WO2014091973A1 - Feuille stratifiée et son procédé de fabrication, feuille arrière de cellule solaire, module de cellule solaire et procédé de fabrication de feuille arrière de cellule solaire - Google Patents

Feuille stratifiée et son procédé de fabrication, feuille arrière de cellule solaire, module de cellule solaire et procédé de fabrication de feuille arrière de cellule solaire Download PDF

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WO2014091973A1
WO2014091973A1 PCT/JP2013/082533 JP2013082533W WO2014091973A1 WO 2014091973 A1 WO2014091973 A1 WO 2014091973A1 JP 2013082533 W JP2013082533 W JP 2013082533W WO 2014091973 A1 WO2014091973 A1 WO 2014091973A1
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layer
resin
solar cell
laminated sheet
acid
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PCT/JP2013/082533
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English (en)
Japanese (ja)
Inventor
堀江　将人
規行 巽
柴田　優
高橋　弘造
崇 荒井
網岡　孝夫
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東レ株式会社
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Priority to KR1020157013902A priority Critical patent/KR20150095635A/ko
Priority to JP2014508619A priority patent/JP6287829B2/ja
Priority to CN201380064004.XA priority patent/CN104822528B/zh
Publication of WO2014091973A1 publication Critical patent/WO2014091973A1/fr

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • 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 laminated sheet capable of achieving both durability and adhesion with a sealing material.
  • the present invention relates to a laminated sheet that can be suitably used as a solar battery backsheet, and a method for producing the laminated sheet. Furthermore, it is related with the back seat
  • a solar cell is composed of a power generation element sealed with a transparent sealing material such as ethylene-vinyl acetate copolymer (EVA), and a transparent substrate such as glass and a resin sheet called a back sheet bonded together.
  • EVA ethylene-vinyl acetate copolymer
  • the Sunlight is introduced into the solar cell through the transparent substrate. Sunlight introduced into the solar cell is absorbed by the power generation element, and the absorbed light energy is converted into electrical energy. The converted electric energy is taken out by a lead wire connected to the power generation element and used for various electric devices.
  • polyethylene terephthalate PET
  • PET biaxially-stretched polyethylene terephthalate
  • polyolefin resin is a material generally used as a back sheet because of its good adhesion to the sealing material.
  • Patent Document 1 a backsheet in which a polybutylene terephthalate resin and a polycarbonate resin are laminated or a polybutylene terephthalate resin.
  • Patent Document 2 A back sheet (Patent Document 2) using a lip has been developed.
  • the solar cell module is easily deteriorated in a high-temperature and high-humidity environment, and there is an urgent need to improve the heat and humidity resistance.
  • EVA is often used from the viewpoints of weather resistance, transparency, productivity, etc., but generation of acetic acid has been a concern due to high-temperature steam. .
  • Patent Document 4 there is also an invention of a solar cell module sealing material in which output characteristics do not change for a long time by suppressing acetic acid generated from EVA.
  • JP 2009-141345 A International Publication No. 2010/018662 JP 2012-199379 A JP 2008-115344 A
  • polybutylene terephthalate resin generally has inferior moisture and heat resistance, and further has a drawback of poor adhesion to a sealing material.
  • the back sheet described in Patent Document 1 in which a polybutylene terephthalate resin and a polycarbonate resin are laminated has improved moisture and heat resistance, but does not provide adhesion to a sealing material, and has a problem of delamination.
  • the backsheet described in Patent Document 2 is also difficult to achieve both wet heat resistance and adhesion between the sealing material. Therefore, in view of the conventional problems, the present invention provides a laminated sheet that has high productivity and can be suitably used for a solar battery backsheet that has both durability and adhesion with a sealing material.
  • Patent Document 3 an inorganic vapor deposition film or the like is often used when the water vapor transmission rate is lowered, and when the inorganic vapor deposition film is used, there is a problem that the cost becomes very high as compared with the case where it is not used. there were.
  • the water vapor transmission rate is high, each metal material used in the solar battery cell is corroded by moisture, and in particular, discoloration may occur due to corrosion of the collecting electrode of the solar battery cell.
  • Patent Document 4 there is a concern about the effect of adding an additive to EVA, and the change of EVA adjacent to the solar battery cell requires a large amount of verification work for change.
