WO2012029499A1 - Films de copolymère de téréphtalate de 1,4-cyclohexylènediméthylène/isophtalate de 1,4-cyclohexylènediméthylène, feuilles protectrices pour un module de cellule solaire et module de cellule solaire - Google Patents

Films de copolymère de téréphtalate de 1,4-cyclohexylènediméthylène/isophtalate de 1,4-cyclohexylènediméthylène, feuilles protectrices pour un module de cellule solaire et module de cellule solaire Download PDF

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WO2012029499A1
WO2012029499A1 PCT/JP2011/067967 JP2011067967W WO2012029499A1 WO 2012029499 A1 WO2012029499 A1 WO 2012029499A1 JP 2011067967 W JP2011067967 W JP 2011067967W WO 2012029499 A1 WO2012029499 A1 WO 2012029499A1
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Prior art keywords
solar cell
film
cell module
cyclohexylenedimethylene
copolymer
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PCT/JP2011/067967
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English (en)
Japanese (ja)
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佳幸 柚原
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長瀬産業株式会社
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Priority to TW100131059A priority Critical patent/TW201229102A/zh
Priority to TW100131060A priority patent/TW201223995A/zh
Publication of WO2012029499A1 publication Critical patent/WO2012029499A1/fr

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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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a copolymer film of 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate, a protective sheet for a solar cell module, and a solar cell module.
  • Solar cell power generation systems are expected as a clean energy source to replace fossil fuels.
  • a solar cell power generation system uses a solar cell module in which an element group in which several to several tens of solar cell elements are wired in series or in parallel is protected by various packages.
  • the solar cell module is generally covered with white plate tempered glass on the surface directly irradiated with sunlight, a solar cell element group is arranged below it, and the gap is filled with transparent ethylene, vinyl, acetate resin, etc.
  • the back surface is protected by a sheet made of a weather resistant plastic material or the like (for example, Patent Documents 1 and 2).
  • the solar cell module protective sheet (particularly the back surface protective sheet) is required to have weather resistance, particularly hydrolysis resistance. This is because the protective sheet may be decomposed and peeled off by moisture such as rain while being used outdoors for a long time, which may cause corrosion of the exposed wiring and affect the output of the module. .
  • a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film has insufficient hydrolysis resistance and cannot be practically used as a base material for a back protective sheet for a solar cell module.
  • an object of the present invention is to provide a film excellent in hydrolysis resistance, a protective sheet for a solar cell module using the film, and a solar cell module.
  • a copolymer film of specific 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate has excellent hydrolysis resistance and is used for a solar cell module.
  • the present invention has been conceived by finding it suitable for a base material for a protective sheet.
  • the present invention provides a copolymer film of 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate having a glass transition temperature measured by DMA method of 130 ° C. or higher.
  • the present invention also provides a copolymer film of 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate having a glass transition temperature measured by the TMA method of 200 ° C. or higher. .
  • the present invention provides a co-polymerization of 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate having a maximum peak in the range of 22 ° ⁇ 2 ⁇ ⁇ 24 ° in X-ray diffraction.
  • These copolymer films of 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate are excellent in hydrolysis resistance.
  • the present invention provides a protective sheet for a solar cell module, comprising at least one copolymer film of any of the above 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate.
  • a protective sheet for a solar cell module is excellent in hydrolysis resistance and can withstand long-term use of the solar cell module.
  • the protective sheet for a solar cell module is particularly preferably used as a back surface protective sheet for a solar cell module.
  • the present invention includes a filling layer including a solar cell element, a surface protection sheet disposed on the surface of the filling layer, and a back surface protection sheet disposed on the back surface of the filling layer, the surface protection sheet and the back surface protection sheet.
  • a solar cell module having a copolymer film of any of the aforementioned 1,4-cyclohexylenedimethylene terephthalate and 1,4-cyclohexylenedimethylene isophthalate.
  • the present invention it is possible to provide a film excellent in hydrolysis resistance, a solar cell module protective sheet, and a solar cell module.
