performed using a tenter.
- the vertically stretched white polyester film is guided to a tenter, and stretched in the transverse direction (TD stretching) in an atmosphere heated to a temperature (stretching temperature) of 80 ° C. or higher and 180 ° C. or lower, for example.
- TD stretching transverse direction
- the polyester film can be stretched in the transverse direction by holding both ends of the polyester film with the clip and expanding the clip in the direction perpendicular to the longitudinal direction, that is, in the transverse direction while transporting the heat treatment zone.
- transverse stretching step it is preferable to perform transverse stretching in which the stretching stress is 8 MPa or more and 20 MPa or less and the stretching ratio is 3.4 times or more and 5 times or less, the stretching stress is 10 MPa or more and 18 MPa or less, and the stretching ratio is It is more preferable to perform transverse stretching of 3.6 times or more and 4.5 times or less.
- the stretching area ratio (longitudinal stretching ratio ⁇ lateral stretching ratio) by biaxial stretching is preferably 9 to 20 times.
- the area magnification is 9 times or more and 20 times or less, for example, the thickness after stretching is 250 ⁇ m or more and 500 ⁇ m or less, the degree of plane orientation is high, the crystallinity is 30% or more and 40% or less, and the equilibrium moisture content Is obtained, a biaxially oriented polyester film having a content of 0.1 mass% to 0.25 mass%.
- the simultaneous biaxial stretching method in addition to the sequential biaxial stretching method in which the longitudinal direction and the transverse direction are separated separately, the simultaneous biaxial stretching method in which the longitudinal direction and the transverse direction are simultaneously stretched. Either may be sufficient.
- the biaxially stretched film is heat set at a temperature of Tm-70 ° C. or higher and Tm-30 ° C. or lower with respect to the melting point Tm ° C. of the raw material polyester.
- Tm-70 ° C. or higher and Tm-30 ° C. or lower with respect to the melting point Tm ° C. of the raw material polyester.
- the heat setting temperature here is the highest surface temperature of the film during the heat setting treatment, and can be measured by a radiation thermometer.
- the state of crystals and tensioned amorphous state of the biaxially stretched film can be controlled. If the heat setting temperature is (Tm-70) ° C. or higher with respect to the melting point Tm of the raw material polyester, the tan ⁇ peak temperature does not become too high, the TD tear strength can be improved, and the cleavage strength can be improved. Can do. On the other hand, if the heat setting temperature is (Tm ⁇ 30) ° C. or less with respect to the melting point Tm of the raw material polyester, the tan ⁇ peak temperature does not become too low, and the weather resistance can be improved.
- the heat setting is preferably performed in the state of being gripped by the chuck in the tenter after the transverse stretching, and the chuck interval is performed at the width at the end of the transverse stretching, further widened, or reduced in width. May be.
- the film is preferably subjected to heat treatment for 1 second to 60 seconds, more preferably 5 seconds to 50 seconds.
- a part of the volatile basic compound having a boiling point of 200 ° C. or less may be volatilized.
- a heat relaxation process is a process which shrinks a film by applying heat for stress relaxation to a film.
- relaxation is preferably performed in at least one of length and width, and the amount of relaxation is preferably 1% to 30% (ratio to the width after transverse stretching), more preferably 2% to 20%. Preferably, it is 3% to 15%.
- the thermal relaxation temperature Tr is 100 ° C. or higher and 15 ° C. or lower than Ts (100 ° C. ⁇ Tr ⁇ Ts ⁇ 15 ° C.). It is more preferable that the temperature range is 110 ° C.
- Ts 110 ° C. ⁇ Tr ⁇ Ts ⁇ 25 ° C.
- Ts 110 ° C. ⁇ Tr ⁇ Ts ⁇ 25 ° C.
- the region (120 ° C. ⁇ Tr ⁇ Ts ⁇ 30 ° C.) is particularly preferable.
- the polyester film is thermally relaxed under the conditions within the above range, and the tension of the polyester molecules is somewhat released, so that the dimensional stability is improved while maintaining hydrolysis resistance, and the obtained polyester film Failures in downstream processes such as machining are less likely to occur.
- Lateral relaxation can be carried out by reducing the interval between the opposing clips of the tenter (interval between the annular rails 60a and 60b). Moreover, longitudinal relaxation can be implemented by narrowing the interval between adjacent clips of the tenter. This can be achieved by connecting adjacent clips in a pantograph shape and shrinking the pantograph. Moreover, after taking out a film from a tenter, it can also relieve
- Tension is preferably cross-sectional area per 0N / mm 2 ⁇ 0.8N / mm 2 of film, more preferably 0N / mm 2 ⁇ 0.6N / mm 2, more preferably 0N / mm 2 ⁇ 0.4N / mm 2 It is. 0 N / mm 2 can be carried out by providing two or more pairs of nip rolls during conveyance and slacking them in a suspended manner.
- the film coming out of the tenter is trimmed at both ends held by the clip and subjected to knurling (embossing) at both ends, and then wound up into a roll to obtain a film roll.
- the preferred width of the film to be wound is 0.8 m to 10 m, more preferably 1 m to 6 m, and still more preferably 1.2 m to 4 m.
- the thickness is preferably 30 ⁇ m to 500 ⁇ m, more preferably 40 ⁇ m to 480 ⁇ m, still more preferably 45 ⁇ m to 450 ⁇ m.
- Such adjustment of the thickness can be achieved by adjusting the discharge amount from the die of the extruder and adjusting the film forming speed (adjusting the speed of the cooling roll and the stretching speed linked to the speed of the cooling roll).
- the film for recycling such as the trimmed film edge is collected and recycled as a resin mixture.
- the film for reproduction becomes a film raw material for the white polyester film of the next lot, and returns to the drying process as described above, and the manufacturing process is sequentially repeated.
- the white polyester film of the present disclosure can be manufactured through the above steps.
- the solar cell backsheet of the present disclosure includes the white polyester film of the present disclosure.
- a functional layer can be provided on at least one surface of the solar cell backsheet of the present disclosure and the white polyester film of the present disclosure as necessary.
- an easy-adhesive layer, an ultraviolet absorbing layer, a weather-resistant layer and the like that increase the adhesion to the adherend can be used. Since the solar cell backsheet of the present disclosure includes the white polyester film of the present disclosure, it exhibits stable weather resistance, adhesion, and light reflectivity during long-term use.
- a known coating technique such as a roll coating method, a knife edge coating method, a gravure coating method, or a curtain coating method can be used.
- the solar cell backsheet has any of weather resistance, light reflectivity, and adhesion. Further improvement or other functions can be added.
- surface treatment flame treatment, corona treatment, plasma treatment, ultraviolet treatment, etc.
- another functional film is bonded to the white polyester film of the present disclosure via an adhesive layer.
- a solar cell module of the present disclosure includes a solar cell element, a sealing material that seals the solar cell element, a front substrate that is disposed outside the sealing material on the light receiving surface side of the solar cell element, and the solar cell element
- the solar cell backsheet of the above-described embodiment which is disposed on the side opposite to the light receiving surface side and outside the sealing material. That is, the solar cell module of the present disclosure includes a solar cell element that converts light energy of sunlight into electric energy, a transparent front substrate (surface protection member) on which sunlight is incident, and the solar cell of the present disclosure described above.
- the solar cell module includes the solar cell backsheet including the white polyester film of the present disclosure, the occurrence of peeling and cracking due to hydrolysis of the solar cell backsheet is suppressed.
- the light generation efficiency can be improved by reflecting the light rays in the visible light region and the near infrared region with high reflectivity. Therefore, the solar cell module of the present disclosure can maintain high power generation efficiency over a long period outdoors.
- the members other than the solar cell module and the back sheet are described in detail in, for example, “Photovoltaic power generation system constituent materials” (supervised by Eiichi Sugimoto, Kogyo Kenkyukai, published in 2008).