  • the present invention has been conceived in view of the above problems. That is, the present invention provides a back sheet for a solar cell module that is inexpensive, can maintain the power generation characteristics of the solar cell module for a long period of time, and prevents discoloration of the current collecting electrode of the solar cell.
  • the purpose is to do.
  • the present invention has the following configuration.
  • 1st invention is a lamination sheet which has a layer (P1 layer) which uses polybutylene terephthalate resin as the main component, and a layer (P3 layer) which uses polyolefin resin as the main component.
  • the second invention has a layer (P2 layer) mainly composed of an adhesive polyolefin-based resin, and the P1 layer and the P3 layer are in contact with each other through the P2 layer.
  • P2 layer mainly composed of an adhesive polyolefin-based resin
  • the third invention is characterized in that the thickness of the P2 layer is 15 to 50 ⁇ m.
  • the fourth invention is characterized in that the crystallization parameter ⁇ Tcg of the P1 layer measured using differential scanning calorimetry (DSC) is 7 to 30 ° C.
  • the polybutylene terephthalate resin that is the main component of the P1 layer is And end-capped polybutylene terephthalate resin.
  • the sixth invention is characterized in that the P3 layer contains 0.1 to 30% by mass of inorganic particles.
  • the seventh invention is characterized in that the rigid amorphous amount of the P1 layer is 30 to 50%.
  • the eighth invention is characterized in that the P1 layer contains 0.1 to 5% by mass of a crystal nucleating agent.
  • the ninth invention is characterized in that the P3 layer contains 5 to 30% by mass of inorganic particles having a particle diameter of 3 to 20 ⁇ m and 0.5 to 5% by mass of an adhesive polyolefin resin.
  • the acetic acid permeability Pa (g / m 2 / day) at 85 ° C. and the water vapor permeability Pw (g / m 2 / day) at 40 ° C. and 90% RH are expressed by the formula (1) 200 ⁇ Pa and the expression (2) Pw ⁇ 2.5 are satisfied.
  • 11th invention is a solar cell backsheet which consists of a lamination sheet concerning one of the above-mentioned inventions.
  • the twelfth invention is a solar cell using the solar cell backsheet according to the eleventh invention.
  • a thirteenth invention is a method for manufacturing a laminated sheet according to any one of the second to tenth inventions, wherein the raw material for the P1 layer mainly comprises a polybutylene terephthalate resin, and the main structure is an adhesive polyolefin resin.
  • the raw material for the P2 layer, which is the component, and the raw material for the P3 layer, the main component of which is a polyolefin resin, are supplied to different extruders, and after melting, the P1, P2, and P3 layers are joined together in this order. It is made to laminate
  • the acetic acid permeability Pa (g / m 2 / day) at 85 ° C. and the water vapor permeability Pw (g / m 2 / day) at 40 ° C. and 90% RH are expressed by the formula (1) 200 ⁇ It is a solar cell back sheet
  • filling Pa and Formula (2) Pw ⁇ 2.5.
  • the layer which is one of the main constituents selected from the group consisting of a polyester resin, a polyamide resin, and a fluororesin, is a P4 layer, it has a P4 layer.
  • a sixteenth aspect of the present invention is the solar cell backsheet according to the fifteenth aspect of the present invention, wherein the layer mainly composed of the olefin resin is a P6 layer, and the P6 layer has a P4 layer and a P6 layer.
  • the P4 layer is located on the surface layer
  • the P6 layer is located on the surface opposite to the P4 layer
  • the thickness of the entire backsheet is Ta ( ⁇ m)
  • the thickness of the P4 layer is T4 ( ⁇ m)
  • the P6 layer When the thickness of T6 ( ⁇ m) and the content of inorganic particles in the P6 layer is M (mass%), the formula (3) 0.05 ⁇ M / T6 ⁇ 0.5 and the formula (4) 200 ⁇ Ta ⁇ 500 and all of formula (5) 0.3 ⁇ T4 / Ta ⁇ 0.5) are satisfied.
  • the seventeenth invention is characterized in that, in any one of the fifteenth and sixteenth inventions, the P4 layer is mainly composed of polyamide resin or polybutylene terephthalate (PBT).
