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WO2012081385A1 - Procédé pour la production de film de polyester, film de polyester pour photopile et module de production d'énergie électrique photovoltaïque - Google Patents

Procédé pour la production de film de polyester, film de polyester pour photopile et module de production d'énergie électrique photovoltaïque Download PDF

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Publication number
WO2012081385A1
WO2012081385A1 PCT/JP2011/077401 JP2011077401W WO2012081385A1 WO 2012081385 A1 WO2012081385 A1 WO 2012081385A1 JP 2011077401 W JP2011077401 W JP 2011077401W WO 2012081385 A1 WO2012081385 A1 WO 2012081385A1
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Prior art keywords
polyester
polyester film
amount
solar cell
film
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PCT/JP2011/077401
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English (en)
Japanese (ja)
Inventor
竜太 竹上
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN201180059659.9A priority Critical patent/CN103260847B/zh
Publication of WO2012081385A1 publication Critical patent/WO2012081385A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91—Heating, e.g. for cross linking
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling drums
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/9165—Electrostatic pinning
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92219—Degree of crosslinking, solidification, crystallinity or homogeneity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/387—Plasticisers, homogenisers or feeders comprising two or more stages using a screw extruder and a gear pump
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a method for producing a polyester film, a polyester film for solar cells, and a solar cell power generation module.
  • the solar cell power generation module used for this solar power generation has a structure in which (sealant) / solar cell element / sealant / back sheet is laminated in this order on glass on which sunlight is incident. is there.
  • Resin materials such as polyester have been used for the back surface protective film (so-called back sheet) disposed on the side opposite to the sunlight incident side of the solar cell power generation module.
  • Polyesters such as polyethylene terephthalate (PET) usually have a large amount of carboxyl groups and hydroxyl groups on the surface thereof, are prone to hydrolysis in an environment where moisture exists, and tend to deteriorate over time.
  • polyesters used in solar cell power generation modules and the like that are constantly exposed to wind and rain such as outdoors are required to have particularly low hydrolyzability. Further, same applies to the polyester to be applied to outdoor applications other than the solar cell power generation module applications, it is required to hydrolyzable is suppressed.
  • the amount of terminal COOH of the polyester that is, the concentration of terminal COOH, can be evaluated by an acid value (AV; Acid Value). If a polyester having a small acid value is polymerized and applied to a film, a film having hydrolysis resistance can be produced.
  • AV Acid Value
  • polyester film for sealing a back surface of a solar cell which contains a titanium compound and a phosphorus compound in amounts satisfying two predetermined relational expressions, and the terminal COOH concentration of the polyester is 40 equivalents / ton or less
  • environmental resistance such as hydrolysis resistance and weather resistance is improved (see, for example, JP-A-2007-204538).
  • solid phase polymerized polyester that undergoes solid phase polymerization under specific conditions in an inert gas atmosphere with an oxygen concentration of 300 ppm or less Is disclosed (for example, see Japanese Patent Application Laid-Open No. 2009-052041). Furthermore, a method of drying granular PET resin with a high-temperature gas for crystallization of the PET resin has been disclosed (for example, see JP-T-2001-519522). H. Zimmerman, N .; T.A. Kim, Polymer Eng. & Sci. , 20, 680 (1980) shows that the lower the amount of terminal carboxy groups, the faster the hydrolysis reaction rate decreases.
  • the present invention relates to a method for producing a polyester film that obtains a polyester film in which variation in hydrolysis resistance is suppressed as compared with a conventional method for producing a polyester film, and a polyester film for solar cells in which variation in hydrolysis resistance is suppressed. And it aims at providing the solar cell power generation module which can obtain the stable power generation performance over a long period of time, and makes it a subject to achieve the object.
  • a solid-phase polymerization step in which a polyester having a crystallinity distribution ⁇ of 3% ⁇ ⁇ 15% is supplied to a reaction vessel and solid-phase polymerized; An extrusion process for extruding the solid-phase polymerized polyester into a film; and It is a manufacturing method of the polyester film which has this.
  • ⁇ 2> The method for producing a polyester film according to ⁇ 1>, wherein the crystallinity distribution ⁇ of the polyester is 5% ⁇ ⁇ ⁇ 13%.
  • the polyester is a method for producing a polyester film according to ⁇ 1> or ⁇ 2>, wherein the crystallite size distribution ⁇ D is 10% or less.
  • ⁇ 4> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 3>, wherein the polyester has a crystallite size distribution ⁇ D of 3% to 9%.
  • ⁇ 5> Any one of the above ⁇ 1> to ⁇ 4>, wherein a hot gas is supplied to the polyester before the solid phase polymerization step, and the polyester is heated and crystallized by the supplied hot gas. It is a manufacturing method of the polyester film as described in one.
  • ⁇ 6> supply amount of the thermal gas [Nm 3 / Kg] is, relative to the polyester 1 kg, is a method for producing a polyester film according to the a 0.1Nm 3 ⁇ 1.5Nm 3 ⁇ 5> .
  • ⁇ 7> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 6>, wherein the temperature of the polyester when entering the reaction vessel is 180 ° C. to 220 ° C.
  • ⁇ 8> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 7>, wherein the solid phase polymerization time is 5 hours to 100 hours.
  • ⁇ 9> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 8>, wherein the crystallite diameter D of the polyester before solid phase polymerization is 80 to 120 mm.
  • ⁇ 10> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 9>, wherein the crystallinity ⁇ of the polyester before the solid phase polymerization is 47% to 58%.
  • the solar cell polyester film according to ⁇ 11> which has a long shape and includes at least terminal COOH, and variation in the amount of the terminal COOH in the longitudinal direction is less than 2 eq / ton.
  • ADVANTAGE OF THE INVENTION compared with the manufacturing method of the conventional polyester film, the manufacturing method of the polyester film which obtains the polyester film in which the variation in hydrolysis resistance was suppressed can be provided. Also, ADVANTAGE OF THE INVENTION According to this invention, the polyester film for solar cells by which the variation in hydrolysis resistance was suppressed compared with the conventional polyester film can be provided. Furthermore, ADVANTAGE OF THE INVENTION According to this invention, the solar cell power generation module from which stable power generation performance is obtained over a long term can be provided.
  • polyester film production method of the present invention and the solar cell polyester film and solar cell power generation module using the same will be described in detail.
  • the method for producing a polyester film according to the present invention includes a solid phase polymerization step in which a polyester having a crystallinity distribution ⁇ of 3% ⁇ ⁇ 15% is supplied to a reaction vessel and subjected to solid phase polymerization, and the solid phase polymerization is performed. And an extrusion process for extruding polyester into a film.
  • the manufacturing method of the polyester film of this invention may have another process as needed, and may be comprised.
  • polyester has a terminal carboxy group (terminal COOH), the terminal carboxy group (terminal COOH) serves as a catalyst and is easily hydrolyzed.
  • the amount of terminal COOH contained in the polyester can be confirmed by the size of the terminal COOH amount (AV) of the polyester, and it can be said that the smaller the terminal COOH amount, the better the hydrolysis resistance.
  • the amount of terminal COOH of the polyester tends to increase when the polyester is heated and melted during extrusion molding or the like. This is considered to be because thermal decomposition occurs due to the polyester being overheated, and terminal COOH is generated. It is considered that polyester overheating is likely to occur due to fluctuations in pressure for extruding polyester in the extruder (pressure fluctuations).
  • the terminal COOH amount (acid value), crystallinity ⁇ , intrinsic viscosity (IV), moisture content, and the like of the polyester can be controlled.
  • the manufacturing method of the polyester film of this invention is demonstrated in detail.
  • Solid-state polymerization process In the solid phase polymerization step, a polyester having a crystallinity distribution ⁇ of 3% ⁇ ⁇ 15% is supplied to the reaction vessel and subjected to solid phase polymerization.
  • polyester First, polyester will be described.
  • the kind of polyester is not particularly limited. It may be synthesized using a dicarboxylic acid component and a diol component, or a commercially available polyester may be used.
  • the polyester when synthesized, for example, it can be obtained by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or a transesterification reaction by a well-known method.
  • dicarboxylic acid component examples include 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, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, and the like, terephthalic acid, isophthalic acid, phthalic acid, 1,4- Naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, 4,4
  • 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.
  • Diols cycloaliphatic dimethanol, spiroglycol, isosorbide and other alicyclic diols, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl)
  • Diol compounds such as aromatic diols such as fluorene.
  • the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component.
  • the "main component” refers to the proportion of the aromatic dicarboxylic acid in the dicarboxylic acid component is 80% 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.
  • at least one aliphatic diol is used as the (B) diol component.
  • the aliphatic diol can contain ethylene glycol, and preferably contains ethylene glycol as a main component.
  • the main component means that the proportion of ethylene glycol in the diol component is 80% or more.
  • the amount of the aliphatic diol (eg, ethylene glycol) used is in the range of 1.015 mol to 1.50 mol with respect to 1 mol of the aromatic dicarboxylic acid (eg, terephthalic acid) and, if necessary, its ester derivative. Is preferred.