- the transparent front substrate only needs to have a light transmission property through which sunlight can pass, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, a substrate with higher light transmittance is preferable, and as such a substrate, for example, a glass substrate, a substrate made of a transparent resin such as an acrylic resin, or the like can be suitably used.
- Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group VI compound semiconductor can be applied.
- the white polyester film of this indication is suitable as a substrate film of a back sheet for solar cells
- the use of the white polyester film of this indication is not limited to a back sheet for solar cells, and is used outdoors for a long time. It can be used as a film. Specific examples include a protective film for solar cells, a film for building materials, a film for outdoor advertising, a heat shield film, and the like.
- Example 1 ⁇ Synthesis of raw material polyester resin 1> As shown below, terephthalic acid and ethylene glycol are directly reacted to distill off water, esterify, and then use a direct esterification method in which polycondensation is performed under reduced pressure, and a polyester resin (Ti Catalyst system PET) was obtained.
- the obtained reaction product (oligomer) was transferred to the second esterification reaction tank, and reacted with stirring at a reaction tank temperature of 250 ° C. and an average residence time of 1.2 hours, and an acid value of 200 equivalents / ton. Got.
- the inside of the second esterification reaction tank is partitioned into three zones, and an ethylene glycol solution of magnesium acetate is continuously supplied from the second zone so that the amount of Mg added is 75 ppm in terms of element, From the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the added amount of P was 65 ppm in terms of element.
- the reaction product that has passed through the first polycondensation reaction tank is further transferred to the second double condensation reaction tank. While stirring in this reaction tank, the reaction tank temperature is 276 ° C., the reaction tank pressure is 5 torr (6.67 ⁇ 10 6). -4 MPa) at a residence time of about 1.2 hours (polycondensation).
- the reaction product that passed through the second double condensation reaction tank was further transferred to the third triple condensation reaction tank.
- the reaction vessel internal temperature was 278 ° C.
- the reaction vessel internal pressure was 1.5 torr (2.0 ⁇ 10 -4 MPa) and a residence time of 1.5 hours (polycondensation) to obtain polyethylene terephthalate (PET).
- the obtained PET was measured using high resolution high frequency inductively coupled plasma mass spectrometry (HR-ICP-MS; AttoM manufactured by SII Nanotechnology).
- HR-ICP-MS high resolution high frequency inductively coupled plasma mass spectrometry
- Ti 9 ppm
- Mg 67 ppm
- P 58 ppm.
- P is slightly decreased with respect to the initial addition amount, but is estimated to have volatilized during the polymerization process.
- the polyester polymerized by the esterification reaction described above was preliminarily crystallized for the purpose of preventing fixation during solid phase polymerization by heating at 140 ° C. for 7 minutes with nitrogen having a dew point temperature of ⁇ 30 ° C. Next, it was dried at 180 ° C. for 7 hours using heated nitrogen having a dew point temperature of ⁇ 30 ° C., and the water content in the resin was reduced to 50 ppm or less.
- the dried polyester resin was preheated to 210 ° C., and then solid-state polymerization was advanced by circulating nitrogen at 195 ° C. for 50 hours.
- the gas ratio (the amount of nitrogen gas circulated with respect to the amount of resin discharged) is 1.3 m 3 / kg, the superficial velocity is 0.08 m / sec, the ethylene glycol concentration is 240 ppm, the water concentration is 12 ppm, the ethylene glycol and water
- the solid phase polymerization was allowed to proceed by using nitrogen having a molar partial pressure ratio of 20 (methylene partial pressure of ethylene glycol / molar partial pressure of water) of 20.
- Titanium oxide was added to a part of the pellet before solid phase polymerization so that the content ratio was 50% by mass of the whole pellet and kneaded to prepare a master pellet (master batch).
- titanium oxide was used as titanium oxide.
- melt discharge temperature T1 and the cooling roll landing point temperature T2 were measured using a radiation thermometer (IT-545S, manufactured by Horiba, Ltd.) as follows.
- -Melt discharge temperature T1 The discharge temperature T1 of the melt (melt) is measured until the measurement visual field of the radiation thermometer is in close contact with the cast drum from the die discharge portion and at the location closest to the die discharge portion. At this time, it is generally the highest melt temperature that can be measured with a radiation thermometer.
- the landing point temperature T2 of the cooling roll is measured at the base part (unstretched film) after the measurement visual field of the radiation thermometer is brought into close contact with the cast drum and at the place closest to the contact start point.
- PET polyethylene terephthalate
- transverse stretching After longitudinal stretching, transverse stretching was performed.
- the transverse stretching was performed in the tenter under the following conditions.
- Examples 2 to 13 and Comparative Examples 1 to 7 The biaxially stretched white polyester films of Examples 2 to 13 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1 except that the production conditions ( ⁇ T, heat setting temperature) and film properties were changed as shown in Table 1. Manufactured. ⁇ T was adjusted by changing the position and range of the windshield cover and the distance between the discharge part of the die and the cooling roll.
- ⁇ Terminal carboxyl group concentration> A 0.1 g sample obtained by cutting the film was dissolved in 10 mL of benzyl alcohol, and then a phenol red indicator was added dropwise to the mixed solution to which chloroform was added. This was used as a reference solution (0.01 mol / L KOH-benzyl alcohol mixed solution). Titration with. The concentration of the terminal carboxyl group [equivalent / ton] was calculated from the amount dropped.
- the thickness of the film is an average thickness of the film measured using a contact-type film thickness meter (ID-F125, manufactured by Mitutoyo Corporation). Specifically, with a contact-type film thickness meter, 50 points were sampled at equal intervals over the length of 0.5 m in the length direction of the polyester film, and were equally spaced over the entire width of the film in the width direction (divided into 50 equal parts in the width direction). 50 points are sampled at point), and the thicknesses of these 100 points are measured. The average value of the obtained 100 points of thickness is calculated
- ⁇ sp / C [ ⁇ ] + K [ ⁇ ] 2 ⁇ C
- ⁇ sp (solution viscosity / solvent viscosity) ⁇ 1
- C is the dissolved polymer mass per 100 mL of solvent (1 g / 100 mL in this measurement)
- K is the Huggins constant (0.343) ).
- the solution viscosity and the solvent viscosity were each measured using an Ostwald viscometer.
- ⁇ Tan ⁇ peak temperature> After the produced polyester film was conditioned at 25 ° C. and a relative humidity of 60% for 2 hours or more, using a commercially available dynamic viscoelasticity measuring device (Vibron: DVA-225 (manufactured by IT Measurement Control Co., Ltd.)) The tan ⁇ peak temperature was measured under the conditions of a temperature increase rate of 2 ° C./min, a measurement temperature range of 30 ° C. to 200 ° C., and a frequency of 1 Hz.
- the tear strength of the polyester film obtained in each example was measured as follows. Cut out the sample film in the MD and TD directions to 2 cm width (short side) ⁇ 10 cm length (long side), respectively. -A notch with a length of 5 cm is put in the center of the short side in parallel with the long side direction, and the stress is measured by the following method using a tensile tester. The measurement is performed at 25 ° C. and a relative humidity of 50%. (1-1) One end of the cut portion is held by one chuck of the tensile tester, and the other end is held by the other chuck. (1-2) Measure the tensile stress of the chuck at 30 mm / min.
- the polyester film obtained in each example was cut into a width of 20 mm ⁇ 150 mm to prepare two sample pieces.
- An EVA sheet (EVA sheet manufactured by Mitsui Chemicals Fabro Co., Ltd .: SC50B) is sandwiched between the two sample pieces, and a vacuum laminator (vacuum laminator manufactured by Nisshinbo Co., Ltd.) is used. It was bonded to the EVA sheet by hot pressing.