  • the P4 layer is mainly composed of polyamide resin or polybutylene terephthalate (PBT).
  • the main constituent is one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer.
  • the layer is a P5 layer
  • the P5 layer is located between the P4 layer and the P6 layer.
  • the nineteenth invention is a solar cell module having the solar cell backsheet according to any one of the fourteenth to eighteenth inventions.
  • a twentieth aspect of the invention is a method for manufacturing a back sheet for a solar cell according to the eighteenth aspect of the present invention, which is a raw material mainly comprising a polyamide resin for P4 layer or PBT, and a low crystalline soft polymer for P5 layer.
  • a method for producing a back sheet for a solar cell comprising: a step of feeding a P4 layer, a P5 layer, and a P6 layer after being melted together, laminating them in this order, and extruding them into a sheet form from a T-die. is there.
  • a laminated sheet having excellent durability, sealing material adhesion, and interlayer adhesion that can be suitably used for a solar battery backsheet.
  • Such a laminated sheet can be suitably used for a solar battery backsheet, and a high performance solar battery can be provided by using the backsheet.
  • the acetic acid generated inside the solar cell module is released to the outside of the module by adjusting the acetic acid permeability and water vapor permeability of the backsheet.
  • FIG. 1 It is sectional drawing which shows typically an example of a structure of the solar cell (solar cell module) using the lamination sheet (solar cell backsheet) of this invention. It is a jig sectional view for acetic acid permeability measurement. It is a jig top view for acetic acid permeability measurement.
  • the first to thirteenth inventions are laminated sheets having a layer (P1 layer) containing a polybutylene terephthalate resin as a main constituent component and a layer (P3 layer) containing a polyolefin resin as a main constituent component.
  • the polybutylene terephthalate resin refers to a polyester resin mainly composed of butylene terephthalate composed of terephthalate as a dicarboxylic acid component and 1,4-butanediol as a diol component.
  • the main repeating unit here means that when all the dicarboxylic acid components in the polyester resin are 100 mol%, 80 mol% or more and 100 mol% or less are terephthalate components, and all the diol components in the polyester resin are When it is 100 mol%, it means that 80 mol% or more and 100 mol% or less is a 1,4-butanediol component.
  • the terephthalate component is preferably 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol%.
  • the 1,4-butanediol component is preferably 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol%. It is.
  • terephthalic acid as the dicarboxylic acid component, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethyl Aliphatic dicarboxylic acids such as malonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, and the like, cyclophthalic dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarbox
  • the carboxylic acid terminal of the above-mentioned dicarboxylic acid component may be added with oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of oxyacids. It is suitably used as a polymerization component. Moreover, you may use these in multiple types as needed.
  • diol component examples include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol.
  • Cycloaliphatic diols such as cyclohexanedimethanol, spiroglycol, isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenecenemethanol, 9,9'-bis (4-hydroxyphenyl) fluorene Examples include, but are not limited to, diol components such as aromatic diols, components in which a plurality of the above-mentioned diols are linked, and the like. Moreover, you may use these in multiple types as needed.
  • a polybutylene terephthalate-based resin can be obtained by appropriately combining the above-mentioned dicarboxylic acid component and diol component and polycondensing them.
  • the melting point of the resulting polybutylene terephthalate resin is generally 200 ° C. or higher and 230 ° C. or lower. Furthermore, in the present invention, it is more preferable to use one having a melting point of 215 ° C. or higher and 230 ° C. or lower.
  • the crystallization parameter ⁇ Tcg of the P1 layer measured using differential scanning calorimetry (DSC) is preferably 7 to 30 ° C. If the ⁇ Tcg of the P1 layer is less than 7 ° C., crystallization is likely to cause embrittlement, and moisture and heat resistance may decrease. If ⁇ Tcg of the P1 layer is greater than 30 ° C., moisture may easily enter between layers due to crystallinity, and interlayer adhesion may be deteriorated.
  • the differential scanning calorimetry (DSC) of the polybutylene terephthalate resin which is the main component of the P1 layer is used.
  • the method of setting the crystallization parameter ⁇ Tcg by 7) to 7-30 ° C. is preferred.
  • the rigid amorphous amount of the P1 layer is preferably 30 to 50%. If it is less than 30%, curling tends to occur. If it exceeds 50%, it tends to become brittle after the wet heat treatment, and the heat and humidity resistance is lowered.