  • the copolymer film of 1,4-cyclohexylene dimethylene terephthalate and 1,4-cyclohexylene dimethylene isophthalate of this embodiment is composed of 1,4-cyclohexylene dimethylene terephthalate and 1,4-cyclohexylene dimethylene. It consists of a resin composition containing a copolymer with isophthalate (hereinafter referred to as “copolymer A”).
  • the molar ratio of terephthalate to isophthalate is not particularly limited, but is usually 99.9: 0.1 to 50:50, preferably about 99: 1 to 70:30.
  • the intrinsic viscosity (IV value) of the copolymer A is preferably 0.5 to 1.0 dl / g, and more preferably 0.75 to 1.0 dl / g.
  • the IV value is obtained as follows. That is, copolymer A is dissolved in a mixed solvent of 60% by mass of phenol and 40% by mass of 1,1,2,2-tetrachloroethylene so as to have a concentration of 0.5 g / 100 ml.
  • the drop time of the solution in the capillary viscometer is measured at 25 ° C., and this is taken as ts. Moreover, the drop time in the capillary viscometer only of a solvent is measured, and this is set to.
  • the content ratio of the copolymer A in the resin composition containing the copolymer A is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and 70 to 100% by mass from the viewpoint of further improving the hydrolysis resistance. % Is more preferable.
  • the resin composition containing the copolymer A may appropriately include organic substances other than the copolymer A, inorganic substances, and various additives.
  • organic substances other than the copolymer A include cyclic and linear copolymer A oligomers, monomers of the acid component and glycol component constituting the copolymer A, low molecular weight reactants derived therefrom, and other than the copolymer A And various additives.
  • thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polypropylene naphthalate, polybutylene naphthalate, thermosetting polyester, nylon 6, thermoplastic polyamides such as nylon 66, nylon 11 and nylon 12, polycarbonate, polyacetal, polystyrene, ABS resin, polyurethane, fluororesin, silicone resin, polyphenylene sulfite resin, cellulose, polyphenylene ether resin, etc. Polymerized resin etc. are mentioned.
  • inorganic substances include inorganic fillers such as glass fiber, carbon fiber, talc, mica, wollastonite, kaolin clay, layered silicate, calcium carbonate, titanium dioxide, and silica dioxide, inorganic lubricants, polymerization catalyst residues, and the like.
  • inorganic fillers such as glass fiber, carbon fiber, talc, mica, wollastonite, kaolin clay, layered silicate, calcium carbonate, titanium dioxide, and silica dioxide, inorganic lubricants, polymerization catalyst residues, and the like.
  • Additives include organic and inorganic dyes and pigments, matting agents, heat stabilizers, flame retardants, antistatic agents, antifoaming agents, color adjusting agents, antioxidants, ultraviolet absorbers, crystal nucleating agents. , Whitening agents, lubricants, impurity scavengers, thickeners, surface conditioners and the like. Among these, it is preferable to include a heat stabilizer and a trapping agent for low molecular weight volatile impurities.
  • the heat stabilizer pentavalent and / or trivalent phosphorus compounds, hindered phenol compounds and the like are preferable, and as a trapping agent for low molecular weight volatile impurities, polymers and oligomers of polyamide and polyesteramide, amide groups and amine groups are preferred. Preferred are low molecular weight compounds having
  • the copolymer A film of this embodiment has a glass transition temperature measured by DMA method of 130 ° C. or higher.
  • the glass transition temperature measured by the DMA method is preferably 140 ° C. or higher, more preferably 150 ° C. or higher.
  • there is no upper limit of the glass transition temperature measured by the DMA method it is usually 200 ° C. or lower, preferably 180 ° C. or lower, preferably 170 ° C. or lower, and more preferably 160 ° C. or lower.
  • the DMA method is the following method. That is, the test piece is heated from room temperature at a rate of 5 ° C./min, the dynamic viscoelasticity and loss tangent of the test piece are measured using a viscoelasticity measuring device, and the glass transition temperature is calculated from the peak temperature of the loss tangent. Can be requested.