  • the amount used is more preferably in the range of 1.02 mol to 1.30 mol, and still more preferably in the range of 1.025 mol to 1.10 mol.
  • the esterification reaction proceeds favorably, and if it is in the range of 1.50 mol or less, for example, by-production of diethylene glycol due to dimerization of ethylene glycol is suppressed, Many characteristics such as melting point, glass transition temperature, crystallinity, heat resistance, hydrolysis resistance, and weather resistance can be kept good.
  • a conventionally known reaction catalyst can be used for the esterification reaction and / or the 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, or a titanium compound as a polymerization catalyst at an arbitrary stage before the polyester production method 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 in the step.
  • a process of adding a pentavalent phosphate ester having no sulfite in this order is
  • 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 addition of a magnesium compound and a phosphorus 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 dicarboxylic acid component and the diol component, or after mixing the dicarboxylic acid component (or diol component) and the titanium compound, the diol component (or dicarboxylic acid component) is mixed. May be. Further, the dicarboxylic acid component, the diol component, and the titanium compound may be mixed at the same time.
  • the mixing is not particularly limited, and can be performed by a conventionally known method.
  • PET polyethylene terephthalate
  • PEN polyethylene-2,6-naphthalate
  • PET has a germanium (Ge) compound (Ge-based catalyst), an antimony (Sb) compound (Sb-based catalyst), an aluminum (Al) compound (Al-based catalyst), and a titanium (Ti) compound (Ti-based catalyst) as catalyst components.
  • germanium (Ge) compound Ge-based catalyst
  • Sb antimony
  • Al aluminum
  • Ti titanium
  • titanium compounds excluding titanium oxide
  • the titanium compound has high reaction activity and can lower the polymerization temperature. Therefore, it is possible to suppress the polyester from being thermally decomposed during the polymerization reaction and generating COOH. That is, by using a titanium compound, the amount of terminal carboxylic acid of polyester that causes thermal decomposition can be reduced, and foreign matter formation can be suppressed. By reducing the amount of the terminal carboxylic acid of the polyester, it is possible to suppress thermal decomposition of the polyester film after the production of the polyester film. Of the titanium compounds, titanium oxide used as a whitening agent cannot provide such an effect.
  • the titanium compound used as the catalyst is preferably at least one of organic chelate titanium complexes having an organic acid as a ligand.
  • organic acid include citric acid, lactic acid, trimellitic acid, malic acid and the like.
  • an organic chelate complex having citric acid or citrate as a ligand is preferable.
  • the titanium-based catalyst also has a catalytic effect on the esterification reaction. By adding it at the esterification stage, the oligomer acid value at the end of the esterification reaction is lowered, and the subsequent polycondensation reaction is performed more efficiently.
  • complexes with citric acid as a ligand are more resistant to hydrolysis than titanium alkoxides, etc., and do not hydrolyze in the esterification reaction process, while maintaining the original activity and catalyzing esterification and polycondensation reactions. It is estimated to function effectively as In general, it is known that hydrolysis resistance deteriorates as the amount of terminal carboxyl groups increases, and the hydrolysis resistance is expected to be improved by decreasing the amount of terminal carboxyl groups by the above addition method. .
  • citrate chelate titanium complex for example, VERTEC® AC-420 manufactured by Johnson Matthey can be easily obtained as a commercial product.
  • the aromatic dicarboxylic acid and the aliphatic diol can be introduced by preparing a slurry containing them and continuously supplying it to the esterification reaction step.
  • titanium compounds In addition to the organic chelate titanium complex, titanium compounds generally include oxides, hydroxides, alkoxides, carboxylates, carbonates, oxalates, and halides. Other titanium compounds may be used in combination with the organic chelate titanium complex as long as the effects of the present invention are not impaired.
  • titanium compounds examples include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, Titanium alkoxide such as tetraphenyl titanate, tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium-silicon or zirconium composite oxide obtained by hydrolysis of a mixture of titanium alkoxide and silicon alkoxide or zirconium alkoxide, Titanium acetate, titanium oxalate, potassium potassium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride Down - aluminum chloride mixture, and titanium acetylacetonate.
  • Titanium alkoxide such
  • the polyester When the polyester is polymerized, it is preferable to use a titanium compound (including a titanium-based catalyst) in a range of 1 ppm to 50 ppm, more preferably 2 ppm to 30 ppm, and still more preferably 3 ppm to 15 ppm in terms of titanium element.
  • the raw material polyester contains 1 ppm to 50 ppm of titanium element. If the amount of the titanium compound (including the titanium-based catalyst) contained in the raw material polyester is less than 1 ppm in terms of titanium element, the weight average molecular weight (Mw) of the polyester cannot be increased, and it is easy to thermally decompose. Foreign matter tends to increase in the machine, which is not preferable.
  • the amount of the titanium compound (including the titanium-based catalyst) contained in the raw material polyester exceeds 50 ppmm in terms of titanium element, the titanium compound (including the titanium-based catalyst) becomes a foreign substance, and uneven stretching occurs when the polyester sheet is stretched. Because it causes, it is not preferable.
  • an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound, and at least one of the titanium compounds is an organic chelate titanium complex having an organic acid as a ligand.
  • An esterification reaction step including at least a step of adding an organic chelate titanium complex, a magnesium compound, and a pentavalent phosphate ester having no aromatic ring as a substituent in this order, and an ester formed in the esterification reaction step
  • a polycondensation step in which a polycondensation product is produced by a polycondensation reaction of the chemical reaction product, and is preferably produced by a polyester production method.
  • polyesters that have a color tone and transparency that are inferior to those of other polyesters and that have excellent heat resistance. Moreover, polyester which has high transparency and few yellowishness is obtained, without using color tone adjusting materials, such as a cobalt compound and a pigment
  • This polyester can be used for applications requiring high transparency (for example, optical film, industrial squirrel, etc.), and it is not necessary to use an expensive germanium-based catalyst, so that the cost can be greatly reduced.
  • the foreign material-prone catalyst caused by Sb catalyst systems are avoided, it is generated and quality defects reduce failure at the film formation process, it is possible to achieve even lower cost by yield ratio improvement.
  • esterification reaction a process of adding an organic chelate titanium complex which is a titanium compound and a magnesium compound and a pentavalent phosphorus compound as additives in this order is provided. At this time, the esterification reaction proceeds in the presence of the organic chelate titanium complex, and thereafter, the addition of the magnesium compound is started before the addition of the phosphorus compound.
  • 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
  • phosphoric acid esters having a lower alkyl group having 2 or less carbon atoms as a substituent [(OR) 3 —P ⁇ O; R an alkyl group having 1 or 2 carbon atoms]
  • phosphoric acid Trimethyl and triethyl phosphate are particularly preferable.
  • the addition amount of the phosphorus compound is preferably an amount such that the P element conversion value is in the range of 50 ppm to 90 ppm, more preferably 60 ppm to 80 ppm, and still more preferably 60 ppm to 75 ppm.
  • magnesium compound By including a magnesium compound in the polyester, the electrostatic applicability of the polyester is improved. In this case, although it is easy to color, in this invention, coloring is suppressed and the outstanding color tone and heat resistance are obtained.
  • the magnesium compound include magnesium salts such as magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate. Among these, magnesium acetate is most preferable from the viewpoint of solubility in 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 preferably an amount in the range of 60 ppm to 90 ppm, more preferably an amount in the range of 70 ppm to 80 ppm, from the viewpoint of imparting electrostatic applicability.
  • the value Z calculated from the following formula (i) for the titanium compound as the catalyst component and the magnesium compound and phosphorus compound as the additive satisfies the following relational expression (ii).
  • 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.
  • (I) Z 5 ⁇ (P content [ppm] / P atomic weight) ⁇ 2 ⁇ (Mg content [ppm] / Mg atomic weight) ⁇ 4 ⁇ (Ti content [ppm] / Ti atomic weight) (Ii) 0 ⁇ Z ⁇ 5.0
  • the 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.
  • the titanium compound, phosphorus compound, and magnesium compound which are inexpensive and easily available, are used for color tone and heat while having the reaction activity required for the reaction.
  • a polyester excellent in coloring resistance can be obtained.
  • a chelate titanium complex having 1 ppm to 30 ppm of citric acid or citrate as a ligand to the aromatic dicarboxylic acid and the aliphatic diol
  • 60 ppm to 90 ppm (more preferably 70 ppm to 80 ppm) of a weak acid magnesium salt is added, and after the addition, 50 ppm to 90 ppm (more preferably 60 ppm to 75 ppm) of the aromatic ring is replaced.
  • the aspect which adds the pentavalent phosphate which does not have as a group is mentioned.
  • the esterification reaction may 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 from the system. it can.
  • the esterification reaction described above 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 2. It is preferably ⁇ 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.
  • a polycondensation product is produced by subjecting an esterification reaction product produced by the esterification reaction to a polycondensation reaction.
  • 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 it 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 10 torr ⁇ 3 torr 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 , More preferably from 275 ° C. ⁇ 285 ° C.