  • rigid amorphous refers to an amorphous state in which the molecular motion is frozen even at the glass transition temperature or higher in an intermediate state between the crystal and the complete amorphous.
  • the degree of crystallinity and the amount of complete amorphous are described in “Fiber and Industry” Vol. 65, no. 11 (2009) P.I. 428, and can be quantified using the temperature modulation DSC method. Specific measurement methods are described in the examples.
  • the polybutylene terephthalate resin as the main constituent component means that the polybutylene terephthalate resin is contained in an amount of more than 50% by mass and less than 100% by mass in 100% by mass of all components of the layer. means.
  • the P1 layer constituting the laminated sheet of the present invention preferably contains inorganic particles in the range of 0.1% by mass to 30% by mass.
  • the content of inorganic particles in the P1 layer is more preferably 2% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. These inorganic particles are used for imparting necessary functions to the sheet depending on the purpose.
  • handling properties may be lowered or durability may be lowered.
  • the content of the inorganic particles in the P1 layer is less than 0.1% by mass, the effect due to the inclusion of the inorganic particles is difficult to obtain, and yellowing may occur.
  • the inorganic particles suitably used for the P1 layer include inorganic particles having ultraviolet absorbing ability, particles having a large refractive index difference from the polybutylene terephthalate resin, conductive particles, and pigments. Optical properties such as ultraviolet rays, light reflectivity, and whiteness, antistatic properties, and the like can be imparted.
  • the particle means a particle having a primary particle diameter of 5 nm or more based on the diameter of a projected equivalent equivalent circle. Unless otherwise specified, in the present invention, the particle size means a primary particle size, and the particle means a primary particle.
  • the inorganic particles suitably used for the P1 layer of the present invention include, for example, gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, Metals such as nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, antimony, indium, yttrium, lanthanum, zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, oxidation Metal oxides such as lanthanum soot, zirconium oxide, aluminum oxide, silicon oxide, lithium fluoride, magnesium fluoride soot, aluminum fluoride soot, metal fluorides such as cryolite, metal phosphates such as calcium phosphate, carbonates such as calcium carbonate Salt, barium sulfate And sulfates such as talc, talc and
  • inorganic particles in the P1 layer metal oxides such as titanium oxide, zinc oxide, and cerium oxide, which are inorganic particles having ultraviolet absorbing ability, are used.
  • metal oxides such as titanium oxide, zinc oxide, and cerium oxide, which are inorganic particles having ultraviolet absorbing ability.
  • titanium oxide it is preferable in that it can exhibit the effect of reducing coloration due to deterioration of the sheet over a long period of time by utilizing the ultraviolet resistance by the inorganic particles.
  • titanium oxide as the inorganic particles in the P1 layer in that high reflection characteristics can be imparted, and it is more preferable to use rutile type titanium oxide in terms of higher ultraviolet resistance.
  • the method of incorporating the polybutylene terephthalate resin and inorganic particles in the P1 layer is a method in which the polybutylene terephthalate resin and inorganic particles are melt-kneaded in advance using a vent type twin-screw kneading extruder or a tandem type extruder. preferable.
  • the polybutylene terephthalate-based resin may be deteriorated.
  • a high-concentration master pellet with a large amount of inorganic particles is produced as compared with the amount of inorganic particles to be contained in the P1 layer, and it is mixed with a polybutylene terephthalate resin and diluted to obtain a predetermined P1 layer.
  • Inorganic particle content is preferred from the viewpoint of durability.
  • the P1 layer has a polybutylene terephthalate-based resin as a main constituent, and among them, the polybutylene terephthalate-based resin that is the main constituent of the P1 layer is an end-capped polybutylene terephthalate-based resin. More preferably.
  • the end-capped polybutylene terephthalate-based resin means a resin obtained by reacting the end-capping agent with the polybutylene terephthalate-based resin.
  • a terminal blocking agent is added to the polybutylene terephthalate resin, and the carboxyl group located at the end of the polybutylene terephthalate resin (hereinafter referred to as the carboxyl group located at the terminal)
  • the carboxyl group located at the terminal It is preferable to form a P1 layer after reacting a terminal blocking agent with a terminal blocking agent to eliminate the catalytic activity of the proton of the COOH group of the polybutylene terephthalate resin.