  • the measurement frequency is 1 Hz.
  • the copolymer A film of this embodiment has a glass transition temperature measured by the TMA method of 200 ° C. or higher.
  • the glass transition temperature measured by the TMA method is preferably 210 ° C. or higher, more preferably 220 ° C. or higher, still more preferably 230 ° C. or higher, and particularly preferably 235 ° C. or higher.
  • the glass transition temperature measured by the TMA method it is usually 260 ° C. or lower, preferably 255 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 245 ° C. or lower.
  • the TMA method is the following method. That is, the temperature of the test piece is raised from room temperature at a rate of 10 ° C./min, the amount of thermal expansion in the thickness direction is measured using a thermal analyzer, and a graph showing the relationship between the temperature and the amount of thermal expansion is drawn. . A tangent line is drawn on the curves before and after the glass transition point, and the glass transition temperature can be obtained from the intersection of the tangent lines.
  • the copolymer A film of this embodiment has a maximum peak in the range of 22 ° ⁇ 2 ⁇ ⁇ 24 ° in X-ray diffraction.
  • the copolymer A film of this embodiment is excellent in hydrolysis resistance.
  • the reason why the copolymer A film according to this embodiment has such characteristics is not clear, but one factor is as follows.
  • the characteristics relating to the glass transition temperature and the maximum peak described above are related to the fact that the copolymer A in the copolymer A film of the present embodiment is crystallized to some extent. And it is thought that hydrolysis resistance becomes high when the copolymer A is crystallized to some extent (preferably 20% or more, more preferably 30% or more in crystallinity).
  • the breaking strength of the copolymer A film of this embodiment is preferably 80 MPa or more, more preferably 90 MPa or more, and more preferably 100 MPa or more in both the MD direction and the TD direction. More preferably it is.
  • the elongation at break of the copolymer A film of this embodiment is preferably 150 MPa or less, more preferably 120 MPa or less, and more preferably 80 MPa or less in both the MD direction and the TD direction. More preferably.
  • the dielectric breakdown voltage of the present embodiment is preferably 90 kV / mm or more, more preferably 110 kV / mm or more, and further preferably 130 kV / mm or more in the measurement based on ASTM D-149. .
  • the thermal expansion coefficient (CTE) of this embodiment is preferably 80 ppm / ° C. or less, more preferably 60 ppm / ° C. or less in both the MD and TD directions, as measured by the TMA method (50 to 100 ° C.). Preferably, it is 40 ppm / ° C. or less.
  • the thickness of the copolymer A film of the present embodiment can be appropriately selected depending on the thickness of the back protective sheet for solar cell module and the required performance, but is preferably 10 ⁇ m to 500 ⁇ m, and preferably 20 ⁇ m to 300 ⁇ m. It is more preferable that the thickness is 30 ⁇ m to 200 ⁇ m. By setting it as such a range, while it becomes easy to manufacture a film, intensity
  • the thickness unevenness is preferably within ⁇ 10%, more preferably within ⁇ 7%, and further preferably within ⁇ 5%.
  • the copolymer A film according to this embodiment can be produced as follows. First, a copolymer A resin (for example, pellets) as a raw material is prepared.
  • the copolymer A resin can be produced by polycondensing 1,4-cyclohexanedimethanol, terephthalic acid, and isophthalic acid by a known method.
  • the copolymer A pellet is commercially available from Eastman Corporation under the trade name “Eastman Copolymerester 13319”, for example.
  • copolymer A resin is fuse
  • melt molding method in which a resin composition containing the copolymer A is extruded from a die in a molten state, a solution in which the resin composition is dissolved in a solvent is applied onto a support, and then the solvent The solution cast method etc. which dry is mentioned.
  • the melt molding method is most preferable because it is excellent in productivity and environmental suitability and can obtain a film in one step.
  • a method using a T die or an I die, a water-cooled method, and an air-cooled inflation method are preferable.
