WO2010110119A1 - 太陽電池用ポリエステルフィルム、それを用いた太陽電池バックシート、および太陽電池 - Google Patents
太陽電池用ポリエステルフィルム、それを用いた太陽電池バックシート、および太陽電池 Download PDFInfo
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- WO2010110119A1 WO2010110119A1 PCT/JP2010/054424 JP2010054424W WO2010110119A1 WO 2010110119 A1 WO2010110119 A1 WO 2010110119A1 JP 2010054424 W JP2010054424 W JP 2010054424W WO 2010110119 A1 WO2010110119 A1 WO 2010110119A1
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- Prior art keywords
- polyester film
- film
- solar cell
- polyester
- solar
- Prior art date
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Definitions
- the present invention relates to a polyester film for solar cells excellent in heat resistance and hydrolysis resistance, a solar cell back sheet using the same, and a solar cell using the same.
- JP-A-11-261085 Japanese Patent Laid-Open No. 11-186575 JP 2006-270025 A
- the present invention provides a polyester film for solar cells that has both heat resistance and hydrolysis resistance, a solar cell backsheet using the same, and a solar cell.
- the present invention relates to a polyester film for solar cells having a carboxyl end group concentration of 13 eq / ton or less and a minute endothermic peak temperature Tmeta (° C.) determined by differential scanning calorimetry (DSC) of 220 ° C. or less. It is a solar cell backsheet using this, and a solar cell.
- the present invention it is possible to provide a polyester film for solar cells that has both heat resistance and hydrolysis resistance, a solar cell backsheet using the polyester film, and a solar cell. Further, by using it, it becomes possible to improve the durability and thinning of the solar cell backsheet, and to improve the durability and thinning of the solar cell.
- the film of the present invention needs to be a polyester film.
- the polyester film of the present invention it is preferable from the viewpoint of heat resistance and mechanical properties that the ethylene terephthalate component is 90 mol% or more based on the ester component of the polyester, but as other copolymer components, various dicarboxylic acids or ester-forming derivatives thereof and Diols may be copolymerized.
- Examples of the copolymerizable dicarboxylic acid component include isophthalic acid, phthalic acid, 1,4- ⁇ naphthalene dicarboxylic acid, 1,5- naphthalene dicarboxylic acid, 2,6- naphthalene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid and the like can be mentioned.
- Examples of the alicyclic dicarboxylic acid component that can be copolymerized include 1,4-cyclohexanedicarboxylic acid.
- diol component examples include ethylene glycol, 1,2-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4'- ⁇ -hydroxyethoxyphenyl) propane, etc. And aliphatic, alicyclic, and aromatic diols. These components may be used alone or in combination of two or more.
- the melting point of the polyester preferably used is preferably 250 ° C. or higher in view of heat resistance, and preferably 300 ° C. or lower in terms of productivity. If it is in this range, other components may be copolymerized or blended.
- Various known additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, and organic particles may be added to the polyester.
- inorganic particles and organic particles are effective for imparting easy lubricity to the film surface and enhancing the handleability of the film.
- Polyester can be produced according to conventionally known polyester production methods. That is, it is produced by using a dialkyl ester as an acid component, transesterifying it with a diol component, and then heating the product of this reaction under reduced pressure to perform polycondensation while removing excess diol component. can do. Moreover, it can also manufacture by a conventionally well-known direct polymerization method, using dicarboxylic acid as an acid component. As the reaction catalyst, conventionally known titanium compounds, lithium compounds, calcium compounds, magnesium compounds, antimony compounds, germanium compounds and the like can be used. The polyester thus obtained can be further increased in the degree of polymerization by subjecting it to solid phase polymerization, and the carboxyl end group concentration can be reduced. The solid phase polymerization is carried out in a dryer at a temperature of 200 ° C. to 250 ° C. under a reduced pressure of 1 torr or less or under a nitrogen stream.
- the intrinsic viscosity of the polyester film is preferably in the range of 0.6 to 1.2 dl / g. More preferably, the dl / g is 0.65 to 0.80, and still more preferably 0.70 to 0.80 dl / g. In order to improve the hydrolysis resistance, it is preferable to increase the intrinsic viscosity. However, when the intrinsic viscosity exceeds 1.2 dl / g, it is necessary to lengthen the solid phase polymerization time when producing the polyester resin, and the cost is remarkably high. Therefore, it may not be preferable.
- the carboxyl end group concentration of the polyester film needs to be in the range of 13 eq (equivalent) / ton or less.
- it is 12 eq / ton or less, More preferably, it is 8 eq / ton or less, Most preferably, it is 5 eq / ton or less.
- the lower limit is not particularly limited, but 0 eq / ton is the theoretical lower limit.
- a polyester resin having a low carboxyl end group concentration As a raw material polyester resin.
- it can be achieved by increasing the solid phase polymerization time during the production of the polyester resin.
- an end-blocking agent in order to make the carboxyl end group concentration within the above preferable range, it is also one of preferable embodiments to use an end-blocking agent.
- the terminal blocking agent include carbodiimide compounds, oxazoline compounds, epoxy compounds, carbonate compounds and the like. When added together with the polyester resin during film formation, the effect is higher.
- a carbodiimide compound is used, and the content is 0.3 to 5% by weight based on the entire polyester film.
- solid phase polymerization and a terminal blocking agent may be used simultaneously.
- the film of the present invention needs to have a minute endothermic peak temperature Tmeta (° C.) determined by differential scanning calorimetry (DSC) in a range of 220 ° C. or lower in order to satisfy sufficient hydrolysis resistance.
- Tmeta minute endothermic peak temperature
- DSC differential scanning calorimetry
- it is 205 degrees C or less, More preferably, it is 195 degrees C or less.
- the lower limit is not particularly limited, but it is preferably 150 ° C. or higher because the heat shrinkage rate is remarkably increased below 150 ° C. More preferably, it is 160 ° C. or higher.
- the heat treatment temperature is preferably 220 ° C. or lower, although it varies depending on the thickness of the film during film formation and the film formation speed. The details of the film forming method and the heat treatment step of the film of the present invention will be described later.
- the thermal shrinkage rate of the polyester film for solar cells is large, the polyester film for solar cells or the solar cell backsheet shrinks during the manufacturing process of solar cells, and the solar cell unit The whole may be distorted and cracked. Therefore, the one where the heat shrinkage rate of the film of this invention is small is preferable. Specifically, it is preferable that the thermal shrinkage rate at 150 ° C. for 30 minutes in the longitudinal direction (MD) and the orthogonal direction (TD) (also referred to as the width direction) of the film is 0.6% or less. More preferably, it is 0.4% or less, More preferably, it is 0.2% or less.