  • the pressure is 10torr ⁇ 0.1torr (1.33 ⁇ 10 -3 MPa ⁇ 1.33 ⁇ 10 -5 MPa), more preferably 5torr ⁇ 0.5torr (6.
  • An aspect of 67 ⁇ 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.
  • Crystallinity distribution ⁇ can be calculated as follows. 1) 100 grains of polyester immediately before being supplied to the reaction tank are randomly taken out. 2) The specific gravity of each polyester taken out is measured by the density gradient method, and the crystallinity of each polyester is calculated by the following formula (a).
  • Crystallinity (%) ⁇ (d ⁇ dA) / (dC ⁇ dA) ⁇ ⁇ 100
  • dA is the density when the polyester is completely amorphous
  • dC is the density when the polyester is completely crystallized
  • d is the density of the polyester
  • the average value of the degree of crystallinity ⁇ calculated for the 100 polyesters taken out is calculated. Further, from the difference between the maximum value ⁇ max and the minimum value ⁇ min of the crystallinity ⁇ calculated for 100 polyester grains, a crystallinity distribution ⁇ , which is a variation in crystallinity, is obtained by the following equation (b).
  • the crystallization of the polyester can be performed by heating the polyester.
  • the heating method include bringing the polyester into contact with a metal or supplying a hot gas to the polyester to exchange heat.
  • the method of contacting the metal is a method in which polyester particles are administered to a heated screw-shaped metal plate and the polyester is heated by rotating the screw (torus disk method).
  • the polyester in the above heating method in which the polyester is brought into contact with the metal, friction may occur due to contact between the metal and the polyester or contact between the polyesters, and polyester dust may be generated.
  • the crystallinity ⁇ of the polyester falls within, for example, a range of 39% to 42% (crystallinity distribution ⁇ is 3%), and the distribution tends to be narrow.
  • polyesters having various crystallinities may be prepared by the torus disk method and mixed to prepare a polyester of 3% ⁇ ⁇ 15%.
  • the heating method in which the polyester is heated by the hot gas the temperature unevenness is likely to occur due to indirect heating, and it is easy to obtain a polyester having a wide crystallinity distribution ⁇ .
  • the crystallinity ⁇ of the ester is in the range of 33% to 44% (the crystallinity distribution ⁇ is 11%), and the distribution becomes wide.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a crystallization apparatus for heating polyester.
  • FIG. 1 shows a crystallization apparatus 100.
  • the crystallization apparatus 100 has hot gas supply ports 4 and 6 and hot gas discharge ports 12 and 14 that can supply hot gas (for example, nitrogen gas) to the wall.
  • hot gas for example, nitrogen gas
  • FIG. 1 two hot gas supply ports are shown, but there may be only one or three or more.
  • the crystallization apparatus 100 has an opening 8 for feeding polyester at the upper part and an opening 10 for discharging heated polyester at the lower part.
  • a plurality of rods are attached to the inner wall surface of the crystallization apparatus 100. At least a part of the bar is installed above the hot gas supply port 6.
  • the rod is a triangular prism having a triangular cross section, and is attached so that the axial direction is substantially perpendicular to the direction of gravity. Adjacent bars are arranged with an interval sufficient to allow the polyester to pass through. The polyester introduced from the opening 8 at the top of the crystallization apparatus 100 is scattered by hitting the rod, and the hot gas supplied from the hot gas supply port easily hits the polyester.
  • polyester is easily heated because the contact with the hot gas is prolonged due to slowing down by hitting with a stick and falling apart.
  • polyester is preferably a pellet of such particulate (polyester particles).
  • the rod 2 is only one means for facilitating the supply of hot gas heat to the polyester. Therefore, in FIG. 1, the cross section is a triangular prism, but the cross-sectional shape may be a circle, a polygon such as a quadrangle, a hexagon, etc., a plate having a net like a sieve, or a slit like a grid You may use the board which has 2 layers in piles. For example, five slit plates having triangular prism slits may be used. At this time, it is preferable to adjust the position of the slit so that the lower triangular prism is located below the space between the upper triangular prisms so that the positions of the spaces between the triangular prisms do not overlap in adjacent plates.
  • a polyester crystallization apparatus using a hot gas can be obtained as a roof type dryer manufactured by Buehler, and the apparatus may be used to crystallize the polyester.
  • the polyester heated by the hot gas is returned to the upper part of the opening 8 at the upper part of the crystallization apparatus 100 by a circulation device (not shown), and is heated again by being charged again from the opening 8. After the heating in the crystallization apparatus 100 is completed, it is discharged from the opening 10 at the lower part of the crystallization apparatus 100.
  • a crystallinity distribution ⁇ of 3% ⁇ ⁇ 15% indicates that the crystallinity ⁇ of the polyester varies widely, and the crystallinity ⁇ of the polyester varies due to heating of the polyester. It is thought to mean that there is a variation in time. That is, it is considered that heating with warm gas is more difficult to heat uniformly than heating with metal contact.
  • the variation in crystallite diameter D (crystallite diameter distribution ⁇ D) of the polyester obtained by heating (crystallization) is preferably smaller, and ⁇ D is preferably 10% or less.
  • the crystallite diameter is the size (maximum diameter) of the minimum crystal unit constituting the crystal, and can generally be measured using an X-ray diffractometer.
  • the crystallite diameter D of the polyester is considered to be likely to vary due to variations in the heating temperature of the polyester. Therefore, it is preferable to keep the temperature of the hot gas constant.
  • the temperature of the thermal gas is preferably set to 175 ° C. ⁇ 215 ° C., and more preferably set to 185 °C ⁇ 205 °C.
  • the hot gas is preferably an inert gas, and examples thereof include nitrogen (N 2 ) gas, argon (Ar) gas, carbon dioxide (CO 2 ) gas, and the like.
  • the heating time for the polyester is preferably 3 hours to 10 hours, more preferably 3 hours to 8 hours. When it is 3 hours or more, the heating time varies, and the crystallinity distribution ⁇ is easily increased. When it is 10 hours or less, thermal decomposition due to overheating or overheating of the polyester can be suppressed.
  • the degree of crystallinity ⁇ of the polyester can be varied by controlling the ratio between the supply amount of the hot gas and the input amount of the polyester.
  • the supply amount of heat gas [Nm 3 / Kg] is the polyester 1 kg, it is preferable to 0.1Nm 3 ⁇ 1.5Nm 3.
  • the supply amount of the hot gas is more preferably 0.3 Nm 3 to 1.0 Nm 3 with respect to 1 kg of polyester.
  • the ratio to the supply amount of the hot gas can be adjusted by the wind speed (superficial velocity) of the hot gas passing through the reaction vessel.
  • the hot gas wind speed (superficial velocity) is 0.3 m / sec to 10 m / sec (preferably, 0.5m / sec ⁇ 5.0m / sec ) in a range of from, it is possible to supply the amount of heat gas to polyester 1kg and 0.1Nm 3 ⁇ 1.5Nm 3.
  • the crystallinity distribution ⁇ of polyester obtained by heating (crystallization) is preferably 5% to 13%, particularly preferably 8% to 9%.
  • the crystallite diameter D of the polyester obtained by heating (crystallization) is preferably from 80 to 120 mm, and more preferably from 90 to 100 mm.
  • the crystallite diameter D and the crystallite diameter distribution ⁇ D of the polyester can be obtained as follows.
  • the crystallite diameter D is measured for 100 polyester grains, and from these values, the average value of the crystallite diameter D of the polyester supplied to the reaction vessel is obtained, and the difference between the maximum value and the minimum value of the crystallite diameter D is calculated. Dividing the crystallite diameter D by the average value of the crystallite diameter D (crystallite diameter distribution ⁇ D) is obtained.
  • the crystallite size distribution ⁇ D is preferably 3% to 9%.
  • Solid phase polymerization In the solid phase polymerization step, a polyester having a crystallinity distribution ⁇ of 3% ⁇ ⁇ 15% is supplied to the reaction vessel and subjected to solid phase polymerization.
  • the solid phase polymerization of polyester may be a continuous method (a method in which a tower is filled with a resin, and this is slowly heated for a predetermined period of time while being heated and then sequentially fed out), or a batch method (a resin is placed in a container). Or a method of heating for a predetermined time).
  • the temperature of solid phase polymerization is preferably 170 ° C. to 240 ° C., more preferably 180 ° C. to 230 ° C., and further preferably 190 ° C. to 220 ° C.
  • the amount of terminal COOH (AV) of the polyester is preferably reduced.
  • the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and further preferably 15 hours to 50 hours. When the time is within the above range, it is preferable in that the terminal COOH amount (AV) and intrinsic viscosity (IV) of the polyester can be easily controlled within the preferable ranges of the present invention.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • the temperature of the polyester when it is put into the reaction vessel is preferably 180 ° C. to 220 ° C. Prior to solid phase polymerization, the temperature of the pellets in the reaction vessel can be set to 180 ° C. to 220 ° C. by preheating the polyester to the above temperature range.
  • the temperature of the polyester when entering the reaction vessel is more preferably 190 ° C. to 210 ° C.