  • the above-described copolymer A film according to this embodiment can be obtained by stretching the formed unstretched copolymer A film.
  • the stretching conditions and the stretching method are not particularly limited, and may be appropriately adjusted within a range in which the above glass transition temperature is obtained or a maximum peak is obtained in a predetermined angle range in X-ray diffraction.
  • the stretching direction may be uniaxial or biaxial, but biaxial is preferred.
  • the stretching method is not particularly limited, and various methods such as roll stretching and tenter stretching can be used alone or in any combination.
  • the stretch ratio is not particularly limited. For example, it can be 2 to 5 times in the MD (machine direction) direction and 2 to 5 times in the TD (transverse direction) direction.
  • FIG. 1 shows an example of the configuration of the back surface protection sheet for solar cell modules of the present invention (hereinafter, sometimes simply referred to as “back surface protection sheet”).
  • the back surface protection sheet 1 has a configuration in which film base materials 30 and 32 having heat resistance are laminated on both surfaces of the gas barrier film 20.
  • the gas barrier film 20 is obtained by providing a vapor deposition layer 12 made of an inorganic compound on one surface of a substrate 10.
  • the base material 10 the above-mentioned copolymer A film can be used.
  • the film base materials 30 and 32 having heat resistance used in the present embodiment may be any film having heat resistance, such as a polyethylene terephthalate (PET) film or a vinyl fluoride resin (PVF) film, a vinylidene fluoride resin ( PVDF) film, trifluoroethylene chloride (PCTFE) film, ethylene-tetrafluoroethylene copolymer (ETFE) film, polytetrafluoroethylene (PTFE) film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Examples thereof include a fluorine-based substrate selected from (PFA) films.
  • the copolymer A film can also be used suitably as the film base materials 30 and 32 which have heat resistance.
  • the thickness of the film base materials 30 and 32 is not particularly limited, and is preferably 3 to 200 ⁇ m, and more preferably 6 to 30 ⁇ m.
  • the material of the vapor deposition layer 12 is not particularly limited, and examples thereof include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, zinc oxide, and a mixture of two or more thereof.
  • the thickness of the vapor deposition layer 12 is not particularly limited, and is preferably 5 to 300 nm, for example, and more preferably 10 to 150 nm.
  • the gas barrier film 20 and the heat-resistant film base materials 30 and 32 may be adhesive if necessary. It is possible to perform lamination by adopting a dry lamination lamination method in which the layers are bonded together.
  • a dry lamination lamination method it is necessary that the adhesive strength does not cause delamination due to deterioration when used outdoors for a long period of time, and that the adhesive does not turn yellow, etc., and is compatible with high heat resistance, moisture heat resistance, etc. Therefore, it is desirable to use a resin or the like as a main component of the vehicle constituting the adhesive which can be crosslinked or cured to form a three-dimensional network crosslinked structure.
  • the adhesive constituting the adhesive layer for laminating preferably forms a crosslinked structure by reaction energy consisting of heat or light in the presence of a curing agent or a crosslinking agent.
  • a curing agent or a crosslinking agent for example, laminating by reaction energy consisting of heat or light in the presence of an aliphatic or alicyclic isocyanate such as a two-component curable polyurethane adhesive, or an isocyanate curing agent or crosslinking agent such as an aromatic isocyanate.
  • an aliphatic or alicyclic isocyanate such as a two-component curable polyurethane adhesive
  • an isocyanate curing agent or crosslinking agent such as an aromatic isocyanate.
  • aliphatic isocyanate for example, 1,6-hexamethylene diisocyanate (HDI)
  • alicyclic isocyanate for example, isophorone diisocyanate (IPDI)
  • aromatic isocyanate for example, tri Range isocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), and the like can be used.
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI tri Range isocyanate
  • MDI diphenylmethane diisocyanate
  • NDI naphthylene diisocyanate
  • TODI tolidine diisocyanate
  • XDI xylylene diisocyanate
  • an ultraviolet absorber or a light stabilizer can be added in order to prevent ultraviolet degradation or the like.