- the heat shrinkage rate is preferably ⁇ 0.5% or more.
- the thermal shrinkage rate may increase. Therefore, in order to make the heat shrinkage rate within the above preferable range, it is preferable to employ either of the following methods (1) or (2) (of course, the methods (1) and (2) are used in combination). Also good).
- Method (1) In the heat treatment step, the film is heat-treated and simultaneously contracted by 0.5 to 10% in each of the film MD direction and the TD direction.
- Method (2) A method in which a film after film formation is introduced into another apparatus (for example, an oven) and subjected to heat treatment offline.
- a preferable heating temperature is 150 to 220 ° C.
- a preferable heating time is 10 to 60 seconds.
- the plane orientation coefficient of the film is preferably 0.130 or more. More preferably, it is 0.165 or more, More preferably, it is 0.168 or more, More preferably, it is 0.170 or more, Most preferably, it is 0.174 or more. This is because the hydrolysis resistance can be further improved.
- the plane orientation coefficient referred to in the present invention is obtained from the following formula (A) using an Abbe refractometer.
- Plane orientation coefficient (nMD + nTD) / 2 ⁇ nZD (A)
- nMD represents the refractive index in the longitudinal direction (MD) of the film
- nTD represents the refractive index in the perpendicular direction (TD) of the film
- nZD represents the refractive index in the film thickness direction.
- the draw ratio is adjusted to 2.5 to 6.0 times in both the longitudinal direction (MD) of the film and the orthogonal direction (TD) of the film.
- the plane orientation coefficient of the film In order to set the plane orientation coefficient of the film to 0.165 or more, It is preferable to adjust the draw ratio in the MD and TD directions to 3.0 to 5.0 times, respectively.
- the upper limit of the plane orientation coefficient of the film is not particularly limited, but the film forming stability deteriorates as the draw ratio is increased to increase the plane orientation coefficient. It is preferably 200 or less, more preferably 0.185 or less.
- the minute endothermic peak temperature Tmeta (° C.) obtained by differential scanning calorimetry (DSC) and the plane orientation coefficient B2 of the film satisfy the following formula (B).
- the present invention it is preferable to add a compound that suppresses hydrolysis decomposition into the film.
- the phosphorus compound it is preferable to use one or more phosphorus compounds selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, methyl esters, ethyl esters, phenyl esters, half esters and other derivatives thereof.
- phosphoric acid, phosphorous acid, phosphonic acid methyl ester, ethyl ester, and phenyl ester are particularly preferable.
- a method of containing the phosphorus compound it is preferable to add the phosphorus compound when manufacturing the polyester raw material chip.
- the average reflectance at a wavelength of 400 to 700 nm on at least one film surface is 80% or more. More preferably, it is 85% or more, and particularly preferably 90% or more.
- Examples of the method of setting the average reflectance at a wavelength of 400 to 700 nm to 80% or more include a method of adding inorganic particles to the film and a method of creating voids in the polyester film by adding polyester and an incompatible resin. is there.
- Examples of the inorganic particles suitably used in the former include, for example, wet and dry silica, colloidal silica, calcium carbonate, aluminum silicate, calcium phosphate, alumina, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide (zinc white), and antimony oxide.
- the content of the inorganic particles is 5 to 55% by weight, preferably 5 to 35% by weight, based on the entire polyester film. When the content is less than the above range, the film has poor reflectivity.
- the film of the present invention preferably has two or more polyester layers.
- any one of the polyester layers may contain the inorganic particles in an amount of 5 to 55% by weight based on the polyester layer. More preferably, it is contained in an amount of 5 to 35% by weight.
- the content of the inorganic particles in the other polyester layer is not particularly limited, but productivity can be improved as the content is reduced.
- polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polystyrene resins, polyacrylate resins, polycarbonate resins, polyacrylonitrile resins, polyphenylene sulfides are used. Resins and fluororesins are preferably used.
- These incompatible resins may be homopolymers or copolymers, and two or more incompatible resins may be used in combination.
- polyolefin resins such as polypropylene and polymethylpentene having a low surface tension are preferable, and polymethylpentene is most preferable.
- the polymethylpentene Since the polymethylpentene has a relatively large difference in surface tension from polyester and a high melting point, it has a feature that the effect of forming cavities per added amount is large, and is particularly preferable as an incompatible resin.
- an incompatible resin When an incompatible resin is contained, the amount thereof is 0.5 to 20% by weight, preferably 0.5 to 10% by weight, based on the entire polyester film.
- the content When the content is less than the above range, the film has poor reflectivity. Conversely, when the content is more than the above range, the apparent density of the entire film is too low, so that the film is broken during stretching. It is easy and productivity may be reduced.
- the present invention in order to further improve the hydrolysis resistance, it is preferable to have at least two polyester layers.
- the polyester film for a solar cell of the present invention preferably has an average elongation retention rate of 50% or more after standing for 48 hours under conditions of 125 ° C. and humidity 100%. More preferably, it is 55% or more, more preferably 60% or more, particularly preferably 65% or more, and most preferably 70% or more. If the average elongation retention rate is less than 50%, the mechanical strength decreases when used for a long period of time, and as a result, during use of the solar cell having the back sheet using the solar cell, some impact is applied from the outside. Since the back sheet may be broken when it is added to (for example, when falling rocks or the like hit the solar cell), it is not preferable. In the polyester film for solar cells of the present invention, the durability of the mechanical strength of the back sheet during long-term use can be increased by setting the average elongation retention to 50% or more.
- the polyester film for solar cells of the present invention preferably has an average elongation retention rate of 10% or more after being left for 72 hours under conditions of 125 ° C. and 100% humidity.
- the average elongation retention test after 72 hours under the conditions of 125 ° C. and 100% humidity is a more severe acceleration test than the average elongation retention test after 48 hours. Therefore, in applications that require long-term durability, such as solar cell applications, the average elongation retention after 72 hours is used as an evaluation index.
- the average elongation retention after 72 hours is more preferably 20% or more, still more preferably 30% or more, particularly preferably 40% or more, and most preferably 50% or more.
- the back sheet may be broken when an impact is applied to the solar cell from the outside during use (for example, when a falling rock hits the solar cell).