  • the water content of the polyester, the crystallinity, the acid value of the polyester, that is, the concentration of terminal COOH (AV) and the intrinsic viscosity (IV) of the polyester are further increased by solid phase polymerization.
  • the intrinsic viscosity (IV) [unit dl / g] of the polyester is preferably 0.7 to 0.9. When the intrinsic viscosity is 0.7 or more, the molecular motion of the polyester is hindered and it is difficult to crystallize.
  • IV is more preferably 0.70 to 0.85, and particularly preferably 0.73 to 0.80.
  • a titanium (Ti) -based catalyst is used, and further solid-phase polymerization is performed, whereby the intrinsic viscosity (IV) of the polyester is set to 0.7 to 0.9, which will be described later.
  • IV intrinsic viscosity
  • the amount of terminal COOH (AV) can be measured by a titration method according to the method described in H. A. Pohl, Anal. Chem. 26 (1954) 2145. Specifically, polyester is dissolved in benzyl alcohol at 205 ° C., a phenol red indicator is added, titrated with a water / methanol / benzyl alcohol solution of sodium hydroxide, and calculated from the appropriate amount.
  • the polyester used for the solid phase polymerization of the polyester may be a polyester obtained by polymerizing and crystallizing by the above-described esterification reaction or a commercially available polyester in the form of pellets or the like as a starting material.
  • the solid-phase polymerized polyester is extruded into a film.
  • the polyester film is formed by melt-kneading the solid-phase polymerized polyester using an extruder and extruding it from a die (extrusion die).
  • the thickness of the polyester film is preferably 250 ⁇ m to 500 ⁇ m.
  • the extrusion process is further divided into a melt-kneading and extrusion process in which solid-phase polymerized polyester is melted and extruded from a die, a cooling and solidification process in which an unstretched polyester film is cooled and solidified, and an unstretched state after cooling and solidification. And a stretching process for stretching the film.
  • polyester was dried, after the residual moisture 100ppm or less, can be melted by using an extruder.
  • the melting temperature is preferably 250 ° C to 320 ° C, more preferably 260 ° C to 310 ° C, and further preferably 270 ° C to 300 ° C.
  • the extruder may be uniaxial or multi-axial. It is more preferable that the inside of the extruder is replaced with nitrogen from the viewpoint that generation of terminal COOH due to thermal decomposition can be further suppressed.
  • the melted molten resin (melt) is extruded from an extrusion die through a gear pump, a filter or the like. At this time, it may be extruded as a single layer or may be extruded as a multilayer.
  • the melt extruded from the extrusion die can be solidified using a chill roll (cooling roll).
  • the temperature of the chill roll is preferably 10 ° C. to 80 ° C., more preferably 15 ° C. to 70 ° C., and still more preferably 20 ° C. to 60 ° C.
  • the thickness after stretching is 250 ⁇ m or more films
  • thick film be effectively cooling can be performed.
  • the cooling is insufficient, spherulites are likely to be generated, which may cause uneven stretching and uneven thickness.
  • the polyester film of the present invention can be suitably produced by biaxially stretching the produced extruded film (unstretched film).
  • an unstretched polyester film is led to a group of rolls heated to a temperature of 70 ° C. to 140 ° C., and stretched at a stretch ratio of 3 to 5 times in the longitudinal direction (longitudinal direction, that is, the traveling direction of the film).
  • the film is preferably stretched and cooled by a roll group having a temperature of 20 ° C. to 50 ° C.
  • the film is guided to a tenter while holding both ends of the film with clips, and stretched in a direction perpendicular to the longitudinal direction (width direction) by 3 to 5 times in an atmosphere heated to a temperature of 80 ° C. to 150 ° C. Stretch with.
  • the stretching ratio is preferably 3 to 5 times in each of the longitudinal direction and the width direction.
  • the area ratio (longitudinal draw ratio ⁇ lateral draw ratio) is preferably 9 to 15 times.
  • the area magnification is 9 times or more, the reflectivity, concealability and film strength of the obtained biaxially stretched laminated film are good, and when the area magnification is 15 times or less, tearing during stretching should be avoided. Can do.
  • the simultaneous biaxial stretching method in addition to the sequential biaxial stretching method in which the longitudinal direction and the width direction are separated separately, the simultaneous biaxial stretching method in which the longitudinal direction and the width direction are simultaneously stretched. Either may be sufficient.
  • the melting point (Tm) above the glass transition temperature (Tg) of the resin, which is preferably the raw material, is preferably continued in the tenter.
  • Heat treatment is performed at a temperature less than 1 second to 30 seconds, and after uniform cooling, cool to room temperature.
  • the heat treatment temperature is preferably higher.
  • the heat treatment temperature is too high, the orientation crystallinity is lowered, and as a result, the formed film may be inferior in hydrolysis resistance.
  • the heat treatment temperature (Ts) of the polyester film of the present invention is preferably 40 ° C. ⁇ (Tm ⁇ Ts) ⁇ 90 ° C. More preferably, the heat treatment temperature (Ts) is 50 ° C. ⁇ (Tm ⁇ Ts) ⁇ 80 ° C., more preferably 55 ° C. ⁇ (Tm ⁇ Ts) ⁇ 75 ° C.
  • the polyester film of the present invention can be used as a back sheet constituting a solar cell power generation module
  • the atmospheric temperature may rise to about 100 ° C. when the module is used, so the heat treatment temperature (Ts) is It is preferably 160 ° C. or higher and Tm ⁇ 40 ° C. (where Tm ⁇ 40 ° C.> 160 ° C.) or lower. More preferably Tm-50 °C 170 °C or higher (provided that, Tm-50 °C> 170 °C) or less, more preferably Ts is Tm-55 °C 180 °C or higher (provided that, Tm-55 °C> 180 °C) or less.
  • relaxation treatment of 3% to 12% may be performed in the width direction or the longitudinal direction.
  • the relaxation ratio “3% to 12%” in the relaxation treatment is calculated by the following formula (c), where La is the length of the polyester film before relaxation and Lb is the length of the polyester film after relaxation.
  • Formula (c) 100 ⁇ (La ⁇ Lb) / La
  • the width direction of La and Lb of the polyester film, as well as the longitudinal direction of La and Lb of the polyester film is defined as follows. [Width direction]
  • the maximum width of the polyester film at the time of stretching when the polyester film is stretched with a tenter is defined as the length La of the polyester film before relaxation.
  • tensile_strength (relaxing) and taking out a polyester film from a tenter be length Lb of the polyester film after relaxation
  • Longitudinal direction When the polyester film is stretched by applying tension to the polyester film with a tenter, two points are marked in the longitudinal direction, and the distance between the two points is the length La of the polyester film before relaxation. Further, the distance between the two points after the tension is released (relaxed) and taken out from the tenter is defined as the length Lb of the relaxed polyester film.
  • the intrinsic viscosity (IV) and terminal COOH amount (AV) of the polyester film produced by the method for producing a polyester film of the present invention are controlled through the solid phase polymerization.
  • the intrinsic viscosity (IV) [unit dl / g] of the polyester film is preferably in the range of 0.7 to 0.9, more preferably 0.7 to 0.85, and particularly preferably 0.73 to 0. .80.
  • IV is 0.7 or more, the molecular weight of the polyester is maintained in a desired range, and when the polyester film has a multilayer structure, good adhesion without cohesive failure can be obtained at the adhesion interface with other layers.
  • IV is 0.9 or less, the melt viscosity during film formation is good, thermal decomposition of the polyester due to shearing heat generation is suppressed, and the amount of terminal COOH (AV) can be suppressed low.
  • the polyester film produced by the method for producing a polyester film of the present invention can make the terminal COOH amount (AV) in the longitudinal direction difficult to vary.
  • AV terminal COOH amount
  • a film or sheet in order to obtain a constant film thickness, it is desired to melt and extrude with a constant discharge amount.
  • uniaxial tandem extrusion or gear pump assist is desired.
  • a twin screw extruder of the type is preferred and used.
  • a film having a constant thickness can be obtained with the above apparatus, but in that case, the screw rotation speed of the extruder fluctuates, and as a result, thermal decomposition of PET in the extruder (increase in terminal COOH) ) Occurs in response to fluctuations in the screw speed.
  • the terminal COOH varies in the longitudinal direction of the film, resulting in non-uniform hydrolysis resistance in the longitudinal direction.
  • the fluctuation of the discharge amount when the polyester is melt-extruded with a constant screw rotation is reduced, and as a result, a constant film thickness can be obtained while the terminal COOH due to the fluctuation of thermal decomposition is obtained. Fluctuations can be suppressed. This is considered to be a phenomenon similar to the effect of reducing the extrusion load by the lubricant.
  • FIG. 2 is a schematic view of a polyester film having a long shape for explaining a method for evaluating the variation in the amount of terminal COOH of the polyester film.
  • FIG. 2 shows a polyester film 20, and arbitrary points P 1 , P 2 , P 3, P n + 1 , P n (these are collectively referred to as “point P”) are shown on the polyester film 20.