  • the end-capping agent is a compound that reacts with and binds to the carboxyl end group of the polyester to eliminate the catalytic activity of the proton of the COOH group.
  • the oxazoline group, epoxy group, carbodiimide group, etc. The compound etc. which have these substituents are mentioned.
  • Examples of the carbodiimide compound having a carbodiimide group suitable as a terminal blocking agent include a monofunctional carbodiimide and a polyfunctional carbodiimide.
  • Examples of monofunctional carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide and the like.
  • dicyclohexylcarbodiimide and diisopropylcarbodiimide are particularly preferred.
  • the polyfunctional carbodiimide carbodiimide having a polymerization degree of 3 to 15 is preferable.
  • a carbodiimide compound having high heat resistance is preferable.
  • the molecular weight (degree of polymerization) is high, and it is more preferable that the terminal of the carbodiimide compound has a structure having high heat resistance. Further, once thermal decomposition occurs, further thermal decomposition is likely to occur. Therefore, it is necessary to devise measures such as setting the extrusion temperature of polyester (polybutylene terephthalate resin) as low as possible.
  • epoxy compound suitable as the end-capping agent include glycidyl ester compounds and glycidyl ether compounds.
  • Specific examples of the glycidyl ester compound include benzoic acid glycidyl ester, t-Bu-benzoic acid glycidyl ester, P-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, and lauric acid glycidyl ester.
  • glycidyl ether compound examples include phenyl glycidyl ether, O-phenyl glycidyl ether, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) butane, 1,6-bis ( ⁇ , ⁇ -epoxypropoxy).
  • a bisoxazoline compound is preferable, and specifically, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline) ), 2,2′-bis (4,4-dimethyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-) 2-oxazoline), 2,2'-bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2- Oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline) 2,2'-p-fu Nylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2
  • the bisoxazoline compounds listed above may be used singly or in combination of two or more as long as the object of the present invention is achieved.
  • the concentration of the end blocker added is 0.25 to 5 with respect to 100% by mass of the polybutylene terephthalate resin. % By mass is preferable, and more preferably 0.5 to 2% by mass. If it is less than 0.25% by mass, the effect of addition is small, and there is a problem that the heat and humidity resistance is lowered.
  • the concentration is higher than 5% by mass, the carboxyl end groups are considerably reduced, and there is a problem that interlayer adhesion is lowered.
  • the P1 layer and the P3 layer of the laminated sheet of the present invention may have other additives (for example, a heat stabilizer, an ultraviolet absorber, a weather stabilizer, an organic lubricant, as long as the effects of the present invention are not impaired). Pigments, dyes, fillers, antistatic agents, nucleating agents, etc.
  • the inorganic particles referred to in the present invention may not be included in the additives herein.
  • an ultraviolet absorber is selected as an additive and contained in the P1 layer and / or the P3 layer
  • the ultraviolet resistance of the laminated sheet of the present invention can be further improved.
  • an antistatic agent or the like is contained in the P1 layer and / or the P3 layer, an improvement in withstand voltage can be expected.
  • the P1 layer preferably contains 0.1 to 5% by mass of a crystal nucleating agent.
  • the crystal nucleating agent can be preferably selected from the group of talc, aliphatic carboxylic acid amide, aliphatic carboxylate, aliphatic alcohol, aliphatic carboxylic acid ester, sorbitol compound, and organic phosphoric acid compound.
  • the crystal nucleating agent is preferably one type of crystal nucleating agent comprising an aliphatic carboxylic acid amide, an aliphatic carboxylate and a sorbitol compound. If the crystal nucleating agent is less than 0.1% by mass, the crystallinity may be low and strength may not be obtained. When it is larger than 5% by mass, the crystallinity is high and brittleness tends to occur.
  • aliphatic carboxylic acid amides include aliphatic monocarboxylic acids such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxy stearic acid amide.
  • Acid amides N-oleyl palmitic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide N-substituted aliphatic monocarboxylic amides such as methylol behenic acid amide, methylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis capric acid amide, ethylene bis oleic acid amide, ethylene bis Arynic acid amide, ethylene biserucic acid amide, ethylene bis behenic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, butylene bisstearic acid amide, hexamethylene bisoleic acid amide, hexamethylene bisstearic acid Alipha
  • aliphatic monocarboxylic acid amides may be one kind or a mixture of two or more kinds.