  • the amount used varies depending on the particle shape, density, etc., but is preferably about 0.1 to 10% by weight.
  • the adhesive can be applied, for example, by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method, and the coating amount is 2 to 20 g / m 2 (dry state) ) Position, preferably in the range of 3 to 10 g / m 2 (dry state).
  • a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method
  • the coating amount is 2 to 20 g / m 2 (dry state) ) Position, preferably in the range of 3 to 10 g / m 2 (dry state).
  • the film base material 30 and 32 which has heat resistance showed the aspect which laminates
  • a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, a printing method, or the like can be applied.
  • the coating amount is desirably in the range where the thickness of the coated film after curing is 1 to 100 ⁇ m (dry state), preferably 5 to 50 ⁇ m (dry state).
  • the back protective sheet for a solar cell module of the present invention thus obtained is particularly excellent in hydrolysis resistance because it has the above-mentioned copolymer A film. Therefore, such a back surface protection sheet for solar cells can protect the solar cells over a long period of time and is inexpensive.
  • the structure of the back surface protection sheet for solar cell modules is not limited to said structure.
  • a transparent primer layer may be provided between the vapor-deposited layer 12 and the base material 10 in order to improve their adhesion.
  • the resin for the transparent primer layer include a composite of a silane coupling agent or a hydrolyzate thereof, a polyol and an isocyanate compound.
  • silane coupling agent examples include ethyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane.
  • silane couplings such as ⁇ -methacryloxypropylmethyldimethoxysilane or hydrolysates thereof can be used.
  • those containing isocyanate groups such as ⁇ -isocyanatopropyltriethoxysilane and ⁇ -isocyanatopropyltrimethoxysilane
  • those containing mercapto groups such as ⁇ -mercaptopropyltriethoxysilane
  • ⁇ -aminopropyltriethoxysilane There are those containing amino groups such as silane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltriethoxysilane, and ⁇ -phenylaminopropyltrimethoxysilane.
  • silane coupling agent may be added with alcohol or the like and added with a hydroxyl group or the like, and one or more of these may be used.
  • polystyrene examples include those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxylbutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene. Is preferably used.
  • isocyanate compound examples include monomers such as aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI), and polymers thereof. Or a derivative thereof can be used, and one or more of these can be used.
  • TDI aromatic tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • XDI aliphatic xylene diisocyanate
  • HMDI hexadiisocyanate
  • the thickness of the transparent primer layer is not particularly limited, but is preferably 0.001 to 2 ⁇ m, and preferably 0.03 to 0.5 ⁇ m.
  • an overcoat layer having a gas barrier property may be further provided between the vapor deposition layer 12 and the film substrate 32.
  • the overcoat layer includes, for example, a water-soluble polymer and one or more metal alkoxides or a hydrolyzate thereof, and a coating solution containing water or a water-alcohol mixed solution as a solvent is applied to the vapor deposition layer 12. Can be formed.
  • water-soluble polymers examples include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate.
  • metal alkoxide examples include tetraethoxysilane and triisopropoxyaluminum.
  • the vapor deposition layer 12 may be formed on both surfaces of the base material 10. In this case, you may form the above-mentioned transparent primer layer and overcoat layer with respect to both vapor deposition surfaces.
  • the back protection sheet for solar cell modules when the back protection sheet for solar cell modules is applied to a solar cell module having a low necessity for gas barrier properties, the back protection sheet for solar cell modules may not have the vapor deposition layer 12.
  • the film base materials 30 and 32 having heat resistance are formed on one side or both sides of the base material 10.
  • the back surface protection sheet 1 for solar cell modules may not have any one or both of the film base materials 30 and 32, and may be comprised only from the above-mentioned base material 10.
  • FIG. 2 is a schematic cross-sectional view showing a layer configuration of one embodiment of the solar cell module 100 including the solar cell back surface protective sheet of the present invention.