- the average elongation retention after standing for 48 hours under conditions of 125 ° C. and 100% humidity is preferably 50% or more.
- the average elongation retention determined by the above method is 55% or more, more preferably 60% or more, particularly preferably 65% or more, and most preferably 70% or more.
- the thickness ratio of the polyester film for solar cells of the present invention is preferably 5 to 100% with respect to the total thickness of the back sheet. That is, in order to further increase the average elongation retention rate, it is preferable to increase the thickness of the solar cell polyester film of the present invention.
- PET polyethylene terephthalate
- the dried polyester resin is supplied to a single-screw or twin-screw extruder, melt-extruded, and discharged from a T-die onto a cooling drum in a sheet form to obtain an unstretched sheet.
- the unstretched film is stretched in the longitudinal direction, and then stretched in the width direction, or after being stretched in the width direction and then stretched in the longitudinal direction, or the longitudinal direction and the width direction of the film.
- the film is stretched by a simultaneous biaxial stretching method that stretches the films almost simultaneously.
- heat treatment of the film is performed.
- the heat treatment can be performed by any conventionally known method such as in a tenter, a heating oven, or on a heated roll. This heat treatment is generally performed at a temperature lower than the melting point of the polyester.
- the heat treatment temperature is preferably 220 ° C. or lower in order to set Tmeta (° C.) to 220 ° C. or lower. More preferably, it is 210 degrees C or less, More preferably, it is 200 degrees C or less, Most preferably, it is 190 degrees C or less.
- the lower limit of the heat treatment temperature is not particularly limited, it is preferably 150 ° C. or higher, more preferably 160 ° C. or higher because the heat shrinkage rate is remarkably increased below 150 ° C.
- the heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. And the film which heat-treated in this way is wound up, and the film of this invention is obtained.
- the heat treatment temperature of the heat treatment step that is the highest temperature is 220 ° C. or less. More preferably, it is 210 degrees C or less, More preferably, it is 200 degrees C or less, Most preferably, it is 190 degrees C or less.
- Carboxyl end group concentration film 0.5 g was dissolved in o-cresol and subjected to potentiometric titration using potassium hydroxide to determine the carboxyl end group concentration.
- Tmeta Minute endothermic peak temperature Tmeta (° C.) determined by differential scanning calorimetry (DSC) Slight endothermic peak temperature Tmeta (° C.) was measured using a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Electronics Industry Co., Ltd. according to JIS K7122-1987 (referred to JIS Handbook 1999 edition). Was measured using a disk session “SSC / 5200”. 5 mg of the film was weighed on a sample pan, and the temperature was increased from 25 ° C. to 300 ° C. at a rate of temperature increase of 20 ° C./min. In the obtained differential scanning calorimetry chart, Tmeta (° C.) was defined as the minute endothermic peak temperature before the crystal melting peak. When it was difficult to observe a minute endothermic peak, the peak was read by enlarging the vicinity of the peak in the data analysis section.
- the area is also obtained for 17 points at 240 ° C.
- the endothermic amount of the minute peak is usually 0.2 to 5.0 J / g
- data having an area of 0.2 J / g or more and 5.0 J / g or less is treated as effective data.
- the peak temperature of the endothermic peak in the temperature region of the data that is effective data and indicates the largest area is defined as Tmeta (° C.). If there is no valid data, Tmeta (° C.) is assumed to be none.
- nMD represents the refractive index in the longitudinal direction (MD) of the film
- nTD represents the refractive index in the perpendicular direction (TD) of the film
- nZD represents the refractive index in the film thickness direction.
- An integrating sphere attachment device (ISR2200 manufactured by Shimadzu Corporation) is attached to an average reflectance spectrophotometer (Shimadzu Corporation UV2450) having a wavelength of 400 to 700 nm, barium sulfate is used as a standard plate, and the standard plate is 100 It is a value obtained by measuring the relative reflectance in%. At wavelengths of 400 to 700 nm, the relative reflectance for each wavelength of 0.5 nm is measured, and the average value thereof is taken as the average reflectance.
- the sample was cut into a size of 1 cm ⁇ 20 cm, and treated for 48 hours under conditions of 125 ° C. and 100% humidity using an advanced acceleration life test apparatus EHS-221MD manufactured by Espec Co., Ltd.
- EHS-221MD manufactured by Espec Co., Ltd.
- ASTM-D882-97 the elongation at break (after treatment) when the sample was pulled at 5 cm between chucks and at a pulling speed of 300 mm / min. It was measured.
- the measurement was performed on five samples, and the elongation at break (after treatment) was A1 based on the average value.
- the elongation retention was calculated by the following formula (1).
- Elongation retention (%) A1 / A0 ⁇ 100 (1)
- the average elongation retention was calculated by the following formula (2).
- Average elongation retention (%) (MD elongation retention + TD elongation retention) / 2 (2)
- Hirayama Seisakusho High Acceleration Life Test Equipment (HAST equipment) Even if measured using PC-304R8D, the value is the same as the value measured using EHS Corp. Advanced Acceleration Life Test Equipment EHS-221MD Therefore, measurement may be performed using the Hirayama Seisakusho High Acceleration Life Test Device (HAST device) PC-304R8D.
- the sample was cut into a size of 1 cm ⁇ 20 cm, and subjected to treatment for 72 hours under conditions of 125 ° C. and 100% humidity using Hirayama Seisakusho Co., Ltd., High Acceleration Life Test Device (HAST device) PC-304R8D
- HAST device High Acceleration Life Test Device
- ASTM-D882 (1999) -97 referred to 1999 edition ANNUAL BOOK OF ASTMSTANDARDS
- Example 1 (Raw material PET-1) To a mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.08 part by weight of calcium acetate and 0.03 part by weight of antimony trioxide were added, and the mixture was heated and heated by a conventional method to carry out a transesterification reaction. Subsequently, 0.16 part by weight of lithium acetate and 0.11 part by weight of trimethyl phosphate are added to the transesterification reaction product, and then transferred to a polymerization reaction tank. Next, the reaction system was gradually depressurized while being heated and heated, and polymerization was performed at 290 ° C.
- polyester polyethylene terephthalate
- the polyester is cut into rectangular parallelepipeds of 2 mm ⁇ 4 mm ⁇ 4 mm on each side, and heat-treated at 230 ° C. for 20 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus, with an intrinsic viscosity [ ⁇ ] of 0.79, carboxyl end groups
- a polyester having a concentration of 10.5 eq / ton was obtained.