  • the points P are lined up at 100 m intervals in the longitudinal direction (MD; Machine Direction) of the polyester film 20. Between the point P3 and the point P n + 1, may have a point which is not further shown, may not have. Further, the point P is located at the center of the polyester film 20 in the width direction (TD; Transverse Direction).
  • MD Machine Direction
  • the point P is a position where the terminal COOH amount of the polyester film is measured, and the variation in the terminal COOH amount of the polyester film is calculated by measuring the terminal COOH amount at n points P.
  • a rectangular (a broken line frame shown in FIG. 2) sample piece is cut so that the point P is the center, and the terminal COOH amount is measured for the obtained n sample pieces, and the terminal COOH amount is measured.
  • the average value of the terminal COOH, the maximum value of the terminal COOH amount, and the minimum value of the terminal COOH amount are examined.
  • the variation of the terminal COOH amount is evaluated from the average value, the maximum value, and the minimum value of the measured terminal COOH amount.
  • the number (n) of positions for measuring the terminal COOH amount of the polyester film is 20 points.
  • the terminal COOH amount of the polyester film is preferably such that the variation in the amount of terminal COOH in the longitudinal direction of the film is less than 2 (eq / ton) with respect to the terminal COOH of the polyester. “The variation in the amount of terminal COOH is less than 2 (eq / ton)” means that the difference between the maximum value and the minimum value of the terminal COOH amount is in the range of less than 2 (eq / ton).
  • the variation in the amount of the terminal COOH in the longitudinal direction of the polyester film is more preferably 1 (eq / ton) or less. In the present specification, “eq / ton” represents a molar equivalent per ton.
  • the breaking elongation after storage is higher than the breaking elongation before storage. Therefore, the storage time (breaking elongation half-life) of 50% is preferably 70 hours or more.
  • the elongation at break half time is more preferably 100 hours or more, and still more preferably 120 hours or more.
  • the hydrolysis resistance of the polyester film can be evaluated by the half elongation time at break. This is calculated
  • the elongation at break [%] is a value obtained by cutting a sample piece having a size of 1 cm ⁇ 20 cm from a polyester film and pulling the sample piece at a rate of 5 cm between chucks and 20% / min.
  • Polyester films generally have poor hydrolysis resistance with increasing thickness, and tend not to withstand long-term use in harsh use environments such as exposure to wind and rain or direct sunlight.
  • the polyester film obtained by the method for producing a polyester film of the present invention has excellent hydrolysis resistance, and further, there is little variation in the amount of terminal COOH in the longitudinal direction of the polyester film. Because the variation in the amount of terminal COOH in the longitudinal direction of the polyester film is small, the variation in the half elongation time of the polyester film can be reduced, and the variation in the half elongation time of the polyester film is less likely to occur. Over time, the film functionality is less likely to vary. Therefore, when the polyester film obtained by the method for producing a polyester film of the present invention is configured as a solar cell power generation module, for example, desired power generation performance can be stably obtained over a long period of time.
  • the polyester film produced by the method for producing a polyester film of the present invention preferably has a thickness after stretching of 250 ⁇ m to 500 ⁇ m.
  • the polyester film obtained by the method for producing a polyester film of the present invention can be constituted by providing at least one functional layer such as an easy-adhesive layer, a UV absorbing layer, and a white layer.
  • the following functional layer may be applied to a polyester film after uniaxial stretching and / or biaxial stretching.
  • 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.
  • surface treatment flame treatment, corona treatment, plasma treatment, ultraviolet treatment, etc.
  • the polyester film may have an easy-adhesive layer on the side facing the sealing material of the battery side substrate in which the solar cell element is sealed with a sealing agent.
  • the easy-adhesive layer By providing the easy-adhesive layer, the back sheet and the sealing material can be firmly bonded.
  • the easily adhesive layer has an adhesive force of 10 N / cm or more, preferably 20 N / cm or more, particularly with EVA (ethylene-vinyl acetate copolymer) used as a sealing material.
  • EVA ethylene-vinyl acetate copolymer
  • the easy-adhesion layer needs to prevent the back sheet from peeling off during use of the solar cell power generation module, and therefore, the easy-adhesion layer desirably has high moisture and heat resistance.
  • Binder The easy-adhesion layer can contain at least one binder.
  • the binder for example, polyester, polyurethane, acrylic resin, polyolefin, or the like can be used. Among these, acrylic resins and polyolefins are preferable as the binder from the viewpoint of durability.
  • acrylic resin a composite resin of acrylic and silicone is also preferable. The following can be mentioned as an example of a preferable binder.
  • polyolefins include Chemipearl S-120 and S-75N (both trade names, manufactured by Mitsui Chemicals, Inc.).
  • Examples of the acrylic resin include Julimer ET-410 and SEK-301 (both trade names, manufactured by Nippon Pure Chemical Industries, Ltd.).
  • Examples of the composite resin of acrylic and silicone include Ceranate WSA 1060, WSA 1070 (both manufactured by DIC Corporation), and H7620, H7630, H7650 (both trade names, manufactured by Asahi Kasei Chemicals Corporation).
  • the amount of the binder in the easy adhesion layer is preferably in the range of 0.05g / m 2 ⁇ 5g / m 2, the range of 0.08g / m 2 ⁇ 3g / m 2 is particularly preferred.
  • the binder amount is more good adhesion is obtained by at 0.05 g / m 2 or more, a better surface is obtained by at 5 g / m 2 or less.
  • the easy-adhesion layer can contain at least one kind of fine particles.
  • the easy-adhesive layer preferably contains 5% or more of fine particles with respect to the mass of the entire layer.
  • fine particles inorganic fine particles such as silica, calcium carbonate, magnesium oxide, magnesium carbonate, tin oxide and the like are preferably exemplified. In particular in this, in that reduction of adhesiveness is small when exposed to wet heat atmosphere, tin oxide, silica fine particles are preferred.
  • the particle size of the fine particles can be measured by observing the cross section of the coated film with a scanning electron microscope, preferably about 10 nm to 700 nm, more preferably about 20 nm to 300 nm.
  • the shape of the fine particles is not particularly limited, and those having a spherical shape, an indefinite shape, a needle shape, or the like can be used.
  • the addition amount of the fine particles in the easy-adhesive layer is preferably 5 to 400% by mass, more preferably 50 to 300% by mass, based on the binder in the easy-adhesive layer. When the addition amount of the fine particles is 5% by mass or more, the adhesiveness when exposed to a wet heat atmosphere is excellent, and when it is 400% by mass or less, the surface state of the easily adhesive layer is better.
  • the easy-adhesion layer can contain at least one crosslinking agent.
  • the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of securing adhesiveness after wet heat aging.
  • oxazoline-based crosslinking agent examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2 -Oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl) 2-oxazoline), 2,2'-p-pheny
  • (co) polymers of these compounds can also be preferably used.
  • a compound having an oxazoline group Epocros K2010E, K2020E, K2030E, WS500, WS700 (all trade names, manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like can be used.
  • a preferable addition amount of the crosslinking agent in the easy-adhesive layer is preferably 5 to 50% by mass, more preferably 20 to 40% by mass, based on the binder of the easy-adhesive layer.
  • the addition amount of the crosslinking agent is 5% by mass or more, a good crosslinking effect is obtained, and the strength of the reflective layer is not reduced and adhesion failure hardly occurs, and when it is 50% by mass or less, the pot life of the coating liquid is further increased. I can keep it long.
  • a known matting agent such as polystyrene, polymethylmethacrylate or silica, or a known surfactant such as anionic or nonionic is added to the easily adhesive layer. May be.
  • Formation method of an easily-adhesive layer As a formation method of an easily-adhesive layer, there exist the method of pasting the polymer sheet which has easy-adhesiveness to a polyester film, and the method by application
  • the method by coating is preferable in that it can be formed with a simple and highly uniform thin film.
  • a coating method for example, a known method such as a gravure coater or a bar coater can be used.
  • the solvent of the coating solution used for coating may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 ⁇ m to 8 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m.
  • the thickness of the easy-adhesive layer is 0.05 ⁇ m or more, the required easy adhesion can be easily obtained, and when the thickness is 8 ⁇ m or less, the planar shape can be maintained better.
  • an easily bonding layer has transparency from a viewpoint which does not impair the effect of this colored layer when a colored layer (especially reflective layer) is arrange
  • the polyester film may be provided with an ultraviolet absorbing layer containing an ultraviolet absorber.
  • An ultraviolet absorption layer can be arrange
  • the ultraviolet absorber is preferably dissolved and dispersed together with an ionomer resin, polyester resin, urethane resin, acrylic resin, polyethylene resin, polypropylene resin, polyamide resin, vinyl acetate resin, cellulose ester resin, and the like.
  • the transmittance is preferably 20% or less.
  • a colored layer can be provided on the polyester film.
  • the colored layer is a layer arranged in contact with the surface of the polyester film or through another layer, and can be constituted using a pigment or a binder.
  • the first function of the colored layer is to increase the power generation efficiency of the solar power generation module by reflecting the incident light that reaches the back sheet without being used for power generation in the solar cells and returning it to the solar cells. It is in.