  • the solar cell module 100 of the present embodiment includes a solar cell module surface protection sheet 60, a front surface side filler layer 51, a solar cell element 50 as a photovoltaic element provided with a wiring 52, a back surface side filler layer 53, And the film base material 30 which has the said hydrolysis resistance of the said back surface protection sheet 1 is set as the structure arrange
  • the above-described layers can be thermocompression-molded as an integrally formed body.
  • the solar cell module 100 can be mounted with, for example, an aluminum frame (not shown).
  • the normal solar cell module surface protection sheet 60 constituting the solar cell module has sunlight permeability, insulation, etc., and further has weather resistance, heat resistance, light resistance, water resistance, moisture resistance, It has various characteristics such as antifouling properties, etc., is excellent in physical or chemical strength, toughness, etc., is extremely durable, and further, because it protects solar cell elements as photovoltaic elements, It must be excellent in scratch resistance, shock absorption, and the like.
  • known glass plates and the like and further, for example, polyamide resins (various nylons), polyester resins, cyclic polyolefin resins, polystyrene resins, (meth) acrylic resins, polycarbonate resins, acetals
  • polyamide resins various nylons
  • polyester resins such as polyethylene glycol dimethacrylate resins
  • cyclic polyolefin resins such as polystyrene resins
  • (meth) acrylic resins polycarbonate resins
  • acetals Various resin films and sheets such as a resin and others can be used, and the copolymer A can also be suitably used.
  • the resin film or sheet a biaxially stretched stretched film or sheet can be used.
  • the thickness of the resin film or sheet may be a minimum thickness necessary to maintain strength, rigidity, waist, etc. If it is too thick, there is a disadvantage that the cost increases, and the thickness is thin.
  • the thickness of the resin film or sheet is preferably 12 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • the filler layer for example, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid, or acid-modified polyolefin resin, polyvinyl butyral resin, silicone resin, epoxy resin , (Meth) acrylic resins, and other resins can be used as a mixture of one or more.
  • the resin constituting the filler layer is, for example, a crosslinking agent within a range that does not impair its transparency in order to improve weather resistance such as heat resistance, light resistance, and water resistance. Additives such as thermal antioxidants, light stabilizers, ultraviolet absorbers, photo-antioxidants, etc. can be arbitrarily added and mixed.
  • the filler on the sunlight incident side is preferably an ethylene-vinyl acetate resin in consideration of performance and price such as weather resistance such as light resistance, heat resistance, and water resistance. It is a material.
  • the thickness of the filler layer is preferably 200 to 1000 ⁇ m, more preferably 350 to 600 ⁇ m.
  • the solar cell element 50 as a photovoltaic element constituting the solar cell module, a conventionally known one, for example, a crystalline silicon solar electronic element such as a single crystal silicon type solar cell element or a polycrystalline silicon type solar cell element, a single Amorphous silicon solar cell elements of junction type or tandem structure type, III-V compound semiconductor solar electronic elements such as gallium arsenide (GaAs) and indium phosphorus (InP), cadmium tellurium (CdTe) and copper indium selenide (CuInSe) 2 ) Group II-VI compound semiconductor solar electronic device, organic solar cell device, etc. can be used. Furthermore, a thin film polycrystalline silicon solar cell element, a thin film microcrystalline silicon solar cell element, a hybrid element of a thin film crystalline silicon solar cell element and an amorphous silicon solar cell element, or the like can also be used.
  • a crystalline silicon solar electronic element such as a single crystal silicon type solar cell element or a polycrystalline silicon type solar cell element, a single A
  • the back-side filler layer 53 laminated under the photovoltaic element constituting the solar cell module is made of the same material as the front-side filler layer 51 laminated under the surface protection sheet for the solar cell module. Can be used. It is also necessary to have adhesiveness with the back surface protection sheet, and it has thermoplasticity to fulfill the function of maintaining the smoothness of the back surface of the solar cell element as a photovoltaic element, and further, the photovoltaic element From the viewpoint of protecting the solar cell element, it is necessary to have excellent scratch resistance, shock absorption and the like.