  • aliphatic monocarboxylic acid amides, N-substituted aliphatic monocarboxylic acid amides, and aliphatic biscarboxylic acid amides are preferably used, particularly palmitic acid amide, stearic acid amide, erucic acid amide, and behenic acid.
  • Amide, ricinoleic acid amide, hydroxystearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, ethylene biscapric acid amide, ethylene bisoleic acid amide, ethylene bislauric acid amide, ethylene biserucic acid amide, m -Xylylene bis-stearic acid amide and m-xylylene bis-12-hydroxystearic acid amide are preferably used.
  • aliphatic carboxylate examples include acetates such as sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium laurate, potassium laurate, potassium hydrogen laurate, magnesium laurate, calcium laurate, zinc laurate , Laurates such as silver laurate, lithium myristate, sodium myristate, potassium hydrogen myristate, magnesium myristate, calcium myristate, zinc myristate, silver myristate, myristate, lithium palmitate, palmitic acid Palmitates such as potassium, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, lead palmitate, thallium palmitate, cobalt palmitate, etc., sodium oleate Oleates such as potassium oleate, magnesium oleate, calcium oleate, zinc oleate, lead oleate, thallium oleate, copper oleate, nickel oleate, sodium stearate, lithium stearate, magnesium steacetate,
  • stearic acid salts and montanic acid salts are preferably used, and in particular, sodium stearate, potassium stearate, zinc stearate, barium stearate, sodium montanate, and the like are suitably used.
  • aliphatic alcohols include aliphatic monoalcohols such as pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, and melyl alcohol, 1,6-hexane.
  • aliphatic carboxylic acid ester examples include lauric acid cetyl ester, lauric acid phenacyl ester, myristic acid cetyl ester, myristic acid phenacyl ester, palmitic acid isopropylidene ester, palmitic acid dodecyl ester, and palmitic acid tetraethyl ester.
  • Aliphatic monocarboxylic acid esters such as dodecyl ester, palmitic acid pentadecyl ester, palmitic acid octadecyl ester, palmitic acid cetyl ester, palmitic acid phenyl ester, palmitic acid phenacyl ester, stearic acid cetyl ester, behenic acid ethyl ester, monolaurin Monoesters of ethylene glycol such as acid glycol, glycol monopalmitate, glycol monostearate, glycol dilaurate, Diesters of ethylene glycol such as glycol palmitate and glycol distearate, monolaurate glycerin ester, monomyristic acid glycerin ester, monopalmitic acid glycerin ester, glycerin monoesters such as monostearic acid glycerin ester, dilauric acid glycerin ester, Glycerin diesters such as dimy
  • aliphatic / aromatic carboxylic acid hydrazides include sebacic acid dibenzoic acid hydrazide, specific examples of melamine compounds, specific examples of melamine cyanurate, polymelate melamine, and phenylphosphonic acid metal salts.
  • phenylphosphonic acid zinc salt, phenylphosphonic acid calcium salt, phenylphosphonic acid magnesium salt, and phenylphosphonic acid magnesium salt can be used.
  • sorbitol compounds include 1,3-di (P-methylbenzylidene) sorbitol, 2,4-di (P-methylbenzylidene) sorbitol, 1,3-dibenzylidenesorbitol, 2,4-dibenzylidenesorbitol, Examples include 3-di (P-ethyldibenzylidene) sorbitol and 2,4-di (P-ethyldibenzylidene) sorbitol.
  • organic phosphate compound examples include sodium bis (4-t-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, and cyclic organic phosphate ester
  • examples thereof include a mixture selected from basic polyvalent metal salts and alkali metal carboxylates, alkali metal ⁇ -diketonates and alkali metal ⁇ -ketoacetate organic carboxylic acid metal salts.
  • sodium montanate is preferably used from the viewpoint of strength.
  • the P1 layer and the P3 layer are in contact with each other via the P2 layer means that the P1 layer, the P2 layer, and the P3 layer are directly laminated in this order.
  • the adhesive polyolefin-based resin means one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate-based copolymer.