- the bonding conditions at this time were as follows.
- the EVA non-bonded portion of the obtained adhesion evaluation sample was sandwiched between upper and lower clips with Tensilon (RTC-1210A manufactured by ORIENTEC), a tensile test was performed at a peeling angle of 180 °, and a pulling speed of 300 mm / min, and the adhesion was measured. .
- Ranking was performed according to the following evaluation criteria based on the average value obtained from the measured EVA adhesion strength of MD and TD. Of these, ranks A and B are practically acceptable ranges.
- Table 1 shows the physical properties, manufacturing conditions, and evaluation of the film.
- the white polyester films of the examples are all weather resistance and adhesion evaluation A or B, and have weather resistance and adhesion.
- the thickness is equivalent to 250 ⁇ m and the TD tear strength F TD is 2 to 4 N, it can be seen that the white polyester film is excellent in weather resistance, particularly excellent in weather resistance and adhesion.
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Abstract
Description
太陽電池モジュールは、太陽電池素子と、太陽電池素子を包囲(封止)する封止材と、太陽電池素子の受光面側に配置されている透明なフロント基板と、受光面側とは反対側(裏面側)を保護する太陽電池用裏面保護シート(「太陽電池用バックシート」又は「バックシート」とも呼ばれる)などの部材から構成されている。
太陽電池モジュールは、屋外で長期にわたり使用されることから、これらの構成部材には、耐侯性すなわち自然環境に対する耐久性が求められる。
<1> ポリエステルと白色粒子とを含み、
厚さ250μm相当で、縦延伸方向の引裂強度FMDが2.5~6.0N、横延伸方向の引裂強度FTDが2.0~5.0N、及び、横延伸方向の引裂強度FTDに対する縦延伸方向の引裂強度FMDの比が1.05~4.00であり、
末端カルボキシル基濃度が5~25当量/トンである、
白色ポリエステルフィルム。
<2> 動的粘弾性測定装置で測定したtanδのピーク温度が122~133℃である<1>に記載の白色ポリエステルフィルム。
<3> フィルム全質量に対する白色粒子の含有量が2~10質量%である<1>又は<2>に記載の白色ポリエステルフィルム。
<4> 固有粘度が0.65~0.90dL/gである<1>~<3>のいずれか1つに記載の白色ポリエステルフィルム。
<5> 厚さ250μm相当での横延伸方向の引裂強度FTDが、2.0~4.0Nである<1>~<4>のいずれか1つに記載の白色ポリエステルフィルム。
<6> ロール状に巻かれたフィルムロールである<1>~<5>のいずれか1つに記載の白色ポリエステルフィルム。
原料ポリエステル及び白色粒子を含む混合物を溶融した溶融物をダイから吐出し、冷却ロール上に着地させて未延伸フィルムを形成する際に、ダイから吐出される溶融物の吐出温度と冷却ロールへの着地点温度との差が20℃以下である未延伸フィルム形成工程と、
冷却ロールによって冷却された未延伸フィルムを縦方向及び横方向に延伸して2軸延伸フィルムを形成する延伸工程と、
原料ポリエステルの融点をTm℃とした場合に、2軸延伸フィルムを、Tm-70℃以上、Tm-30℃以下の温度で熱固定する熱固定工程と、
を有する白色ポリエステルフィルムの製造方法。
<8> <1>~<6>のいずれか1つに記載の白色ポリエステルフィルムを含む太陽電池用バックシート。
<9> 太陽電池素子と、
太陽電池素子を封止する封止材と、
太陽電池素子の受光面側で封止材よりも外側に配置されたフロント基板と、
太陽電池素子の受光面側とは反対側で封止材よりも外側に配置された<1>~<5>のいずれか1つに記載の白色ポリエステルフィルムを含む太陽電池用バックシートと、
を含む太陽電池モジュール。
なお、本願明細書において、数値範囲を示す「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。また、数値範囲において上限値のみ単位が記載されている場合は、下限値も上限値と同じ単位であることを意味する。
本開示の白色ポリエステルフィルム(以下、「ポリエステルフィルム」又は「フィルム」と記す場合がある。)とは、ポリエステルと白色粒子とを含み、厚さ250μm相当で、縦延伸方向の引裂強度FMDが2.5~6.0N、横延伸方向の引裂強度FTDが2.0~5.0N、及び、横延伸方向の引裂強度FTDに対する縦延伸方向の引裂強度FMDの比(FMD/FTD)が1.05~4.00であり、末端カルボキシル基濃度が5~25当量/トンである。
白色ポリエステルフィルムを封止材等の他の樹脂層と接着させた場合、白色ポリエステルフィルムと樹脂層との剥がれは、二軸延伸して白色ポリエステルフィルムを製造する際の縦延伸した方向に起きやすいことがわかった。これはポリエステルと白色粒子を含む原料を押出機で混練溶融した溶融物(メルト)がダイから吐出されて冷却ロール上に着地した後、未延伸フィルムは縦方向(搬送方向)に引き取るため、その段階で白色粒子の存在によりポリエステルの球晶生成、縦方向への配向が促進される。縦方向に配向した球晶が延伸後も一部存在することで、相対的に縦方向に剥がれが起きやすくなると考えられる。
本開示の白色ポリエステルフィルムに含まれるポリエステルは、特に制限されず、例えば、芳香族二塩基酸又はそのエステル形成性誘導体とジオール又はそのエステル形成性誘導体とから合成される線状飽和ポリエステルが挙げられる。
具体例として、ポリエチレンテレフタレート(PET)、ポリエチレンイソフタレート、ポリブチレンテレフタレート(PBT)、ポリ(1,4-シクロヘキシレンジメチレンテレフタレート)、ポリエチレン-2,6-ナフタレート(PEN)などを挙げることができる。このうち、力学的物性及びコストのバランスの点で、ポリエチレンテレフタレート及びポリエチレン-2,6-ナフタレートが好ましく、ポリエチレンテレフタレートが特に好ましい。
なお、本開示の白色ポリエステルフィルムは、樹脂成分としてポリエステルのほかに他の種類の樹脂、例えばポリイミド等を少量ブレンドしたフィルムでもよい。
本開示の延伸白色ポリエステルフィルムに含まれるポリエステルの種類は特に制限されず、公知のポリエステルを使用することができる。