- the raw material PET-1 obtained above was dried under reduced pressure for 2 hours under the conditions of a temperature of 180 ° C. and a vacuum degree of 0.5 mmHg, supplied to an extruder heated to 295 ° C., and filtered with a 50 ⁇ m cut filter. Later, it was introduced into the T-die base. Next, from the inside of the T die die, it is extruded into a sheet shape to form a molten single layer sheet. The molten single layer sheet is closely cooled and solidified by electrostatic application on a drum maintained at a surface temperature of 20 ° C. A layer film was obtained.
- the unstretched single layer film is preheated with a roll group heated to a temperature of 85 ° C., and then stretched at a stretch ratio of 3.3 times in the longitudinal direction (MD) using a heated roll having a temperature of 90 ° C. And cooled with a roll group having a temperature of 25 ° C. to obtain a uniaxially stretched film (uniaxially oriented film).
- the both ends of the obtained uniaxially stretched film are held by clips while being guided to a preheating zone at a temperature of 95 ° C. in the tenter, and subsequently continuously heated at a temperature of 105 ° C. in a direction perpendicular to the longitudinal direction (TD).
- the film was stretched at a stretch ratio of 6 times.
- the solar cell backsheet was created with the following method.
- the film of the present invention having a thickness of 125 ⁇ m obtained above is used as the first layer.
- Example 2-4 Except having set it as the film forming conditions shown to a table
- Example 5 (Raw material PET-2) The intrinsic viscosity [ ⁇ ] was 0.82 and the carboxyl end group concentration was 8.5 eq / ton in the same manner as the raw material PET-1, except that it was heat-treated at 230 ° C. for 40 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. Polyester (polyethylene terephthalate) was obtained.
- a polyester film was obtained in the same manner as in Example 1 except that the raw material PET-2 was used as a raw material. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 6-8 Except having set it as the film forming conditions shown to a table
- Example 9 (Raw material PET-3) 10 parts by weight of Stabaxol P100 (polycarbodiimide) manufactured by Rhein Chemie was added to 90 parts by weight of the raw material PET-1 and compounded. This compound product is used as raw material PET-3.
- a film was formed in the same manner as in Example 1 except that 90 parts by weight of the raw material PET-1 and 10 parts by weight of the raw material PET-3 (corresponding to 1 part by weight of polycarbodiimide) were used as the raw material.
- a polyester film was obtained. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Examples 10-12 A polyester film was obtained in the same manner as in Example 9 except that the film forming conditions shown in the table were used. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Examples 13-14 A polyester film was obtained in the same manner as in Example 6 except that the film forming conditions shown in the table were used. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 15 Intrinsic viscosity [triggered by the same method as the raw material PET-1 except that the amount of trimethyl phosphate added was 0.13 parts by weight and heat treatment was performed at 230 ° C. for 40 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. A polyester (polyethylene terephthalate) having [ ⁇ ] 0.82 and a carboxyl end group concentration of 8.5 eq / ton was obtained.
- a polyester film was obtained in the same manner as in Example 13 except that the above-mentioned PET-4 was used as a raw material. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 16 Intrinsic viscosity [in the same manner as the raw material PET-1, except that the amount of trimethyl phosphate added was 0.25 parts by weight, and heat treatment was performed at 230 ° C. for 40 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. A polyester (polyethylene terephthalate) having [ ⁇ ] 0.82 and a carboxyl end group concentration of 8.5 eq / ton was obtained.
- a polyester film was obtained in the same manner as in Example 13 except that the above-described PET-5 was used as a raw material. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 17 The raw material PET-5 was dried under reduced pressure for 2 hours under the conditions of 180 ° C. and 0.5 mmHg vacuum, supplied to an extruder heated to 295 ° C., and filtered with a 50 ⁇ m cut filter. Introduced into the base. Next, from the inside of the T die die, it is extruded into a sheet shape to form a molten single layer sheet. The molten single layer sheet is closely cooled and solidified by electrostatic application on a drum maintained at a surface temperature of 20 ° C. A layer film was obtained.
- the unstretched monolayer film was preheated with a roll group heated to a temperature of 85 ° C., and then stretched 3.5 times in the longitudinal direction (MD) using a heating roll having a temperature of 90 ° C.
- a uniaxially stretched film was obtained by cooling with a roll group at a temperature of 5 mm.
- the obtained uniaxially stretched film is guided to a preheating zone at a temperature of 95 ° C. in the tenter while holding both ends of the film with clips, and then continuously in a heating zone at a temperature of 105 ° C. in a direction perpendicular to the longitudinal direction (TD). Stretched by 0.
- a heat treatment for 20 seconds was performed at a temperature of 205 ° C. (first heat treatment temperature) in a heat treatment zone in the tenter.
- the film is relaxed at a relaxation rate of 3% in the width direction (TD), and by 1.5% relaxation in the longitudinal direction (MD) by reducing the clip interval of the tenter. Relaxed at a rate.
- After cooling uniformly to 25 degreeC it wound up and obtained the polyester film.
- the evaluation results are shown in the table. As a result of evaluating the hydrolysis resistance with this film, the film was good.
- Example 18 A polyester film was obtained in the same manner as in Example 17 except that the relaxation rate in the longitudinal direction (MD) was 2.0% by reducing the clip interval of the tenter. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 19 A composite film forming apparatus having an extruder (a) and an extruder (b) was used.
- the polymer from the extruder (a) and the polymer from the extruder (b) are merged so as to be laminated in two layers, and then co-extruded into a sheet to melt-laminated sheet It was.
- the extrusion amount of both extruders was controlled, and the composite ratio [extruder (a) layer / ([extruder (a) layer + [extruder (b) layer]]) was 12%.
- the melt-laminated sheet extruded into a sheet form from the inside of the T die die was closely cooled and solidified by an electrostatic application method on a drum maintained at a surface temperature of 20 ° C. to obtain an unstretched laminated film.
- the unstretched film was preheated with a roll group heated to a temperature of 85 ° C., and then stretched 3.5 times in the longitudinal direction (MD) using a heating roll having a temperature of 90 ° C., and a temperature of 25 ° C.
- a uniaxially stretched film was obtained by cooling with a roll group.
- the obtained uniaxially stretched film is guided to a preheating zone at a temperature of 95 ° C.
- a solar battery back sheet was created by the following method.
- the two-layer laminated film obtained above is used as the first layer.