  • the second function is to improve the decorativeness of the appearance when the solar cell power generation module is viewed from the front side. In general, when the solar battery power generation module is viewed from the front side, a back sheet can be seen around the solar battery cell, and the decorativeness can be improved by providing a colored layer on the back sheet.
  • the colored layer can contain at least one pigment.
  • the pigment is preferably contained in the range of 2.5 g / m 2 to 8.5 g / m 2 .
  • a more preferable pigment content is in the range of 4.5 g / m 2 to 7.5 g / m 2 .
  • the pigment content is 2.5 g / m 2 or more, necessary coloring can be easily obtained, and the light reflectance and decorativeness can be adjusted to be more excellent.
  • the pigment content is 8.5 g / m 2 or less, the planar shape of the colored layer can be maintained better.
  • the pigment examples include inorganic pigments such as titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. It is done.
  • a white pigment is preferable from the viewpoint of constituting a colored layer as a reflective layer that reflects incident sunlight.
  • titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc and the like are preferable.
  • the average particle size of the pigment is preferably 0.03 ⁇ m to 0.8 ⁇ m, more preferably about 0.15 ⁇ m to 0.5 ⁇ m. When the average particle size is within the above range, the light reflection efficiency is good.
  • the preferred addition amount of pigment in the reflective layer varies depending on the type of pigment used and the average particle diameter, but cannot be generally stated, but 1.5 g / m 2 ⁇ is preferably 15 g / m 2, more preferably from 3g / m 2 ⁇ 10g / m 2 approximately. When the addition amount is 1.5 g / m 2 or more, the required reflectance is easily obtained, and when the addition amount is 15 g / m 2 or less, the strength of the reflection layer can be kept higher.
  • the colored layer can contain at least one binder.
  • the binder is included, the amount is preferably in the range of 15% by mass to 200% by mass and more preferably in the range of 17% by mass to 100% by mass with respect to the pigment.
  • the amount of the binder is 15% by mass or more, the strength of the colored layer can be more favorably maintained, and when it is 200% by mass or less, the reflectance and decorativeness are prevented from being lowered.
  • a binder suitable for the colored layer for example, polyester, polyurethane, acrylic resin, polyolefin, or the like can be used. From the viewpoint of durability, the binder is preferably an acrylic resin or a polyolefin.
  • the acrylic resin a composite resin of acrylic and silicone is also preferable.
  • Examples of preferred binders include the following.
  • Examples of the polyolefin include Chemipearl S-120 and S-75N (both trade names, manufactured by Mitsui Chemicals, Inc.).
  • Examples of the acrylic resin include Julimer ET-410 and SEK-301 (both trade names, manufactured by Nippon Pure Chemical Industries, Ltd.).
  • Examples of the composite resin of acrylic and silicone include Ceranate WSA1060, WSA1070 (both trade names, manufactured by DIC Corporation), H7620, H7630, H7650 (both trade names, manufactured by Asahi Kasei Chemicals Corporation), and the like. Can do.
  • ком ⁇ онент In addition to the binder and the pigment, a crosslinking agent, a surfactant, a filler, and the like may be further added to the colored layer as necessary.
  • crosslinking agent examples include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • the addition amount of the crosslinking agent in the colorant is preferably 5% by mass to 50% by mass and more preferably 10% by mass to 40% by mass with respect to the binder of the colored layer.
  • the addition amount of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, the strength and adhesiveness of the colored layer can be maintained high, and when it is 50% by mass or less, the coating solution The pot life can be maintained longer.
  • the surfactant a known surfactant such as an anionic or nonionic surfactant can be used.
  • the addition amount of the surfactant is preferably 0.1 mg / m 2 to 15 mg / m 2 , more preferably 0.5 mg / m 2 to 5 mg / m 2 .
  • the amount of the surfactant added is 0.1 mg / m 2 or more to effectively suppress the occurrence of repelling, and the amount added is 15 mg / m 2 or less to provide excellent adhesion.
  • a filler such as silica may be added to the colored layer in addition to the above pigment.
  • the addition amount of the filler is preferably 20% by mass or less, more preferably 15% by mass or less per binder of the colored layer.
  • the strength of the colored layer can be increased.
  • the ratio of a pigment can be maintained because the addition amount of a filler is 20 mass% or less, favorable light reflectivity (reflectance) and decorativeness are obtained.
  • a forming method of the colored layer there are a method of pasting a polymer sheet containing a pigment on a polyester film, a method of co-extruding a colored layer at the time of forming a polyester film, a method by coating, and the like.
  • the method by coating is preferable in that it can be formed with a simple and highly uniform thin film.
  • a coating method for example, a known method such as a gravure coater or a bar coater can be used.
  • the solvent of the coating solution used for coating may be water or an organic solvent such as toluene or methyl ethyl ketone. However, from the viewpoint of environmental burden, it is preferable to use water as a solvent.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the colored layer preferably contains a white pigment and is configured as a reflective layer.
  • the light reflectance at 550 nm in the case of the reflective layer is preferably 75% or more. When the reflectance is 75% or more, sunlight that has passed through the solar battery cell and has not been used for power generation can be returned to the cell, and the effect of increasing power generation efficiency is high.
  • the thickness of the reflective layer is preferably 1 ⁇ m to 20 ⁇ m, more preferably about 1.5 ⁇ m to 10 ⁇ m.
  • the film thickness is 1 ⁇ m or more, necessary decoration and reflectance are easily obtained, and when it is 20 ⁇ m or less, the surface shape may be deteriorated.
  • An undercoat layer can be provided on the polyester film.
  • the undercoat layer may be provided between the colored layer and the polyester film.
  • the undercoat layer can be formed using a binder, a crosslinking agent, a surfactant, and the like.
  • binder contained in the undercoat layer examples include polyester, polyurethane, acrylic resin, and polyolefin.
  • an epoxy, isocyanate, melamine, carbodiimide, oxazoline, or other crosslinking agent, anionic or nonionic surfactant, silica or other filler may be added to the undercoat layer.
  • the solvent may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • Coating may be applied to a polyester film after biaxial stretching, it may be applied to a polyester film after uniaxial stretching. In this case, the film may be further stretched in a direction different from the initial stretching after coating. Furthermore, you may extend
  • the thickness of the undercoat layer is preferably 0.05 ⁇ m to 2 ⁇ m, more preferably about 0.1 ⁇ m to 1.5 ⁇ m. When the film thickness is 0.05 ⁇ m or more, the necessary adhesiveness is easily obtained, and when it is 2 ⁇ m or less, the surface shape can be favorably maintained.
  • -Fluorine resin layer / Si resin layer- It is preferable to provide at least one of a fluorine-type resin layer and a Si-type resin layer in a polyester film.
  • a fluorine-based resin layer or the Si-based resin layer it is possible to prevent contamination of the polyester surface and improve weather resistance.
  • it is also preferable to stick together fluorine resin films such as Tedlar (trade name, manufactured by DuPont).
  • each of the fluorine-based resin layer and the Si-based resin layer is preferably in the range of 1 ⁇ m to 50 ⁇ m, more preferably in the range of 3 ⁇ m to 40 ⁇ m.
  • the polyester film is provided with an inorganic layer.
  • the inorganic layer By providing the inorganic layer to prevent ingress of water or gas into the polyester, it is possible to provide a function as a vapor barrier and gas barrier layer.
  • the inorganic layer may be provided on either the front or back side of the polyester film, but from the viewpoint of waterproofing, moisture proofing, etc., the side opposite to the battery side substrate of the polyester film (the side on which the colored layer or easy adhesion layer is formed) Are preferably provided.
  • the water vapor transmission rate (moisture permeability) of the inorganic layer is preferably 10 0 g / m 2 ⁇ d to 10 -6 g / m 2 ⁇ d, more preferably 10 -1 g / m 2 ⁇ d to 10 -5 g. / M 2 ⁇ d, and more preferably 10 -2 g / m 2 ⁇ d to 10 -4 g / m 2 ⁇ d.
  • the following dry method is preferably used.
  • a gas barrier inorganic layer (hereinafter also referred to as a gas barrier layer) by a dry method, resistance heating vapor deposition, electron beam vapor deposition, induction heat vapor deposition, and vacuum vapor deposition such as an assist method using plasma or ion beam for these.
  • Examples include chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a vacuum vapor deposition method in which a film is formed by a vapor deposition method under vacuum is preferable.
  • the material forming the gas barrier layer is mainly composed of inorganic oxide, inorganic nitride, inorganic oxynitride, inorganic halide, inorganic sulfide, etc.
  • the same material as the composition of the gas barrier layer to be formed It is possible to directly volatilize and deposit it on a substrate or the like.
  • this method when this method is used, the composition changes during volatilization, and as a result, the formed film may not exhibit uniform characteristics. is there.
  • a material having the same composition as the barrier layer formed as a volatilization source is used, oxygen gas in the case of inorganic oxide, nitrogen gas in the case of inorganic nitride, oxygen gas and nitrogen in the case of inorganic oxynitride
  • An inorganic group is used as a volatile source. And this After forming an inorganic group layer, it is an oxygen gas atmosphere in the case of an inorganic oxide, a nitrogen gas atmosphere in the case of an inorganic nitride, and an oxygen gas and a nitrogen gas in the case of an inorganic oxynitride.