  • the copolymer A film is used for at least one of the above-described back surface protection sheet and the surface protection sheet, the hydrolysis resistance of the back surface protection sheet or the surface protection sheet. High nature. Therefore, compared with the case where the conventional polyethylene terephthalate (PET) film or polyethylene naphthalate (PEN) film is used, it becomes possible to maintain the power output characteristics as a solar cell over a long period of time.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the solar cell module is not limited to the above configuration, and various configurations are possible.
  • the back surface protection sheet 1 those having various configurations as described above can be adopted. If necessary, it is provided with a filling layer including the solar cell element 50, a surface protection sheet 60 disposed on the surface of the filling layer, and a back surface protection sheet 1 disposed on the back surface of the filling layer. It suffices that at least one of the back surface protective sheets 1 includes the above-mentioned copolymer A film.
  • PEN polyethylene naphthalate.
  • Copolymer A Eastman Co., Ltd., trade name: Eastman Copolyester 13319
  • PEN manufactured by Teijin DuPont Films, trade name: Teonex Q51
  • 1,4-cyclohexanedimethanol / 2,2,4,4-tetramethyl-1,3-cyclobutanediol / terephthalic acid polycondensate (manufactured by Eastman, trade name: Eastman Tritan Copolyester FX200) , Referred to as “Copolymer B”.)
  • Example 1 The copolymer A (in the form of pellets) was melt-extruded to form a film, and further biaxially stretched to obtain a stretched copolymer A film having a thickness of 50 ⁇ m.
  • Example 2 A copolymer A film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the thickness was changed to 100 ⁇ m by changing the draw ratio.
  • PEN pellet form
  • PEN pellet form
  • Copolymer A (pellet form) was melt-extruded to form a film, and an unstretched copolymer A film having a thickness of 110 ⁇ m was obtained.
  • Copolymer B (pellet form) was melt-extruded to form a film, and an unstretched copolymer B film having a thickness of 100 ⁇ m was obtained.
  • ⁇ Hydrolysis test> The films of Examples 1 and 2 and Comparative Examples 1 to 3 were subjected to a pressure cooker test (120 ° C., 100% RH (relative humidity), 2 atm). For each film, the tensile strength retention and tensile elongation retention after 50 hours, 100 hours, 150 hours and 200 hours were measured. The results are shown in FIGS. The films of Examples 1 and 2 had a slower decrease in tensile strength retention and tensile elongation retention than the films of Comparative Examples 1 to 3.
  • Example 1 About the film of Example 1, Example 2, and the comparative example 2, the powder X-ray diffraction by CuK (alpha) ray was performed, confirmation of the diffraction pattern and calculation of the crystallinity degree were performed.
  • the measurement method and measurement conditions are as follows.
  • FIG. 5 shows the relationship between the angle 2 ⁇ formed by the X-ray incident direction and the reflection direction and the diffraction intensity.
  • a clear sharp maximum peak was confirmed in the range of 22 ° ⁇ 2 ⁇ ⁇ 24 °, but no sharp peak was observed anywhere in the film of Comparative Example 2, and the film was amorphous. There was found.
  • the crystallinity degree of the film of Example 1 and Example 2 was calculated
  • SYMBOLS 1 Back surface protection sheet for solar cell modules, 10 ... Base material, 12 ... Deposition layer, 20 ... Gas barrier film, 30, 32 ... Film base material, 50 ... Solar cell element, 51 ... Surface side filler layer, 52 ... Wiring, 53 ... back side filler layer, 60 ... surface protection sheet for solar cell module, 100 ... solar cell module.

Abstract

L'invention concerne un film d'un copolymère de téréphtalate de 1,4-cyclohexylènediméthylène et d'isophtalate de 1,4-cyclohexylènediméthylène présentant une température de transition vitreuse d'au moins 130°C mesurée à l'aide de l'AMD. Elle concerne également un film d'un copolymère de téréphtalate de 1,4-cyclohexylènediméthylène et d'isophtalate de 1,4-cyclohexylènediméthylène présentant une température de transition vitreuse d'au moins 200°C mesurée à l'aide de l'ATM. L'invention concerne en outre un film d'un copolymère de téréphtalate de 1,4-cyclohexylènediméthylène et d'isophtalate de 1,4-cyclohexylènediméthylène présentant un pic de diffraction des rayons X maximum dans la plage de 22° ≤ 2θ ≦ 24°.