- 90 parts by weight of "Takelac (registered trademark)" A310 (manufactured by Mitsui Takeda Chemical Co., Ltd.) and "Takenate (registered trademark)” A3 (manufactured by Mitsui Takeda Chemical Co., Ltd.) as the adhesive layer are applied to the surface of the layer (b)
- a 12 ⁇ m-thick barrier locks “HGTS” alumina-deposited PET film manufactured by Toray Film Processing Co., Ltd.
- HGTS alumina-deposited PET film manufactured by Toray Film Processing Co., Ltd.
- Example 20 30 parts by weight of titanium oxide (surface untreated, rutile type) having an average particle size of 0.2 ⁇ m, 0.15 parts by weight of fluorescent brightening agent “OB-1” (manufactured by Eastman Kodak Company), and raw material PET-5 Except that the mixture of 69.85 parts by weight was dried under reduced pressure for 2 hours under the conditions of a temperature of 180 ° C. and a vacuum degree of 0.5 mmHg, and then supplied to the extruder (a) side. A film was formed in the same manner as in 19 to obtain a polyester film. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- OB-1 fluorescent brightening agent
- Example 21 (Raw material PET-6) Polyester with intrinsic viscosity [ ⁇ ] of 0.65 and carboxyl end group concentration of 18 eq / ton using the same process as PET-1, except that it was heat-treated at 230 ° C. for 5 hours under reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. (Polyethylene terephthalate) was obtained.
- Polyester was formed by the same method as in Example 6 except that 90 parts by weight of raw material PET-6 and 10 parts by weight of raw material PET-7 (corresponding to 1 part by weight of polycarbodiimide) were used as raw materials. A film was obtained. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 22 (Raw material PET-8) In the same manner as the raw material PET-1, except that heat treatment was performed at 230 ° C. for 100 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus, intrinsic viscosity [ ⁇ ] 1.2, carboxyl end group concentration 8.0 eq / ton Of polyester was obtained.
- a polyester film was obtained in the same manner as in Example 6 except that the raw material PET-8 was used as the raw material. The results of evaluating the obtained film are shown in the table. When the hydrolysis resistance of this film was evaluated, it was good.
- Example 23 The same method as in Example 6 was performed to obtain a film having a thickness of 125 ⁇ m. The evaluation results are shown in the table.
- a solar battery back sheet was created by the following method.
- the film having a thickness of 125 ⁇ m obtained above is used as the first layer.
- an adhesive layer similar to the above-mentioned adhesive layer is applied on the second layer, and a biaxially oriented polyester film “Lumirror (registered trademark)” S10 (250 ⁇ m thick) is formed as a third layer on the adhesive layer. Toray Industries, Inc.). Further, an adhesive layer similar to the above-mentioned adhesive layer is applied on the third layer, and a biaxially oriented polyester film “Lumirror (registered trademark)” E20 (manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m is applied on the adhesive layer. A back sheet having a total thickness of 437 ⁇ m was formed by lamination. The evaluation results are shown in the table. As a result of evaluating the hydrolysis resistance of this back sheet, it was good.
- Example 24 A polyester film was obtained by the same production method as in Example 6 except that the thickness of the polyester film was 50 ⁇ m. The results of evaluating the film are shown in the table.
- the solar cell backsheet was created with the following method.
- the film having a thickness of 50 ⁇ m obtained above is used as the first layer.
- 90 parts by weight of “Takelac (registered trademark)” A310 (manufactured by Mitsui Takeda Chemical Co., Ltd.) and “Takenate (registered trademark)” A3 (manufactured by Mitsui Takeda Chemical Co., Ltd.) were applied to the first layer as an adhesive layer.
- HGTS alumina vapor-deposited PET film manufactured by Toray Film Processing Co., Ltd.
- HGTS alumina vapor-deposited PET film manufactured by Toray Film Processing Co., Ltd.
- an adhesive layer similar to the above-described adhesive layer is applied on the second layer, and a 250 ⁇ m thick biaxially oriented polyester film “Lumirror (registered trademark)” S10 (Toray ( )).
- an adhesive layer similar to the above-mentioned adhesive layer is applied on the third layer, and a biaxially oriented polyester film “Lumirror (registered trademark)” E20 (manufactured by Toray Industries, Inc.) having a thickness of 188 ⁇ m is applied on the adhesive layer.
- a back sheet having a total thickness of 500 ⁇ m was formed by lamination. The evaluation results are shown in Table 1. As a result of evaluating the hydrolysis resistance of this back sheet, it was good.
- Examples 25-42 Except having set it as the film forming conditions shown to a table
- Comparative Example 1 (Raw material PET-9) To a mixture of 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol, 0.08 part of calcium acetate and 0.03 part of antimony trioxide were added, and the mixture was heated and heated in a conventional manner to conduct a transesterification reaction. Next, 0.16 part of lithium acetate and 0.11 part of trimethyl phosphate are added to the transesterification product, and then transferred to a polymerization reaction tank. Next, the reaction system was gradually depressurized while being heated and heated, and polymerization was conducted at 290 ° C. under a reduced pressure of 1 mmHg by a conventional method to obtain a polyester having an intrinsic viscosity [ ⁇ ] of 0.52.
- the polyester is cut into 2 mm ⁇ 4 mm ⁇ 4 mm rectangular parallelepipeds and heat-treated at 230 ° C. for 8 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus, with an intrinsic viscosity [ ⁇ ] of 0.74, carboxyl end groups.
- a polyester having a concentration of 13 eq / ton was obtained.
- a film having a thickness of 125 ⁇ m was obtained in the same manner as in Example 1 except that the raw material PET-9 was used as a raw material. The evaluation results are shown in the table. When this film was evaluated, it was found to be inferior in hydrolysis resistance.
- a back sheet having a thickness of 187 ⁇ m was formed in the same manner as in Example 1. The evaluation results are shown in the table. When this back sheet was evaluated, it was found to be inferior in hydrolysis resistance.
- Comparative Example 2 Except having set it as the film forming conditions shown to a table
- a back sheet was prepared by the method of Example 1 to obtain a back sheet having a thickness of 187 ⁇ m.
- the evaluation results are shown in Table 1. In particular, the hydrolysis resistance was poor.
- Comparative Example 3 Except having set it as the film forming conditions shown to a table
- a back sheet was prepared by the method of Example 1 to obtain a back sheet having a thickness of 187 ⁇ m.
- the evaluation results are shown in Table 1. In particular, the hydrolysis resistance was poor.