例えば、芳香族二塩基酸又はそのエステル形成性誘導体とジオール又はそのエステル形成性誘導体とから合成される線状飽和ポリエステルが挙げられる。線状飽和ポリエステルの具体例としては、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ(1,4-シクロヘキシレンジメチレンテレフタレート)、ポリエチレン-2,6-ナフタレート等が挙げられる。このうち、力学的物性及びコストのバランスの点で、ポリエチレンテレフタレート、ポリエチレン-2,6-ナフタレート、ポリ(1,4-シクロヘキシレンジメチレンテレフタレート)等が特に好ましい。
5価のリン化合物として、置換基として芳香環を有しない5価のリン酸エステルの少なくとも一種が用いられる。例えば、炭素数2以下の低級アルキル基を置換基として有するリン酸エステル〔(OR)3-P=O;R=炭素数1又は2のアルキル基〕が挙げられ、具体的には、リン酸トリメチル、リン酸トリエチル等が特に好ましい。
マグネシウム化合物としては、例えば、酸化マグネシウム、水酸化マグネシウム、マグネシウムアルコキシド、酢酸マグネシウム、炭酸マグネシウム等のマグネシウム塩が挙げられる。中でも、エチレングリコール等の脂肪族ジオールへの溶解性の観点から、酢酸マグネシウムが最も好ましい。
(i)Z=5×(P含有量[ppm]/P原子量)-2×(Mg含有量[ppm]/Mg原子量)-4×(Ti含有量[ppm]/Ti原子量)
(ii)0≦Z≦5.0
式(i)は、反応可能な全リン量から、マグネシウムに作用するリン分を除き、チタンに作用可能なリンの量を表現した式である。値Zが正の場合は、チタンを阻害するリンが余剰な状況にあり、逆に負の場合はチタンを阻害するために必要なリンが不足する状況にあるといえる。反応においては、Ti、Mg、Pの各原子1個は等価ではないことから、式中の各々のモル数に価数を乗じて重み付けを施してある。
エステル化反応工程を一段階で行なう場合、エステル化反応温度は230℃~260℃が好ましく、240℃~250℃がより好ましい。
エステル化反応工程を多段階に分けて行なう場合、第一反応槽のエステル化反応の温度は230℃~260℃が好ましく、より好ましくは240℃~250℃であり、圧力は1.0kg/cm2~5.0kg/cm2が好ましく、より好ましくは2.0kg/cm2~3.0kg/cm2である。第二反応槽のエステル化反応の温度は230℃~260℃が好ましく、より好ましくは245℃~255℃であり、圧力は0.5kg/cm2~5.0kg/cm2、より好ましくは1.0kg/cm2~3.0kg/cm2である。さらに3段階以上に分けて実施する場合は、中間段階のエステル化反応の条件は、第一反応槽と最終反応槽の間の条件に設定するのが好ましい。
特に、固相重合開始時のエチレングリコール(EG)ガス濃度を固相重合終了時のEGガス濃度よりも200ppm~1000ppmの範囲で高くすることが好ましく、より好ましくは250ppm~800ppm、さらに好ましくは300ppm~700ppmの範囲で高くして固相重合することが好ましい。この時、平均EGガス濃度(固相重合開始時と終了時のガス濃度の平均)を添加することで末端COOH濃度を制御できる。即ちEG添加により末端COOHと反応させ末端COOH濃度を低減できる。EGは100ppm~500ppmが好ましく、より好ましくは150ppm~450ppm、さらに好ましくは200ppm~400ppmである。
また、固相重合時間は10時間~40時間が好ましく、より好ましくは14時間~35時間、さらに好ましくは18時間~30時間である。
ポリエステル中のカルボキシル基含量は、重合触媒種、製膜条件(製膜温度及び時間)、固相重合、添加剤(末端封止剤等)等により調整することが可能である。
本開示の白色ポリエステルフィルムは、末端封止剤を添加することでさらに耐加水分解性(耐候性)を向上させることができる。
末端封止剤の添加量が、ポリエステルの全質量に対して0.1質量%以上であれば、耐候性向上効果が発現し易く、10質量%以下であればポリエステルに対して可塑剤として作用することが抑制され、力学強度、耐熱性の低下が抑制される。
なお、末端封止剤の分子量は、重量平均分子量を意味する。
カルボジイミド基を有するカルボジイミド化合物は、一官能性カルボジイミドと多官能性カルボジイミドがあり、一官能性カルボジイミドとしては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジメチルカルボジイミド、ジイソブチルカルボジイミド、ジオクチルカルボジイミド、t-ブチルイソプロピルカルボジイミド、ジフェニルカルボジイミド、ジ-t-ブチルカルボジイミド、ジ-β-ナフチルカルボジイミド等が挙げられる。特に好ましくは、ジシクロヘキシルカルボジイミド及びジイソプロピルカルボジイミドである。
芳香族環状カルボジイミドは、環状構造を複数有していてもよい。
芳香族環状カルボジイミドは分子内に2つ以上のカルボジイミド基の第一窒素と第二窒素とが連結基により結合した環構造を有さない芳香族カルボジイミドであること、すなわち単環である芳香族カルボジイミドも好ましく用いることができる。
エポキシ化合物の好ましい例としては、グリシジルエステル化合物及びグリシジルエーテル化合物等が挙げられる。
オキサゾリン化合物としては、ビスオキサゾリン化合物が好ましく、具体的には、2,2’-ビス(2-オキサゾリン)、2,2’-ビス(4-メチル-2-オキサゾリン)、2,2’-ビス(4,4-ジメチル-2-オキサゾリン)、2,2’-ビス(4-エチル-2-オキサゾリン)、2,2’-ビス(4,4’-ジエチル-2-オキサゾリン)、2,2’-ビス(4-プロピル-2-オキサゾリン)、2,2’-ビス(4-ブチル-2-オキサゾリン)、2,2’-ビス(4-ヘキシル-2-オキサゾリン)、2,2’-ビス(4-フェニル-2-オキサゾリン)、2,2’-ビス(4-シクロヘキシル-2-オキサゾリン)、2,2’-ビス(4-ベンジル-2-オキサゾリン)、2,2’-p-フェニレンビス(2-オキサゾリン)、2,2’-m-フェニレンビス(2-オキサゾリン)、2,2’-o-フェニレンビス(2-オキサゾリン)、2,2’-p-フェニレンビス(4-メチル-2-オキサゾリン)、2,2’-p-フェニレンビス(4,4-ジメチル-2-オキサゾリン)、2,2’-m-フェニレンビス(4-メチル-2-オキサゾリン)、2,2’-m-フェニレンビス(4,4-ジメチル-2-オキサゾリン)、2,2’-エチレンビス(2-オキサゾリン)、2,2’-テトラメチレンビス(2-オキサゾリン)、2,2’-ヘキサメチレンビス(2-オキサゾリン)、2,2’-オクタメチレンビス(2-オキサゾリン)、2,2’-デカメチレンビス(2-オキサゾリン)、2,2’-エチレンビス(4-メチル-2-オキサゾリン)、2,2’-テトラメチレンビス(4,4-ジメチル-2-オキサゾリン)、2,2’-9,9’-ジフェノキシエタンビス(2-オキサゾリン)、2,2’-シクロヘキシレンビス(2-オキサゾリン)、2,2’-ジフェニレンビス(2-オキサゾリン)等を例示することができる。これらの中では、ポリエステルとの反応性の観点から、2,2’-ビス(2-オキサゾリン)が最も好ましく用いられる。さらに、上記で挙げたビスオキサゾリン化合物は本開示の目的を達成する限り、一種を単独で用いても、二種以上を併用してもどちらでもよい。
本開示の白色ポリエステルフィルムは、白色粒子を含有している。白色粒子を含むことでフィルムに光反射性又は意匠性を付与することができる。
無機粒子としては、例えば、湿式シリカ、乾式シリカ、コロイダルシリカ、炭酸カルシウム、珪酸アルミ、リン酸カルシウム、アルミナ、炭酸マグネシウム、炭酸亜鉛、酸化チタン、酸化亜鉛(亜鉛華とも呼ばれる)、酸化アンチモン、酸化セリウム、酸化ジルコニウム、酸化錫、酸化ランタン、酸化マグネシウム、炭酸バリウム、炭酸亜鉛、塩基性炭酸鉛(鉛白とも呼ばれる)、硫酸バリウム、硫酸カルシウム、硫酸鉛、硫化亜鉛、マイカ、雲母チタン、タルク、クレー、カオリン、フッ化リチウム、フッ化カルシウム等を使用することができる。