PCT/JP2011/067967 2010-08-30 2011-08-05 Films de copolymère de téréphtalate de 1,4-cyclohexylènediméthylène/isophtalate de 1,4-cyclohexylènediméthylène, feuilles protectrices pour un module de cellule solaire et module de cellule solaire WO2012029499A1 (fr)

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TW100131059A TW201229102A (en) 2010-08-30 2011-08-30 Polyester film and method for producing same
TW100131060A TW201223995A (en) 2010-08-30 2011-08-30 Polyester film and method for producing same

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PCT/JP2011/069564 WO2012029760A1 (fr) 2010-08-30 2011-08-30 Film polyester et son procédé de production
PCT/JP2011/069565 WO2012029761A1 (fr) 2010-08-30 2011-08-30 Film de polyester et procédé de production dudit film

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JP5918604B2 (ja) * 2012-04-09 2016-05-18 倉敷紡績株式会社 離型フィルムを用いた転写フィルム
JP6306109B2 (ja) * 2012-04-13 2018-04-04 富士フイルム株式会社 ポリエステルフィルム、太陽電池モジュール用バックシートおよび太陽電池モジュール
JP5993613B2 (ja) * 2012-04-13 2016-09-14 富士フイルム株式会社 ポリエステルフィルム、太陽電池モジュール用バックシートおよび太陽電池モジュール
KR101605413B1 (ko) 2014-02-12 2016-03-22 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR101594542B1 (ko) * 2013-12-30 2016-02-16 에스케이씨 주식회사 투명 이축연신 폴리에스테르 필름 및 이의 제조방법
KR101647470B1 (ko) * 2014-01-14 2016-08-10 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR101605411B1 (ko) 2014-02-21 2016-03-22 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR101647475B1 (ko) * 2014-12-26 2016-08-10 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR102426418B1 (ko) * 2014-09-17 2022-07-28 닛산 가가쿠 가부시키가이샤 열경화성 수지를 포함하는 막형성 조성물
CN107075151B (zh) * 2014-10-28 2020-12-15 日本瑞翁株式会社 树脂膜以及树脂膜的制造方法
WO2016111091A1 (fr) * 2015-01-10 2016-07-14 三菱樹脂株式会社 Film stratifié métallique double face
JP6467927B2 (ja) * 2015-01-10 2019-02-13 三菱ケミカル株式会社 両面金属積層フィルム
JP6467928B2 (ja) * 2015-01-10 2019-02-13 三菱ケミカル株式会社 両面金属積層フィルム
JP6467942B2 (ja) * 2015-01-24 2019-02-13 三菱ケミカル株式会社 両面金属積層フィルム
JP6763126B2 (ja) * 2015-09-30 2020-09-30 三菱ケミカル株式会社 金属積層フィルム
KR20180018686A (ko) * 2015-09-30 2018-02-21 미쯔비시 케미컬 주식회사 금속막 적층용 필름
JP6763125B2 (ja) * 2015-09-30 2020-09-30 三菱ケミカル株式会社 金属積層フィルム
JP6805520B2 (ja) * 2016-03-29 2020-12-23 三菱ケミカル株式会社 金属層付きポリエステルフィルムの製造方法
DE112018005965T5 (de) * 2017-11-22 2020-07-30 Sk Chemicals Co., Ltd. Polyesterharzzusammensetzung und diese umfassende biaxial orientierte polyesterfolie
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JPWO2012029761A1 (ja) 2013-10-28
TW201221544A (en) 2012-06-01
WO2012029761A1 (fr) 2012-03-08
TW201223995A (en) 2012-06-16

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