  • Examples of the method include a method of reacting an introduced gas with an inorganic layer by holding in a mixed gas atmosphere, a halogen-based gas atmosphere in the case of an inorganic halide, and a sulfur-based gas atmosphere in the case of an inorganic sulfide.
  • 2) or 3) is more preferably used because it is easy to volatilize from a volatile source.
  • the method 2) is more preferably used because the film quality can be easily controlled.
  • the barrier layer is an inorganic oxide
  • the inorganic group is used as a volatilization source, volatilized to form an inorganic group layer, and then left in the air to naturally oxidize the inorganic group.
  • the method is also preferable because it is easy to form.
  • the thickness is preferably 1 ⁇ m to 30 ⁇ m.
  • the thickness is 1 ⁇ m or more, water hardly penetrates into the polyester film during the lapse of time (thermo) and hardly causes hydrolysis, and when it is 30 ⁇ m or less, the thickness of the barrier layer does not become too thick, and the barrier layer The stress does not cause the film to bend.
  • the polyester resin composition of the present invention is particularly suitably used as a polyester film or a polyester sheet for outdoor use that requires weather resistance.
  • a polyester film or polyester sheet for outdoor use for example, a back sheet provided in a solar cell power generation module (a sheet for protecting the back surface that is disposed on the side opposite to the side on which sunlight is incident to protect the solar cell element), lighting Film, agricultural sheet, and the like, and particularly suitable as a back sheet provided in a solar cell power generation module.
  • the solar cell power generation module of the present invention includes a polyester film (including a back sheet) obtained by the above-described method for producing a polyester film of the present invention.
  • a transparent substrate on which sunlight is incident eg, a glass substrate
  • a solar cell element that converts light energy of sunlight into electric energy e.g., a sealing agent that seals the solar cell element, and the like Constructed using.
  • the polyester film obtained by the method for producing a polyester film of the present invention is applied to a back sheet, the back sheet is provided on the side of the solar cell element opposite to the side on which the transparent substrate is disposed. .
  • Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as a group VI compound semiconductor can be applied.
  • Example 1 Production of polyester (solid phase polymerization process) -Polymerization (esterification reaction)- [Step (A)]
  • 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed for 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. Supplied to.
  • an ethylene glycol solution of a citric acid chelate titanium complex (VERTEC AC-420, trade name, manufactured by Johnson Matthey) in which citric acid is coordinated to Ti metal is continuously supplied, and the temperature in the reaction vessel is 250 ° C. with stirring.
  • the reaction was carried out with an average residence time of about 4.3 hours.
  • the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element.
  • the acid value of the obtained oligomer was 600 eq / ton.
  • This reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having an acid value of 200 eq / ton.
  • 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. As a result, an esterification reaction product was obtained.
  • Ti / P (element content ratio of Ti and P) was 0.14.
  • the ethylene glycol solution of trimethyl phosphate was prepared by adding a 25 ° C. trimethyl phosphate solution to a 25 ° C. ethylene glycol solution and stirring at 25 ° C. for 2 hours (phosphorus compound content in the solution: 3 .8%).
  • Step (B) The esterification reaction product obtained in the step (A) is continuously supplied to the first polycondensation reaction tank, and with stirring, the reaction temperature is 270 ° C. and the reaction tank pressure is 20 torr (2.67 ⁇ 10 ⁇ 3 MPa). The polycondensation (transesterification reaction) was carried out with an average residence time of about 1.8 hours.
  • reaction from the first condensation polymerization reactor tank was transferred to a second condensation polymerization reactor tank, stirring in the reaction vessel, the reaction vessel temperature 276 ° C., the reaction vessel pressure 5torr (6.67 ⁇ 10 - 4 MPa), and the reaction (transesterification reaction) was carried out under the condition that the residence time was about 1.2 hours.
  • this reaction product was further transferred from the second double condensation reaction tank to the third triple condensation reaction tank.
  • the reaction vessel internal temperature was 278 ° C. and the reaction vessel internal pressure was 1.5 torr (2.0 ⁇ 10 6 -4 MPa) at a residence time of 1.5 hours (transesterification reaction) to obtain a polycondensate (polyethylene terephthalate (PET)).
  • PET polyethylene terephthalate
  • PET polycondensate
  • the amount of terminal COOH (AV) [eq / ton] and the intrinsic viscosity (IV) [dl / g] were measured.
  • the amount of terminal COOH was determined by titration according to the method described in H. A. Pohl, Anal. Chem. 26 (1954) 2145. Specifically, PET pellet 1 was dissolved in benzyl alcohol at 205 ° C., phenol red indicator was added, titrated with a water / methanol / benzyl alcohol solution of sodium hydroxide, and the amount of terminal COOH was calculated from the appropriate amount.
  • the intrinsic viscosity and the amount of terminal COOH of the PET pellet 1 before solid phase polymerization are shown in “Before solid phase polymerization”, “Resin”, “IV” column and “AV” column of Table 1.
  • a crystallization apparatus having the structure shown in FIG. 1 is prepared, and PET pellets 1 are charged at an input amount of 300 kg / hr from an opening (opening 8) at the top of the crystallization apparatus, and nitrogen at 180 ° C. is supplied to the crystallization apparatus.
  • the gas was supplied at a supply rate of 200 Nm 3 / hr.
  • the wind speed (superficial velocity) of nitrogen gas was 1.0 m / sec.
  • the PET pellet 1 dropped on the lower part of the crystallizer was heated (crystallized) for 4 hours by repeatedly lifting it up to the opening (opening 8) and dropping it with a circulation device built in the crystallizer.
  • crystallinity ⁇ ⁇ (d ⁇ dA) / (dC ⁇ dA) ⁇ ⁇ 100. ] was calculated.
  • the average value of the obtained crystallinity ⁇ is shown in the “resin after crystallization” and “ ⁇ ” columns in Table 1. Further, the distribution ⁇ of the obtained crystallinity ⁇ is shown in the “ ⁇ ” column.
  • the crystallite diameter D of 100 crystallized PET pellets was measured by X-ray diffraction analysis using Cu—K ⁇ 1 line, using the Scherrer equation described above.
  • ULTIMA IV manufactured by Rigaku Corporation was used as the X-ray diffraction analyzer.
  • the average value of the obtained crystallite diameters D is shown in the “resin after crystallization” and “D” columns in Table 1. Further, the distribution ⁇ D of the obtained crystallite diameter D is shown in the “ ⁇ D” column.
  • the crystallized PET pellet 1 was subjected to a heat treatment at 180 ° C. for 60 hours under a reduced pressure of 50 Pa using a rotary vacuum polymerization apparatus. At this time, the amount of decrease in the terminal COOH concentration when the intrinsic viscosity increased by 0.1 was 1.5 eq / ton. The measurement was performed by the following method. Thereafter, nitrogen gas at 25 ° C. was flowed into the vacuum polymerization apparatus, and the PET pellet 1 was cooled to 25 ° C. to obtain a solid-state polymerized PET pellet 1.
  • the melt (melt) of the PET pellet 1 was passed through a gear pump and a filter (pore diameter 20 ⁇ m), and then extruded from a die onto a 20 ° C. cooling roll to obtain an amorphous sheet having a thickness of 3500 ⁇ m.
  • the extruded melt was brought into close contact with the cooling roll using an electrostatic application method.
  • both ends were trimmed by 10 cm. Then, after extruding (knurling) with a width of 10 mm at both ends, it was wound up with a tension of 25 kg / m. The width was 1.5 m and the winding length was 2000 m.
  • the polyester film 1 was produced as described above.
  • the amount of terminal COOH was measured by a titration method according to the method described in H. A. Pohl, Anal. Chem. 26 (1954) 2145. Specifically, 20 measurement positions (points P) are marked in the longitudinal direction of the obtained polyester film 1 as shown in FIG. 2 (the interval between the points P is 100 m), and the point P is the center. The polyester film 1 was cut so that 20 pieces of 1 cm ⁇ 20 cm sample pieces were obtained.
  • the average value of the calculated amount of terminal COOH is shown in the “film”, “AV”, and “average” columns of Table 1. Further, the variation in the amount of terminal COOH was calculated from the calculated average value, maximum value, and minimum value of the terminal COOH amount, and indicated in the “AV” and “variation” columns.
  • Example 2 Example 3
  • Example 1 Example 1
  • Example 2 Example 3
  • Example 3 Example 1
  • the temperature of nitrogen gas in the crystallization of the PET pellet 1 was changed from 180 ° C. to the temperature shown in Table 1
  • the solid phase polymerization conditions of the PET pellet were changed as shown in Table 1.
  • polyester films 2 and 3 were prepared, and physical properties were evaluated. The results of evaluation are shown in Table 1 below.
  • Example 4 In Example 2, instead of PET pellet 1, PET pellet 2 having different IV and AV before solid-phase polymerization was used, and the pressure fluctuation of the extruder in the extrusion molding process was changed as shown in Table 1, and the same manner was performed. A polyester film 4 was produced and evaluated for physical properties. The results of evaluation are shown in Table 1 below. PET pellet 2 was obtained as follows.