また、白色粒子の表面にアルミナ、シリカ等の無機材料の表面処理を施してもよいし、シリコーン系、アルコール系等の有機材料の表面処理を施してもよい。
紫外線領域の光線は、太陽電池の発電にはほとんど寄与しないことから、ポリエステルの紫外線による劣化を防ぐという観点から、白色粒子の紫外線の分光反射率は、高いことが望ましい。二酸化チタンのルチル型は紫外線の分光反射率が非常に大きいのに対し、アナターゼ型は紫外線の吸収率が大きい(分光反射率が小さい)という特性を有している。二酸化チタンの結晶形態におけるこうした分光特性の違いから、ルチル型の紫外線吸収性能を利用することで、例えば、太陽電池裏面保護用ポリエステルフィルム(太陽電池用バックシート)において、耐光性を向上させることができる。また、ルチル型二酸化チタンの紫外線吸収性能を利用することで、他の紫外線吸収剤を実質的に添加しなくても光照射下でのフィルム耐久性に優れる。そのため、紫外線吸収剤のブリードアウトによる汚染及び密着性の低下が生じにくい。
ルチル型二酸化チタンは、ポリエステルに配合する前に、精製プロセスを用いて、粒子径調整、粗大粒子の除去を行ってもよい。精製プロセスの工業的手段としては、粉砕手段で例えばジェットミル、ボールミルを適用することができ、分級手段としては、例えば乾式もしくは湿式の遠心分離を適用することができる。
かかる観点から、本開示の白色ポリエステルフィルムに含まれる白色粒子の含有量は、より好ましくは2~8質量%であり、さらに好ましくは3~6質量%である。
坩堝にフィルムを測定試料として3gとり、電気オーブン内において900℃で120分間加熱を行う。その後電気オーブン内が冷えてから坩堝を取り出し、坩堝の中に残った灰分の質量を測定する。この灰分がすなわち白色粒子分であり、灰分の質量を測定試料の質量で除し、100を乗じた値を白色粒子の含有量(質量%)とする。
なお、フィルムの製造前であれば、原料として用いる白色粒子(白色顔料)の添加量から含有量を求めてもよい。
フィルムの厚さ方向の断面における白色粒子を走査型電子顕微鏡で観察し、粒子の大きさに応じて適宜倍率を変え、写真撮影して拡大コピーする。ランダムに選んだ少なくとも200個の粒子について、各粒子の外周をトレースする。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、それらの平均値を平均粒径とする。
なお、フィルムの製造前であれば、原料として用いる白色粒子(白色顔料)からランダムに選んだ少なくとも200個の粒子について、上記と同様にして平均粒径を求めてもよい。
本開示の白色ポリエステルフィルムは、厚さ250μm相当で、縦延伸方向の引裂強度FMDが2.5~6.0N、横延伸方向の引裂強度FTDが2.0~5.0N、及び、横延伸方向の引裂強度FTDに対する縦延伸方向の引裂強度FMDの比が1.05~4.00である。
本開示の白色ポリエステルフィルムは、厚さ250μm当たりの縦延伸方向の引裂強度FMDが2.5N以上であることで、密着性が高く、6.0N以下であることでフィルムの裁断時にクラックが発生することが抑制され、また、耐候性を向上させることができる。
かかる観点から、厚さ250μm当たりの縦延伸方向の引裂強度FMDは2.5~5.5Nであることが好ましく、3.0~5.0Nであることが好ましい。
本開示の白色ポリエステルフィルムは、厚さ250μm当たりの横延伸方向の引裂強度FTDが2.0N以上であることで、密着性が高く、5.0N以下であることでフィルムの裁断時にクラックが発生することが抑制される。
かかる観点から、厚さ250μm当たりの横延伸方向の引裂強度FTDは2.0~4.5Nであることが好ましく、2.0~4.0Nであることが好ましい。特に横延伸方向の引裂強度FTDを2.0~4.0Nの範囲内にすることで耐候性を向上させることもできる。
延伸方向の引裂強度FTDに対する縦延伸方向の引裂強度FMDの比(FMD/FTD)が、1.05以上であることで十分な耐候性が得られ、4.00以下であることで他の樹脂層等の異種素材との十分な密着性が得られる。なお、本開示の白色ポリエステルフィルムは、横厚さ250μm相当で、縦延伸方向の引裂強度FMDが2.5~6.0Nであり、かつ、横延伸方向の引裂強度FTDが2.0~5.0Nであっても、引裂強度比が1.05未満であれば耐候性が不十分となり、4.00を超えると密着性が不十分となる。
かかる観点から、MD,TDの引裂強度比FMD/FTDは1.05~3.00であることが好ましく、1.05~2.50であることがより好ましい。
<測定法>
・サンプルフィルムをMD、TD方向にそれぞれ2cm幅(短辺)×10cm長(長辺)に切り出す。
・短辺の中央に長さ5cmの切れ込みを長辺方向に平行に入れ、これを引張試験機を用い、下記の方法で応力を測定する。なお、測定は25℃、相対湿度50%で行う。
(1-1)切れ込み部の一端を、引っ張り試験機の片方のチャックに、もう一端を、もう片方のチャックに把持させる。
(1-2)チャックを30mm/分で引張り応力を測定する。チャック間距離が広がるに連れ応力が増加し、平坦部が出現する。この平端部の応力を引裂強度とし、繰返し数n=3で測定し、平均値を求める。
(1-3)この測定をMD、TDでそれぞれ測定し、各方向ごとに250μmの厚み相当の平均値を求め、それぞれの方向の引裂強度とする。
なお、サンプルフィルムの厚みがtμmであり、引裂強度がFである場合、250μmの厚み相当の引裂強度は、(F/t)×250として求めることができる。
また、二軸延伸等を経て製造されたフィルムは、通常MD方向の緩和がなされないため、熱収縮率が大きい方向をMDとして、MD,TDを特定することができる。
本開示の白色ポリエステルフィルムは、末端カルボキシル基濃度が5~25当量/トンであることが好ましい。末端カルボキシル基濃度は、酸価(Acid value)とも呼ばれ、「AV」と記す場合がある。なお、本明細書において、「当量/トン」とは、1トン当たりのモル当量を表し、「eq/t」と記す場合がある。
一方、ポリエステル分子末端のCOOH基のH+が触媒となって加水分解が促される。ポリエステルフィルムにおける末端カルボキシル基濃度が25当量/トン以下であれば、耐加水分解性の低下を抑制することができる。
本開示の白色ポリエステルフィルムは、動的粘弾性測定装置で測定したtanδのピーク温度が122~135℃であることが好ましい。
動的粘弾性測定装置で測定したtanδのピーク温度が122℃以上であれば耐候性を向上させることができ、135℃以下であれば密着性を向上させることができる。かかる観点から、本開示の白色ポリエステルフィルムは、tanδのピーク温度が122~130℃であることがより好ましく、122~128℃であることが特に好ましい。
tanδのピーク温度は、25℃・相対湿度60%で2時間以上調湿した後に、市販の動的粘弾性測定装置(バイブロン:DVA-225(アイティー計測制御株式会社製))を用いて、昇温速度2℃/分、測定温度範囲30℃~200℃、周波数1Hzの条件で測定した値である。
本開示の白色ポリエステルフィルムは、フィルムの固有粘度(IV:Intrinsic viscosity)が0.65~0.90dL/gであることが好ましい。
フィルムのIVが0.65dL/g以上であれば、十分な耐候性が得られる。一方、フィルムのIVが0.90dL/g以下であれば、フィルムを製造する際に未延伸フィルム形成工程における溶融物(メルト)の押出が容易であり、また、せん断発熱が抑制され、耐加水分解性能の低下が抑制される。