- Comparative Example 4 A polyester film was obtained in the same manner as in Example 9 except that the film forming conditions shown in the table were used. The results of evaluating the obtained film are shown in the table. In particular, the hydrolysis resistance was poor.
- a back sheet was prepared by the method of Example 1 to obtain a back sheet having a thickness of 187 ⁇ m.
- the evaluation results are shown in Table 1. In particular, the hydrolysis resistance was poor.
- Comparative Example 5 Except having set it as the film forming conditions shown to a table
- a back sheet was prepared by the method of Example 1 to obtain a back sheet having a thickness of 187 ⁇ m.
- the evaluation results are shown in Table 1. In particular, the hydrolysis resistance was poor.
- sheet in the table refers to “back sheet”.
- the film of this invention can be used conveniently for the solar cell which uses a backsheet.
Abstract
Description
面配向係数= (nMD+nTD)/2 - nZD ・・・ (A)
上記式(A)におけるnMDはフィルムの長手方向(MD)の屈折率を表し、nTDはフィルムの直行方向(TD)の屈折率を表し、nZDはフィルム厚み方向の屈折率を表している。
フィルムの面配向係数を上記数値範囲内とするためには、製膜時の延伸倍率を大きくすることによって達成できる。好ましくはフィルムの長手方向(MD)、フィルムの直行方向(TD)ともに延伸倍率を2.5~6.0倍に調整するとよく、フィルムの面配向係数を0.165以上とするためには、MDおよびTD方向の延伸倍率をそれぞれ3.0~5.0倍に調整することが好ましい。なお、フィルムの面配向係数の上限は特に限定されるものではないが、面配向係数を上げるために延伸倍率を大きくしていくと製膜安定性が悪化するため、生産性の点から0.200以下であることが好ましく、より好ましくは0.185以下である。
式(B)を満足せしめることにより、耐加水分解性(125℃、湿度100%の条件下、72時間放置後の平均伸度保持率など)を向上せしめることができる。
(1)固有粘度
フィルムをオルトクロロフェノールに溶解せしめ、25℃で測定した溶液粘度から、下式より固有粘度を得た。
ηsp/C=[η]+K[η]2・C
ここで、ηsp=(溶液粘度/溶媒粘度)-1であり、Cは、溶媒100mlあたりの溶解ポリマー重量であり(本測定では1g/100mlとする)、Kはハギンス定数(0.343とする)であり。また、溶液粘度、溶媒粘度はオストワルド粘度計を用いて測定した。
フィルム0.5gをo-クレゾールに溶解し、水酸化カリウムを用いて電位差滴定して測定し、カルボキシル末端基濃度を求めた。
微少吸熱ピーク温度Tmeta(℃)は、JIS K7122-1987(JISハンドブック1999年版を参照した)に準じて、セイコー電子工業(株)製示差走査熱量測定装置”ロボットDSC-RDC220”を、データ解析にはディスクセッション”SSC/5200”を用いて測定した。サンプルパンにフィルムを5mg秤量し、25℃から300℃まで20℃/分の昇温速度で昇温を行って測定を行った。得られた示差走査熱量測定チャートにおける結晶融解ピーク前の微少吸熱ピーク温度でもってTmeta(℃)とした。微小な吸熱のピークが観測しにくい場合は、データ解析部にてピーク付近を拡大して、ピークを読みとった。
JIS-C2318(2007)に準じて、幅10mm、標線間隙約100mmのサンプルを、温度150℃、荷重0.5gで30分間熱処理した。その熱処理前後の標線間隙を(株)テクノニーズ製熱収縮率測定器(AMM-1号機)を用いて測定し、次式より熱収縮率を算出した。
熱収縮率(%)={(L0-L)/L0}×100
L0:加熱処理前の標線間隙
L :加熱処理後の標線間隙
(5)面配向係数
アタゴ社(株)製アッベ屈折率計Type 4Tを用い、光源をナトリウムランプとして、フィルム屈折率の測定を行った。
面配向係数= (nMD+nTD)/2 - nZD ・・・ (A)
上記式(A)におけるnMDはフィルムの長手方向(MD)の屈折率を表し、nTDはフィルムの直行方向(TD)の屈折率を表し、nZDはフィルム厚み方向の屈折率を表している。
蛍光X線法(リガク製ZSX100e)により、リン原子の含有量を測定した。
分光光度計((株)島津製作所UV2450)に積分球付属装置((株)島津製作所製ISR2200)を取り付け、硫酸バリウムを標準板とし、標準板を100%とした相対反射率を測定した値とする。波長400~700nmにおいて、波長0.5nm毎の相対反射率を測定し、それらの平均値を平均反射率とする。
破断伸度の測定はASTM-D882-97(1999年版ANNUAL BOOK OF ASTM STANDARDSを参照した)に準じて、サンプルを1cm×20cmの大きさに切り出し、チャック間5cm、引っ張り速度300mm/minにて引っ張ったときの破断伸度(初期)を測定した。なお、測定は5サンプルについて測定を実施し、その平均値でもって破断伸度(初期)A0とした。
伸度保持率(%)=A1/A0×100 (1)
また、下記式(2)により平均伸度保持率を算出した。
平均伸度保持率(%)=(MD方向の伸度保持率+TD方向の伸度保持率)/2 (2)
なお、平山製作所 高加速寿命試験装置(HAST装置) PC-304R8Dを用いて測定しても、エスペック(株)製高度加速寿命試験装置EHS-221MDを用いて測定される値と同一の値となるので、平山製作所 高加速寿命試験装置(HAST装置) PC-304R8Dを用いて測定しても良い。
破断伸度の測定はASTM-D882-97(1999年版ANNUAL BOOK OF ASTM STANDARDSを参照した)に準じて、サンプルを1cm×20cmの大きさに切り出し、チャック間5cm、引っ張り速度300mm/minにて引っ張ったときの破断伸度(初期)を測定した。なお、測定は5サンプルについて測定を実施し、その平均値でもって破断伸度(初期)A2とした。
伸度保持率(%)=A3/A2×100 (3)
また、下記(4)により平均伸度保持率を算出した。
平均伸度保持率(%)=(MD方向の伸度保持率+TD方向の伸度保持率)/2 (4)
(原料PET-1)