  • PET pellet 2 In the production of the PET pellet 1, each temperature of the first polycondensation reaction tank, the second double condensation reaction tank, and the third triple condensation reaction tank in “1. Production of polyester” and “Step (B)” in Example 1 is set. PET pellet 2 was prepared in the same manner except that the temperature was lowered by 5 ° C. The intrinsic viscosity (IV) and terminal COOH amount (AV) before solid phase polymerization of the obtained PET pellet 2 were measured in the same manner as the IV and AV measurements of the PET pellet 1 before solid phase polymerization.
  • IV intrinsic viscosity
  • AV terminal COOH amount
  • Example 5 Example 5 (Examples 5 to 7 and Comparative Example 5)
  • Example 2 except that the superficial velocity of nitrogen gas in the heating (crystallization) of the PET pellet 1 was changed to the velocity shown in Table 1, and the pressure fluctuation of the extruder in the extrusion molding process was changed as shown in Table 1.
  • polyester films 5 to 7 Examples 5 to 7
  • a polyester film 105 Comparative Example 5 were prepared and evaluated for physical properties. The results of evaluation are shown in Table 1 below.
  • Example 8 In Example 3, the PET pellet 1 was heated (crystallized) by a metal contact method using a torus disk preheater manufactured by Hosokawa Micron Corporation, and the solid phase polymerization conditions of the PET pellet were changed as shown in Table 1. Produced a polyester film 8 of Example 8 in the same manner. The heating temperature and heating time by metal contact are shown in Table 1. The obtained polyester film 8 was measured and evaluated in the same manner as the polyester film 1 of Example 1. The results of measurement and evaluation are shown in Table 1 below.
  • Comparative Examples 1 to 4 In Examples 1 to 4, the PET pellets were heated (crystallized) by a metal contact method using a torus disk preheater manufactured by Hosokawa Micron Corporation, and the solid phase polymerization conditions for the PET pellets and the extruder used in the extrusion process
  • the polyester films 101 to 104 of Comparative Examples 1 to 4 were produced in the same manner except that the pressure fluctuation was changed as shown in Table 1.
  • the heating temperature and heating time by metal contact are shown in Table 1.
  • the obtained polyester films 101 to 104 were measured and evaluated in the same manner as the polyester film 1 of Example 1. The results of measurement and evaluation are shown in Table 1 below.
  • Example 9 In Example 2, the polyester film 9 of Example 9 was produced in the same manner except that polybutylene terephthalate (PBT) pellets were used instead of the PET pellets 1, and physical properties were evaluated. The results of evaluation are shown in Table 1 below. PBT pellets were obtained as follows.
  • PET1 shown in “solid phase polymerization”
  • resin and “seed” indicates that PET pellet 1 is used as a pellet
  • PET2 uses PET pellet 2 as a pellet
  • PBT indicates that PBT pellets are used as pellets.
  • the crystallinity distribution ⁇ of the polyester after crystallization is large and the pressure fluctuation in the extruder is small compared to the comparative example, and the terminal COOH amount of the obtained polyester film is small. And variations in half elongation time at break are small. Therefore, when the crystallinity distribution ⁇ of the polyester after crystallization is larger in the range of 15% or less, pressure fluctuation in the extruder is suppressed, the amount of terminal COOH of the polyester is reduced, and variation in the amount of terminal COOH is reduced. It was found that variations in the half elongation time at break were suppressed.
  • Example 10 4 Production of polyester film for solar cell (back sheet for solar cell) Using the polyester films 1 to 9 of Examples 1 to 9 and the polyester films 101 to 105 of Comparative Examples 1 to 5 produced above, Back sheets 1 to 9 and 101 to 105 included in the battery were produced. Specifically, it is as follows.
  • the reflective layer-forming coating solution obtained above is applied to a sample film with a bar coater and dried at 180 ° C. for 1 minute to form a reflective layer (white layer) with a titanium dioxide coating amount of 6.5 g / m 2. did.
  • the polyester film is provided with the following (iii) undercoat layer, (iv) barrier layer, and (v) antifouling layer on the side opposite to the side where the reflective layer and the easy-adhesion layer of the polyester film are formed. Coated sequentially from the side.
  • Undercoat layer Various components having the following composition are mixed to prepare a coating solution for an undercoat layer, this coating solution is applied to a polyester film, dried at 180 ° C. for 1 minute, and an undercoat layer (dry coating amount: about 0.1 g / m 2 ) was formed.
  • (V) Antifouling Layer As shown below, a coating solution for forming the first and second antifouling layers is prepared, and the first antifouling layer coating solution and the second antifouling layer are formed on the barrier layer. The coating solution was applied in the order, and a two-layer antifouling layer was applied.
  • ⁇ First antifouling layer> Preparation of coating solution for first antifouling layer- Components in the following composition were mixed to prepare a first antifouling layer coating solution.
  • ⁇ Composition of coating solution> ⁇ Ceranate WSA1070 (trade name, manufactured by DIC Corporation) ⁇ ⁇ ⁇ 45.9 parts ⁇ Oxazoline compound (crosslinking agent) ⁇ ⁇ ⁇ ⁇ ⁇ 7.7 parts (Epocross WS-700, trade name, manufactured by Nippon Shokubai Co., Ltd.) , Solid content: 25%) ⁇ Polyoxyalkylene alkyl ether ... 2.0 parts (Naroacty CL95, trade name, manufactured by Sanyo Chemical Industries, solid content: 1%) ⁇ Pigment dispersion used in the reflective layer: 33.0 parts ⁇ Distilled water: 11.4 parts
  • the obtained coating solution was coated on the barrier layer so that the binder coating amount was 3.0 g / m 2 and dried at 180 ° C. for 1 minute to form a first antifouling layer.
  • Second antifouling layer The prepared coating solution for the second antifouling layer was applied on the first antifouling layer formed on the barrier layer so that the binder coating amount was 2.0 g / m 2 , and the mixture was applied at 180 ° C. for 1 minute. A second antifouling layer was formed by drying.
  • a back sheet having a reflective layer and an easy adhesion layer on one side of the polyester film and having an undercoat layer, a barrier layer, and an antifouling layer on the other side was produced.
  • the solar cell backsheets 1 to 9 of the examples are configured using the polyester films 1 to 9 of the examples with small variations in the half elongation time at break, the backsheets 101 to 105 for the solar cells of the comparative examples are used. In comparison, it showed uniform hydrolysis resistance.
  • Example 11 5 Production of Solar Cell Power Generation Module Using the backsheets 1 to 9 and the backsheets 101 to 105 produced as described above, they are bonded to a transparent filler so as to have the structure shown in FIG. 1 of JP-A-2009-158952. Solar cell power generation modules 1 to 9 and 101 to 105 were produced. At this time, it stuck so that the easily-adhesive layer of a backsheet might contact the transparent filler which embeds a solar cell element.
  • the solar cell power generation modules 1 to 9 of the examples are configured using the polyester films 1 to 9 of the examples with small variations in the half elongation time at break, compared with the solar cell power generation modules 101 to 105 of the comparative examples, The power generation performance can be obtained stably over a long period of time.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention porte sur un procédé pour la production d'un film de polyester comprenant : une étape de polymérisation à l'état solide servant à effectuer une polymérisation à l'état solide par introduction de polyester, ayant une distribution de la cristallinité (Δρ) satisfaisant à la relation 3 % < Δρ ≤ 15 %, dans un réacteur ; et une étape de moulage par extrusion servant à mouler par extrusion le polyester soumis à la polymérisation à l'état solide en une forme de film.
PCT/JP2011/077401 2010-12-15 2011-11-28 Procédé pour la production de film de polyester, film de polyester pour photopile et module de production d'énergie électrique photovoltaïque Ceased WO2012081385A1 (fr)

Priority Applications (1)

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CN201180059659.9A CN103260847B (zh) 2010-12-15 2011-11-28 聚酯膜的制造方法、太阳能电池用聚酯膜、以及太阳能电池发电模块

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JP2010279605 2010-12-15
JP2010-279605 2010-12-15

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WO2012081385A1 true WO2012081385A1 (fr) 2012-06-21

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JP (1) JP5836775B2 (fr)
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WO2014021095A1 (fr) * 2012-08-01 2014-02-06 東レ株式会社 Film de polyester durable, son procédé de production, film pour l'étanchéité d'une cellule solaire produit en utilisant ce dernier et cellule solaire
JP2021066881A (ja) * 2019-10-28 2021-04-30 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． ポリエステルフィルムおよびこれを含むフレキシブルディスプレイ装置
US11915167B2 (en) 2020-08-12 2024-02-27 State Farm Mutual Automobile Insurance Company Claim analysis based on candidate functions

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US11915167B2 (en) 2020-08-12 2024-02-27 State Farm Mutual Automobile Insurance Company Claim analysis based on candidate functions

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CN103260847B (zh) 2016-09-14

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