かかる観点から、フィルムのIVは、0.65~0.85dL/gであることがより好ましく、0.67~0.77dL/gであることがさらに好ましい。
本開示の白色ポリエステルフィルムのIVの測定方法は、実施例に記載されている方法を用いる。
本開示の白色ポリエステルフィルムの厚みは220~450μmであることが好ましい。フィルムの厚みが250μm以上であれば、高い耐電圧性を有することができる。一方、フィルムの厚みが500μm以下であれば製膜時のフィルムの昇温冷却能力の低下による耐加水分解性の低下が抑制され、また、フィルム延伸時に延伸機に高い負荷をかけずに延伸を行うことができる。
かかる観点から、フィルムの厚みは250~350μmであることがより好ましい。
本開示の白色ポリエステルフィルムの厚みの測定方法は、実施例に記載されている方法を用いる。
本開示の白色ポリエステルフィルムは、異種素材との密着性をさらに向上させるため、必要に応じて、コロナ処理、火炎処理、グロー放電処理等の表面処理を行ってもよい。
コロナ放電処理は、通常誘導体を被膜した金属ロール(誘電体ロール)と絶縁された電極間に高周波及び高電圧を印加して、電極間の空気の絶縁破壊を生じさせることにより、電極間の空気をイオン化させて、電極間にコロナ放電を発生させる。そして、このコロナ放電の間を、ポリエステルフィルムを通過させることにより表面処理を行う。
本開示で用いる処理条件は、電極と誘電体ロ-ルのギャップクリアランス1~3mm、周波数1~100kHz、印加エネルギー0.2~5kV・A・分/m2程度が好ましい。
交流を用いる場合には50又は60Hzの商用の周波数を用いてもよいし、10~50kHz程度の高周波を用いてもよい。また、13.56MHzの高周波を用いる方法も好ましい。
グロー放電処理の処理時間は、好ましくは0.05~100秒、より好ましくは0.5~30秒程度である。処理時間が0.05秒以上であれば接着性改良効果が充分得られ、100秒以下であれば被処理フィルムの変形、着色等を防ぐことができる。
放電処理強度を0.01kV・A・分/m2以上とすることで充分な接着性改良効果が得られ、10kV・A・分/m2以下とすることで被処理フィルムの変形、着色等を避けることができる。
真空中で被処理フィルムの温度を上げる具体的方法としては、赤外線ヒーターによる加熱、熱ロールに接触させることによる加熱などが挙げられる。
本開示の延伸白色ポリエステルフィルムを製造する方法は特に限定されないが、例えば、本開示の延伸白色ポリエステルフィルムは以下の方法によって好適に製造することができる。
冷却ロールによって冷却された未延伸フィルムを縦方向及び横方向に延伸して2軸延伸フィルムを形成する延伸工程と、
原料ポリエステルの融点をTm℃とした場合に、2軸延伸フィルムを、Tm-70℃以上、Tm-30℃以下の温度で熱固定する熱固定工程と、
を有する。
また、未延伸フィルムを形成した後、延伸工程の前、又は、一方向への延伸を行った後、他方向への延伸を行う前に、下塗り層を形成するためのインラインコートを行ってもよい。
以下、各工程について具体的に説明するが、本開示の白色ポリエステルフィルムの製造方法は以下の方法に限定されない。
未延伸フィルム形成工程では、原料ポリエステル及び白色粒子を含む混合物を溶融した溶融物をダイから吐出し、冷却ロール上に着地させて未延伸フィルムを形成する。このとき、ダイから吐出される溶融物の吐出温度と冷却ロールへの着地点温度との差を20℃以下にする。
(B)ポリエステルに白色粒子を添加し、溶融混練する方法。
(C)上記(A)又は(B)の方法によって白色粒子を多量に添加したマスターバッチ(マスターペレットとも呼ばれる)を製造し、マスターバッチと、白色粒子を含有しない又は少量の白色顔料を含有するポリエステルとを混練して、所定量の白色粒子を含有させる方法。
(D)上記(C)のマスターペレットをそのまま使用して溶融混練する方法。
予備混合を行う方法は特に限定されず、バッチによる方法でもよいし、単軸もしくは2軸以上の混練押出機によって予備混合を行ってもよい。脱気しながらマスターバッチを作製する場合は、250℃~300℃、好ましくは270℃~280℃の温度でポリエステル樹脂を融解し、予備混練機に1つ、好ましくは2つ以上の脱気口を設け、0.05MPa以上、より好ましくは0.1MPa以上の連続吸引脱気を行い、混合機内の減圧を維持すること等の方法を採用することが好ましい。
押出機における溶融温度は使用する原料ポリエステルの融点から融点+80℃以下で行なうことが好ましく、より好ましくは融点+10℃以上、融点+70℃以下、さらに好ましくは融点+20℃以上、融点+60℃以下である。押出機における溶融温度が、融点+10℃以上であると、充分に樹脂が融解し、一方、融点+70℃以下であるとポリエステル等の分解が抑制され好ましい。なお、原料を押出機に投入する前に、原料ポリエステルを乾燥させておくことが好ましく、好ましい含水率は10ppm~300ppm、より好ましくは20ppm~150ppmである。
延伸工程では、冷却ロールによって冷却された未延伸フィルムを縦方向(MD:Machine Direction)及び横方向(TD:Transverse Direction)に延伸して2軸延伸フィルムを形成する。
図1において、把持部材2a、2b、2e、2f、2i、及び、2jは、環状レール60aの縁に沿って反時計回りに移動し、把持部材2c、2d、2g、2h、2k、及び、2lは、環状レール60bの縁に沿って時計回りに移動する。
その結果、ポリエステルフィルム200は、図1における矢印MD方向に移動し、予熱部10と、延伸部20と、熱固定部30と、熱緩和部40と、冷却部50とに、順に搬送される。
把持部材2a~2lの移動速度が、ポリエステルフィルム200の把持部分における搬送速度となる。
従って、2軸延伸機100は、延伸部20において、ポリエステルフィルム200をTD方向に延伸する横延伸を可能とするが、把持部材2a~2lの移動速度を変化させることにより、ポリエステルフィルム200をMD方向にも延伸することができる。
すなわち、2軸延伸機100を用いて同時2軸延伸を行なうことも可能である。
なお、以下、把持部材2a~2lを、「把持部材2」と総称することもある。
予熱部10では、ポリエステルフィルム200を予熱する。ポリエステルフィルム200を延伸する前に予め加熱して、ポリエステルフィルム200の横延伸を容易にする。
予熱部終了点における膜面温度(以下、「予熱温度」とも称する)は、ポリエステルフィルム200のガラス転移温度をTgとするとき、Tg-10℃~Tg+60℃であることが好ましく、Tg℃~Tg+50℃であることがより好ましい。
なお、予熱部終了点は、ポリエステルフィルム200の予熱を終了する時点、すなわち、予熱部10の領域からポリエステルフィルム200が離れる位置をいう。
延伸部20では、予熱されたポリエステルフィルム200を、少なくともポリエステルフィルム200の縦方向(搬送方向、MD)と直交する方向(TD)に横延伸してポリエステルフィルム200に緊張を与える。
ポリエステルフィルム200の縦方向(搬送方向、MD)と直交する方向(TD)への延伸(横延伸)は、ポリエステルフィルム200の縦方向(搬送方向、MD)と垂直(90°)の角度の方向に延伸することを意図する。
2軸延伸では、未延伸フィルム形成工程で形成した未延伸フィルムに対して、ポリエステルフィルムの縦方向に、例えば、延伸応力が5MPa以上15MPa以下、かつ、延伸倍率が2.5倍以上4.5倍以下の縦延伸を行う。