ジメチルテレフタレート100重量部、およびエチレングリコール60重量部の混合物を、酢酸カルシウム0.08重量部、三酸化アンチモン0.03重量部を添加して、常法により加熱昇温してエステル交換反応を行った。次いで、該エステル交換反応生成物を、酢酸リチウム0.16重量部、リン酸トリメチル0.11重量部を添加した後、重合反応槽に移行する。次で、加熱昇温しながら反応系を徐々に減圧して1mmHgの減圧下、290℃で常法により重合し、固有粘度[η]0.52のポリエステル(ポリエチレンテレフタレート)を得た。該ポリエステルは各辺2mm×4mm×4mmの直方体に切断し、回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で20時間加熱処理し、固有粘度[η]0.79、カルボキシル末端基濃度10.5eq/tonのポリエステルを得た。
まず、上記にて得られた厚み125μmの本発明のフィルムを第1層として用いる。次いで、接着層として“タケラック(登録商標)”A310(三井武田ケミカル(株)製)90重量部、“タケネート(登録商標)”A3(三井武田ケミカル(株)製)を第1層の表面に塗布し、さらに当該接着層の上に第2層として厚さ12μmバリアロックス“HGTS”(東レフィルム加工(株)製のアルミナ蒸着PETフィルム)を蒸着層が第1層と反対側になるように貼り合わせた。次に、第2層上に上述の接着層と同様の接着層を塗布し、さらに当該接着層の上に、厚さ50μmの二軸配向ポリエステルフィルム“ルミラー(登録商標)”E20(東レ(株)製)を貼り合わせ、総厚さ187μmのバックシートを作成した。該バックシートを評価した結果を表に示した。このバックシートの耐加水分解性を評価したところ、良好であった。
表に示す製膜条件とした以外は、実施例1と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
(原料PET-2)
回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で40時間加熱処理した以外は原料PET-1と同様製法にて、固有粘度[η]0.82、カルボキシル末端基濃度8.5eq/tonのポリエステル(ポリエチレンテレフタレート)を得た。
表に示す製膜条件とした以外は、実施例5と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
(原料PET-3)
原料PET-1 90重量部に対して、ラインケミー社製スタバクゾールP100」(ポリカルボジイミド)を10重量部加えてコンパウンドした。このコンパウンド品を原料PET-3とする。
表に示す製膜条件とした以外は、実施例9と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
表に示す製膜条件とした以外は、実施例6と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
(原料PET-4)
リン酸トリメチルの添加量を0.13重量部とし、回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で40時間加熱処理した以外は原料PET-1と同様の製法で、固有粘度[η]0.82、カルボキシル末端基濃度8.5eq/tonのポリエステル(ポリエチレンテレフタレート)を得た。
(原料PET-5)
リン酸トリメチルの添加量を0.25重量部とし、回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で40時間加熱処理した以外は原料PET-1と同様の製法で、固有粘度[η]0.82、カルボキシル末端基濃度8.5eq/tonのポリエステル(ポリエチレンテレフタレート)を得た。
原料PET-5を温度180℃、真空度0.5mmHgの条件下で2時間の減圧乾燥を行い、295℃に加熱した押出機に供給し、50μmカットフィルターにより異物濾過を行ったのちにTダイ口金に導入した。次いで、Tダイ口金内より、シート状に押出して溶融単層シートとし、該溶融単層シートを、表面温度20℃に保たれたドラム上に静電印加法で密着冷却固化させて未延伸単層フィルムを得た。続いて、該未延伸単層フィルムを85℃の温度に加熱したロール群で予熱した後、90℃の温度の加熱ロールを用いて長手方向(MD)に3.5倍延伸を行い、25℃の温度のロール群で冷却して一軸延伸フィルムを得た。得られた一軸延伸フィルムの両端をクリップで把持しながらテンター内の95℃の温度の予熱ゾーンに導き、引き続き連続的に105℃の温度の加熱ゾーンで長手方向に直角な方向(TD)に4.0倍延伸した。さらに引き続いて、テンター内の熱処理ゾーンで205℃の温度(第1熱処理温度)で20秒間の熱処理を施した。引き続き、180℃の温度下において、フィルムを幅方向(TD)に3%の弛緩率にて弛緩させ、また、テンターのクリップ間隔を縮めることによって、長手方向(MD)に1.5%の弛緩率にて弛緩させた。次いで、25℃まで均一に冷却後巻取り、ポリエステルフィルムを得た。評価した結果を表に示した。このフィルムで耐加水分解性を評価した結果良好であった。
テンターのクリップ間隔を縮めることによって、長手方向(MD)の弛緩率を2.0%とした以外は、実施例17と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
押出機(a)、押出機(b)を有する複合製膜装置を使用した。
平均粒子径0.2μmの酸化チタン(表面未処理、ルチル型)を30重量部、蛍光増白剤“OB-1”(イーストマンコダック社製)を0.15重量部、原料PET-5を69.85重量部の割合で混合したものを、温度180℃、真空度0.5mmHgの条件下で、2時間の減圧乾燥をした後、押出機(a)側に供給した以外は、実施例19と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
(原料PET-6)
回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で5時間加熱処理した以外は原料PET-1と同じ製法で、固有粘度[η]0.65、カルボキシル末端基濃度18eq/tonのポリエステル(ポリエチレンテレフタレート)を得た。
原料PET-6を90重量部に、ラインケミー社製スタバクゾールP100」(ポリカルボジイミド)を10重量部加えて、コンパウンドした。このコンパウンド品を原料PET-7とする。
(原料PET-8)
回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で100時間加熱処理した以外は原料PET-1と同様の製法で、固有粘度[η]1.2、カルボキシル末端基濃度8.0eq/tonのポリエステルを得た。
実施例6と同じ方法で行い、厚み125μmのフィルムを得た。評価した結果を表に示した。
次いで、接着層として“タケラック(登録商標)”A310(三井武田ケミカル(株)製)90重量部、“タケネート(登録商標)”A3(三井武田ケミカル(株)製)を第1層の表面に塗布し、当該接着層の上に第2層として厚さ12μmバリアロックス“HGTS”(東レフィルム加工(株)製のアルミナ蒸着PETフィルム)を蒸着層が第1層と反対側になるように貼り合わせ、次に第2層上に上述の接着層と同様の接着層を塗布し、当該接着層の上に第3層として厚さ250μmの二軸配向ポリエステルフィルム“ルミラー(登録商標)”S10(東レ(株)製)をはりあわせた。さらに第3層上に上述の接着層と同様の接着層を塗布し、当該接着層の上に厚さ50μmの二軸配向ポリエステルフィルム“ルミラー(登録商標)”E20(東レ(株)製)をはりあわせ、総厚さ437μmのバックシートを形成した。評価した結果を表に示した。このバックシートの耐加水分解性を評価した結果良好であった。