  • the layer (P2 layer) is a layer mainly composed of one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer.
  • the main constituent component is one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer. It means that one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer exceeds 50% by mass and is equal to or less than 100% by mass.
  • Examples of the low crystalline soft polymer that is one of the main components of the P2 layer include acid-modified polyolefins and unsaturated polyolefins.
  • Examples of the acrylic adhesive that is one of the main components of the P2 layer include ethylene-acrylic acid ester-maleic anhydride terpolymer.
  • the P2 layer is preferably made of acid-modified polyolefin as a main constituent.
  • Examples of the acid-modified polyolefin include “Admer” manufactured by Mitsui Chemicals, Inc., “Modic” manufactured by Mitsubishi Chemical, and “Binnel” manufactured by DuPont.
  • the P2 layer preferably further contains a polyolefin elastomer in addition to the adhesive polyolefin resin.
  • the polyolefin-based elastomer generally refers to one obtained by finely dispersing ethylene-propylene rubber in polypropylene or one obtained by copolymerizing polypropylene with another ⁇ -olefin.
  • These polyolefin-based elastomers are preferably contained in a proportion of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of all components of the P2 layer.
  • the content of the polyolefin-based elastomer in the P2 layer is preferably 5% by mass or more and 20% by mass or less.
  • the polyolefin-based elastomer may be a commercially available product, for example, “Thermolan”, “Zeras” manufactured by Mitsubishi Chemical Corporation, “Excellen”, “Tough Selenium”, “Esplen”, “Hibler” manufactured by Kuraray, Preferred examples include “Septon” and “Notio” manufactured by Mitsui Chemicals.
  • the P3 layer in the present invention is a layer mainly composed of a polyolefin-based resin.
  • the polyolefin resin in the present invention include polyethylene, polypropylene, polybutene, polymethylpentene, polycycloolefin, polyhexene, polyoctene, polydecene, and polydodecene.
  • the adhesive polyolefin resin that is the main constituent of the P2 layer does not correspond to the polyolefin resin that is the main constituent of the P3 layer.
  • the polyolefin resin that is the main component of the P3 layer is preferably polyethylene or polypropylene.
  • polyolefin-based resins may be mixed and copolymerized with other olefin components.
  • the melting point of the resin can be lowered, and adhesion with a sealing material can be reduced. It is preferable because of improved properties.
  • the main component of polyolefin resin means that 100% by mass of the total component of the layer contains more than 50% by mass and 100% by mass or less of polyolefin resin.
  • the P3 layer constituting the laminated sheet of the present invention preferably contains inorganic particles in the range of 0.1% by mass to 30% by mass.
  • the content of inorganic particles in the P3 layer is more preferably 2% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. These inorganic particles are used for imparting necessary functions to the sheet depending on the purpose.
  • the content of the inorganic particles in the P3 layer is more than 30% by mass, the adhesion with the sealing material may be lowered.
  • the content of the inorganic particles in the P3 layer is less than 0.1% by mass, it is difficult to obtain the effect due to the inclusion of the inorganic particles, and yellowing may occur.
  • the P3 layer contains 5 to 30% by mass of inorganic particles having a particle diameter of 3 ⁇ m or more and 20 ⁇ m or less.
  • the particle size refers to an average particle size at an integrated value of 50% in a particle size distribution obtained by laser analysis / scattering method. If the inorganic particles having a size of 3 ⁇ m or more and 20 ⁇ m or less are less than 5% by mass, the mechanical strength may be reduced. If the inorganic particles having a size of 3 ⁇ m or more and 20 ⁇ m or less are larger than 30% by mass, the surface may be roughened and the adhesion with the sealant may be lowered.
  • the P3 layer preferably contains 0.5 to 5% by mass of an adhesive polyolefin resin.
  • the adhesive polyolefin-based resin may act as a dispersion aid for inorganic particles having a size of 3 ⁇ m or more and 20 ⁇ m or less. If it is less than 0.5% by mass, the mechanical strength may decrease due to poor dispersion of the inorganic particles of 3 ⁇ m or more and 20 ⁇ m or less. If it is larger than 5% by mass, the heat resistance may decrease.
  • the adhesive polyolefin resin here is the same as that defined for the P2 layer adhesive polyolefin resin.