縦延伸後、横延伸を行う。横延伸はテンターを用いて行なうのが好ましい。縦延伸された白色ポリエステルフィルムをテンターに導き、例えば、80℃以上180℃以下の温度(延伸温度)に加熱された雰囲気中で、横方向に延伸(TD延伸)を行う。テンターでは、ポリエステルフィルムの両端をクリップで把持し、熱処理ゾーンを搬送しながら、クリップを縦方向に直角な方向、すなわち、横方向に拡げることで横延伸を行うことができる。
熱固定工程では、原料ポリエステルの融点Tm℃に対し、2軸延伸フィルムを、Tm-70℃以上、Tm-30℃以下の温度で熱固定する。例えば、原料に用いるPETの融点が257℃である場合、187~227℃で熱固定を行う。
なお、ここでいう熱固定温度とは熱固定処理時のフィルムの最高到達表面温度であり、放射温度計によって測定することができる。
熱固定温度が原料ポリエステルの融点Tmに対して(Tm-70)℃以上であれば、tanδピーク温度が大きくなり過ぎず、TD引裂強度を向上させることができ、また、劈開強度を向上させることができる。一方、熱固定温度が原料ポリエステルの融点Tmに対して(Tm-30)℃以下であれば、tanδピーク温度が小さくなり過ぎず、耐候性を向上させることができる。
熱固定工程に引き続き、熱緩和工程を行なうことが好ましい。熱緩和工程とは、フィルムに対して応力緩和のために熱を加えて、フィルムを収縮させる処理である。熱緩和工程は、緩和は縦、横少なくとも一方に行なうことが好ましく、緩和量は縦横とも1%~30%(横延伸後の幅に対する割合)が好ましく、より好ましくは2%~20%、さらに好ましくは3%~15%である。熱緩和温度をTr、熱固定温度をTsとしたとき、熱緩和温度Trは、100℃以上で、かつTsよりも15℃以上低い温度領域(100℃≦Tr≦Ts-15℃)であることが好ましく、110℃以上で、かつTsよりも25℃以上低い温度領域(110℃≦Tr≦Ts-25℃)であることがより好ましく、120℃以上で、かつTsよりも30℃以上低い温度領域(120℃≦Tr≦Ts-30℃)であることが特に好ましい。
テンターから出てきたフィルムは、クリップで把持していた両端がトリミングされ、両端にナーリング加工(型押し加工)が施された後、ロール状に巻き取られ、フィルムロールが得られる。
巻き取られるフィルムの好ましい幅は0.8m~10m、より好ましくは1m~6m、さらに好ましくは1.2m~4mである。厚みは30μm~500μmが好ましく、より好ましくは40μm~480μm、さらに好ましくは45μm~450μmである。このような厚みの調整は、押出機のダイからの吐出量の調整、製膜速度の調整(冷却ロールの速度及び冷却ロールの速度に連動する延伸速度等の調整)により達成できる。
本開示の太陽電池用バックシートは、本開示の白色ポリエステルフィルムを含む。
本開示の太陽電池用バックシート、本開示の白色ポリエステルフィルムの少なくとも一方の面に必要に応じて機能性層を設けることができる。例えば、被着物に対して接着力を高める易接着性層、紫外線吸収層、耐候性層等が挙げられる。
本開示の太陽電池用バックシートは、本開示の白色ポリエステルフィルムを備えるので、長期使用時において安定した耐候性、密着性、及び光反射性を示す。
また、他の機能性フィルムを接着層を介して本開示の白色ポリエステルフィルムに貼り合わせることも好ましい。
本開示の太陽電池モジュールは、太陽電池素子と、太陽電池素子を封止する封止材と、太陽電池素子の受光面側で封止材よりも外側に配置されたフロント基板と、太陽電池素子の受光面側とは反対側で封止材よりも外側に配置された前述した実施形態の太陽電池用バックシートと、を含む。
すなわち、本開示の太陽電池モジュールは、太陽光の光エネルギーを電気エネルギーに変換する太陽電池素子を、太陽光が入射する透明性のフロント基板(表面保護部材)と既述の本開示の太陽電池用バックシート(裏面保護部材)との間に配置し、フロント基板とバックシートとの間に配置された太陽電池素子をエチレン-ビニルアセテート(EVA)等の封止材で封止して構成される。太陽電池モジュールが、本開示の白色ポリエステルフィルムを含む太陽電池用バックシートを備えていることで、太陽電池用バックシートの加水分解による剥離及び亀裂の発生が抑制され、また、太陽電池素子に対して可視光領域及び近赤外領域の光線を高い反射率で反射して発電効率を高めることができる。そのため、本開示の太陽電池モジュールは、屋外において長期にわたり高い発電効率を維持することができる。
<原料ポリエステル樹脂1の合成>
以下に示すように、テレフタル酸及びエチレングリコールを直接反応させて水を留去し、エステル化した後、減圧下で重縮合を行なう直接エステル化法を用いて、連続重合装置によりポリエステル樹脂(Ti触媒系PET)を得た。
第一エステル化反応槽に、高純度テレフタル酸4.7トンとエチレングリコール1.8トンを90分かけて混合してスラリーを形成し、3800kg/hの流量で連続的に第一エステル化反応槽に供給した。更にクエン酸がTi金属に配位したクエン酸キレートチタン錯体(VERTEC AC-420、ジョンソン・マッセイ社製)のエチレングリコール溶液を連続的に供給し、反応槽内温度250℃、攪拌下で平均滞留時間約4.3時間で反応を行なった。このとき、クエン酸キレートチタン錯体は、Ti添加量が元素換算値で9ppmとなるように連続的に添加した。得られたオリゴマーの酸価は600当量/トンであった。
上記で得られたエステル化反応生成物を連続的に第一重縮合反応槽に供給し、攪拌下、反応温度270℃、反応槽内圧力20torr(2.67×10-3MPa)、平均滞留時間約1.8時間で重縮合させた。
上記で重合したPETをペレット化(直径3mm、長さ7mm)し、得られた樹脂ペレット(固有粘度IV=0.60dL/g、末端カルボキシ基濃度=16当量/トン)を、以下のようにして固相重合を実施した。
次に露点温度-30℃の加熱窒素を用いて180℃で7時間乾燥させ、樹脂中の水分率を50ppm以下にした。
次に反応工程から排出される樹脂(750kg/h)を60℃まで冷却した。
得られた固相重合後のポリエステル樹脂は、固有粘度(IV)=0.78dL/g、末端COOH量(AV)=9当量/トン、融点(Tm)=257℃であった。
固相重合前のペレットの一部に酸化チタンを、含有比率がペレット全体の50質量%になるように加えて混練し、マスターペレット(マスターバッチ)を作製した。
ここで、酸化チタンとしては、石原産業製(商品名:PF-739;平均一次粒径=0.25μm)を用いた。
上記のように固相重合を終えたPET-1とマスターペレットを、それぞれ含水率100ppm以下に乾燥させた後、酸化チタン量が4質量%になるように混合し、混練押出機のホッパーに投入し、290℃で溶融して押出した。なお押出機は、2箇所のベントを備えたダブルベント式同方向回転噛合型の2軸押出機(直径110mm)を用いた。この溶融物(メルト)をギアポンプ、濾過器(孔径20μm)に通した後、ダイから冷却キャストドラム(冷却ロール)に押出した。なお、押出されたメルトは、静電印加法により冷却キャストドラム(冷却ロール)に密着させた。
また、溶融物の吐出温度T1と冷却ロールの着地点温度T2は、それぞれ放射温度計(株式会社 堀場製作所社製、IT-545S)を用いて以下のように測定した。
・溶融物の吐出温度T1:
溶融物(メルト)の吐出温度T1は、放射温度計の測定視野がダイ吐出部からキャストドラムに密着されるまでの間で、かつ、ダイ吐出部に一番近い箇所で測定する。このとき、一般的には放射温度計で測定可能なメルト温度の最高温度となる。
・冷却ロールの着地点温度T2:
冷却ロールの着地点温度T2は、放射温度計の測定視野がキャストドラムに密着させた後のベース部(未延伸フィルム)で、かつ、密着開始点に一番近い箇所で測定する。
-縦延伸-
未延伸フィルムを周速の異なる2対のニップロールの間に通し、下記条件にて縦方向(搬送方向)に延伸した。
・予熱温度:75℃
・延伸温度:92℃