ポリエステルフィルムの厚みを50μmとする以外は、実施例6と同じ製造方法にて、ポリエステルフィルムを得た。フィルムを評価した結果を表に示した。
上記にて得られた厚み50μmのフィルムを第1層として用いる。
次いで、接着層として“タケラック(登録商標)”A310(三井武田ケミカル(株)製)90重量部、“タケネート(登録商標)”A3(三井武田ケミカル(株)製)を第1層に塗布し、当該接着層の上に第2層として厚さ12μmバリアロックス“HGTS”(東レフィルム加工(株)製のアルミナ蒸着PETフィルム)を蒸着層が第1層と反対側になるように貼り合わせ、次に第2層上に上述の接着層と同様の接着層を塗布し、当該接着層の上に第3層として厚さ250μmの二軸配向ポリエステルフィルム“ルミラー(登録商標)”S10(東レ(株)製)をはりあわせた。さらに第3層上に上述の接着層と同様の接着層を塗布し、当該接着層の上に厚さ188μmの二軸配向ポリエステルフィルム“ルミラー(登録商標)”E20(東レ(株)製)をはりあわせ、総厚さ500μmのバックシートを形成した。評価した結果を表1に示した。このバックシートの耐加水分解性を評価した結果良好であった。
表に示す製膜条件とした以外は、実施例5と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。このフィルムの耐加水分解性を評価したところ、良好であった。
(原料PET-9)
ジメチルテレフタレート100部、およびエチレングリコール60部の混合物を、酢酸カルシウム0.08部、三酸化アンチモン0.03部を添加して、常法により加熱昇温してエステル交換反応を行った。次いで、該エステル交換反応生成物を、酢酸リチウム0.16部、リン酸トリメチル0.11部を添加した後、重合反応槽に移行する。次で、加熱昇温しながら反応系を徐々に減圧して1mmHgの減圧下、290℃で常法により重合し、固有粘度[η]0.52のポリエステルを得た。該ポリエステルは各辺2mm×4mm×4mmの直方体に切断し、回転型真空重合装置を用いて、0.5mmHgの減圧下、230℃で8時間加熱処理し、固有粘度[η]0.74、カルボキシル末端基濃度13eq/tonのポリエステルを得た。
表に示す製膜条件とした以外は、比較例1と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。特に耐加水分解性に劣る結果となった。
表に示す製膜条件とした以外は、実施例1と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。特に耐加水分解性に劣る結果となった。
表に示す製膜条件とした以外は、実施例9と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。特に耐加水分解性に劣る結果となった。
表に示す製膜条件とした以外は、実施例5と同じ方法で製膜し、ポリエステルフィルムを得た。得られたフィルムを評価した結果を表に示した。特に耐加水分解性に劣る結果となった。
Claims (18)
- カルボキシル末端基濃度が13eq/ton以下であり、
示差走査熱量測定(DSC)により求められる微少吸熱ピーク温度Tmeta(℃)が220℃以下である太陽電池用ポリエステルフィルム。 - フィルムの長手方向(MD)とその直行方向(TD)の150℃30分の熱収縮率がそれぞれ0.6%以下である請求項1に記載の太陽電池用ポリエステルフィルム。
- 面配向係数B2が0.165以上である請求項1または2に記載の太陽電池用ポリエステルフィルム。
- 蛍光X線測定により求められるリン原子の含有量が200ppm以上である請求項1~3のいずれかに記載の太陽電池用ポリエステルフィルム。
- 前記微少吸熱ピーク温度Tmeta(℃)が205℃以下である請求項1~4のいずれかに記載の太陽電池用ポリエステルフィルム。
- 少なくとも一方の表面における波長400~700nmの平均反射率が80%以上である請求項1~5のいずれかに記載の太陽電池用ポリエステルフィルム。
- 固有粘度が0.6~1.2dl/gの範囲である請求項1~6のいずれかに記載の太陽電池用ポリエステルフィルム。
- カルボキシル末端基濃度が12eq/ton以下である請求項1~7のいずれかに記載の太陽電池用ポリエステルフィルム。
- ポリエステル層を少なくとも2層有する請求項1~8のいずれかに記載の太陽電池用ポリエステルフィルム。
- 125℃、湿度100%の条件下48時間放置後の平均伸度保持率が50%以上である請求項1~9のいずれかに記載の太陽電池用ポリエステルフィルム。
- 温度125℃、湿度100%の条件下72時間放置後の平均伸度保持率が10%以上である請求項1~10のいずれかに記載の太陽電池用ポリエステルフィルム。
- Tmeta(℃)と面配向係数B2が、次の式(B)を満たす請求項1~11のいずれかに記載の太陽電池用ポリエステルフィルム。
B2≧0.000886×Tmeta-0.00286 式(B) - 請求項1~12のいずれかに記載の太陽電池用ポリエステルフィルムの製造方法であって、未延伸ポリエステルフィルムを少なくとも一軸に延伸した後、220℃以下の温度で熱処理する太陽電池用ポリエステルフィルムの製造方法。
- 請求項1~12のいずれかに記載の太陽電池用ポリエステルフィルムを少なくとも1枚含む太陽電池バックシート。
- 125℃、湿度100%の条件下48時間放置後の平均伸度保持率が50%以上である請求項14に記載の太陽電池バックシート。
- 請求項14または15に記載の太陽電池バックシートを用いてなる太陽電池。
- カルボキシル末端基濃度が13eq/ton以下であるポリエステルフィルムの製造方法であって、未延伸ポリエステルフィルムを少なくとも一軸に延伸した後、205℃以下の温度で熱処理する太陽電池用ポリエステルフィルムの製造方法。
- ポリエステルフィルムのカルボキシル末端基濃度が12eq/ton以下である請求項17に記載の太陽電池用ポリエステルフィルムの製造方法。
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CN102365317A (zh) | 2012-02-29 |
TWI467776B (zh) | 2015-01-01 |
CN102365317B (zh) | 2015-03-11 |
JP5728944B2 (ja) | 2015-06-03 |
TW201037840A (en) | 2010-10-16 |
JPWO2010110119A1 (ja) | 2012-09-27 |
KR101660391B1 (ko) | 2016-09-27 |
MY179256A (en) | 2020-11-03 |
KR20120009438A (ko) | 2012-01-31 |
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