・延伸倍率:3.0倍
・延伸速度:300%/秒
縦延伸後、横延伸を行った。横延伸は、テンター内にて下記条件にて行った。
予熱温度:110℃
・延伸温度:150℃
・延伸倍率:4.2倍
・延伸速度:15%/秒
縦延伸及び横延伸を終えた後の二軸延伸フィルムを、190℃で熱固定した(熱固定時間:7秒)。
熱固定した後、テンター幅を縮め熱緩和した(熱緩和温度:160℃)。
熱固定及び熱緩和の後、両端を10cmずつトリミングした。その後、両端に幅10mmで型押し加工(ナーリング)を行なった後、張力25kg/mで巻き取った。フィルム幅は1.5m、巻長は2000mであった。
以上のようにして、実施例1の二軸延伸白色ポリエテルフィルム(厚み250μm)を得た。
製造条件(ΔT、熱固定温度)及びフィルム物性を表1に示すように変更したこと以外は実施例1と同様にして実施例2~13及び比較例1~7の2軸延伸白色ポリエステルフィルムを製造した。
なお、ΔTは、遮風カバーの位置及び範囲、ダイの吐出部と冷却ロールとの間隔を変えることによって調整した。
実施例及び比較例にて得られた2軸延伸白色ポリエテルフィルムについて、以下の評価を行った。それぞれの測定結果及び評価結果を、下記表1に示す。
フィルムを切断して得た試料0.1gをベンジルアルコール10mLに溶解後、クロロホルムを加えた混合溶液にフェノールレッド指示薬を滴下し、これを基準液(0.01mol/L KOH-ベンジルアルコール混合溶液)で滴定した。滴下量から末端カルボキシル基の濃度[当量/トン]を算出した。
フィルムの厚みは、接触式膜厚測定計(株式会社ミツトヨ製、ID-F125)を用いて測定した、フィルムの平均厚みである。具体的には、接触式膜厚測定計により、ポリエステルフィルムの長手方向に0.5mに渡り等間隔に50点をサンプリングし、幅方向に製膜全幅にわたり等間隔(幅方向に50等分した点)に50点をサンプリングし、これらの100点の厚みを測定する。得られた100点の厚みの平均値を求め、これをポリエステルフィルムの厚みとする。
製造したポリエステルフィルムを、1,1,2,2-テトラクロルエタン/フェノール(=2/3[質量比])混合溶媒に溶解し、混合溶媒中の25℃での溶液粘度から、固有粘度(IV;単位:dL/g)を求めた。
ηsp/C=[η]+K[η]2・C
ここで、ηsp=(溶液粘度/溶媒粘度)-1であり、Cは、溶媒100mLあたりの溶解ポリマー質量であり(本測定では1g/100mLとする)、Kはハギンス定数(0.343とする)である。溶液粘度及び溶媒粘度は、それぞれオストワルド粘度計を用いて測定した。
製造したポリエステルフィルムを、25℃・相対湿度60%で2時間以上調湿した後に、市販の動的粘弾性測定装置(バイブロン:DVA-225(アイティー計測制御株式会社製))を用いて、昇温速度2℃/分、測定温度範囲30℃~200℃、周波数1Hzの条件でtanδピーク温度を測定した。
各例で得られたポリエステルフィルムの引裂強度を以下のようにして測定した。
・サンプルフィルムをMD、TD方向にそれぞれ2cm幅(短辺)×10cm長(長辺)に切り出す。
・短辺の中央に長さ5cmの切れ込みを長辺方向と平行に入れ、これを引張試験機を用い、下記の方法で応力を測定する。測定は25℃、相対湿度50%で行う。
(1-1)切れ込み部の一端を、引っ張り試験機の片方のチャックに、もう一端を、もう片方のチャックに把持させる。
(1-2)チャックを30mm/分で引張り応力を測定する。チャック間距離が広がるに連れ応力が増加し、平坦部が出現する。この平端部の応力を引裂強度とし、繰返し数n=3で測定して平均値を求める。
(1-3)この測定をMD、TDでそれぞれ測定し、平均値を各方向での引裂強度とする。
各例で得られたポリエステルフィルムを20mm巾×150mmにカットして、サンプル片を2枚準備した。この2枚のサンプル片の間に20mm巾×100mm長にカットしたEVAシート(三井化学ファブロ(株)製のEVAシート:SC50B)を挟み、真空ラミネータ(日清紡(株)製の真空ラミネート機)を用いてホットプレスすることにより、EVAシートと接着させた。このときの接着条件は、以下の通りとした。
得られた接着評価用試料のEVA未接着部分を、テンシロン(ORIENTEC製 RTC-1210A)にて上下クリップに挟み、剥離角度180°、引っ張り速度300mm/分で引っ張り試験を行ない、密着力を測定した。
<評価基準>
A:5.5N/mm以上
B:5.0N/mm以上5.5N/mm未満
C:5.0/mm未満
得られたフィルムについて、120℃で100%の湿熱条件で所定の時間処理を行ない、その後JIS-K7127法(1999年度)により破断伸度測定を行なって、下記の評価基準にしたがって評価した。このうち、ランクA、Bが実用上許容可能な範囲である。
A:破断伸度が未処理フィルムの50%にまで減少する時間が105時間を超える
B:破断伸度が未処理フィルムの50%にまで減少する時間が90時間を超え105時間以下
C:破断伸度が未処理フィルムの50%にまで減少する時間が90時間以下
本明細書に記載された全ての文献、特許、特許出願、および技術規格は、個々の文献、特許、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (9)
- ポリエステルと白色粒子とを含み、
厚さ250μm相当で、縦延伸方向の引裂強度FMDが2.5~6.0N、横延伸方向の引裂強度FTDが2.0~5.0N、及び、前記横延伸方向の引裂強度FTDに対する前記縦延伸方向の引裂強度FMDの比が1.05~4.00であり、
末端カルボキシル基濃度が5~25当量/トンである、
白色ポリエステルフィルム。 - 動的粘弾性測定装置で測定したtanδのピーク温度が122~133℃である請求項1に記載の白色ポリエステルフィルム。
- フィルム全質量に対する前記白色粒子の含有量が2~10質量%である請求項1又は請求項2に記載の白色ポリエステルフィルム。
- 固有粘度が0.65~0.90dL/gである請求項1~請求項3のいずれか1項に記載の白色ポリエステルフィルム。
- 前記厚さ250μm相当での前記横延伸方向の引裂強度FTDが、2.0~4.0Nである請求項1~請求項4のいずれか1項に記載の白色ポリエステルフィルム。
- ロール状に巻かれたフィルムロールである請求項1~請求項5のいずれか1項に記載の白色ポリエステルフィルム。
- 請求項1~請求項6のいずれか1項に記載の白色ポリエステルフィルムを製造する方法であって、
原料ポリエステル及び白色粒子を含む混合物を溶融した溶融物をダイから吐出し、冷却ロール上に着地させて未延伸フィルムを形成する際に、前記ダイから吐出される前記溶融物の吐出温度と前記冷却ロールへの着地点温度との差が20℃以下である未延伸フィルム形成工程と、
前記冷却ロールによって冷却された未延伸フィルムを縦方向及び横方向に延伸して2軸延伸フィルムを形成する延伸工程と、
前記原料ポリエステルの融点をTm℃とした場合に、前記2軸延伸フィルムを、Tm-70℃以上、Tm-30℃以下の温度で熱固定する熱固定工程と、
を有する白色ポリエステルフィルムの製造方法。 - 請求項1~請求項6のいずれか1項に記載の白色ポリエステルフィルムを含む太陽電池用バックシート。
- 太陽電池素子と、
前記太陽電池素子を封止する封止材と、
前記太陽電池素子の受光面側で前記封止材よりも外側に配置されたフロント基板と、
前記太陽電池素子の受光面側とは反対側で前記封止材よりも外側に配置された請求項1~請求項5のいずれか1項に記載の白色ポリエステルフィルムを含む太陽電池用バックシートと、
を含む太陽電池モジュール。
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