  • the acetic acid permeability Pa (g / m 2 / day) in the laminated sheet of the present invention means the acetic acid permeability when acetic acid is in a saturated vapor pressure state (85 ° C.). And as for the lamination sheet of this invention, it is preferable that the acetic acid permeability Pa in 85 degreeC satisfy
  • the laminated sheet of the present invention has an acetic acid permeability Pa of 200 g / m 2 / day or more.
  • the acetic acid permeability Pa of the laminated sheet of the present invention is preferably 800 g / m 2 / day or more.
  • the acetic acid permeability Pa is preferably as large as possible.
  • the acetic acid permeability Pa is 1500 g / m 2 / day. The following is preferable.
  • the water vapor transmission rate Pw (g / m 2 / day) in the laminated sheet of the present invention means the water vapor transmission rate in an environment of 40 ° C. and 90% RH. And as for the laminated sheet of this invention, it is preferable that the water-vapor-permeation rate Pw (g / m ⁇ 2 > / day) in 40 degreeC90% RH satisfy
  • the water vapor permeability Pw of the laminated sheet of the present invention is 2.5 g / in, from the viewpoint of suppressing corrosion inside the solar cell module due to moisture, particularly discoloration due to corrosion of the collecting electrode portion of the solar battery cell.
  • the water vapor transmission rate Pw is preferably as small as possible.
  • the water vapor transmission rate Pw is 0.5 g / m. 2 / day or more is preferable.
  • the thickness of the P1 layer constituting the laminated sheet of the present invention is preferably 80 ⁇ m or more. If it is less than 80 ⁇ m, the heat resistance may decrease.
  • the thickness of the P2 layer constituting the laminated sheet of the present invention is preferably 15 ⁇ m or more and 50 ⁇ m or less. If it is less than 15 ⁇ m, the adhesion between the layers may be lowered. When the thickness of the P2 layer is larger than 50 ⁇ m, the heat resistance may be lowered.
  • the thickness of the P3 layer constituting the laminated sheet of the present invention is preferably 50 ⁇ m or more. If it is less than 50 micrometers, adhesiveness with a sealing material may fall.
  • the laminated sheet of the present invention has a P1 layer and a P3 layer.
  • the laminated structure of the laminated sheet in the present invention is preferably a structure in which at least the P1 layer is located on the surface layer and the P3 layer is located on the opposite surface layer to the P1 layer.
  • the P1 layer is located on the reverse surface layer of the P1 layer means that the P1 layer is located on one outermost layer of the laminated sheet and the P3 layer is located on the other outermost layer.
  • the laminated sheet of the present invention can be a laminated body laminated with another film or the like. Also in such a laminated body, it is preferable that the P1 layer has a laminated structure provided on any one of the surface layers.
  • other films include polyester layers for increasing mechanical strength, antistatic layers, adhesion layers with other materials, UV resistant layers for further improving UV resistance, and flame resistance for imparting flame resistance
  • a layer, a hard coat layer for improving impact resistance and scratch resistance, and the like can be arbitrarily selected and used depending on applications.
  • the laminated sheet of the present invention is a laminated body laminated with another film or the like, when the laminated sheet of the present invention is used as a solar battery backsheet, other sheet materials or power generation elements are embedded.
  • the sealing material for example, ethylene vinyl acetate
  • the sealing material for example, ethylene vinyl acetate
  • the voltage at which partial discharge phenomenon, which is an index of insulation, is generated is improved.
  • a conductive layer to be formed may be formed.
  • Examples of the method for laminating the P1 layer, P2 layer, and P3 layer in the laminated sheet of the present invention include, for example, a raw material for the P1 layer mainly composed of polybutylene terephthalate resin and a main component composed of an adhesive polyolefin resin.
  • the raw material for P2 layer and the raw material for P3 layer mainly composed of polyolefin resin are supplied to different extruders, and after melting, P1 layer, P2 layer and P3 layer are merged in this order and laminated.
  • a method of processing into a sheet including a step of extruding from a T die into a sheet (coextrusion method), laminating a raw material of a coating layer into a sheet produced by a single film, putting it into an extruder, melting and extruding from a die Method (melt laminating method), each film is prepared separately and thermocompression-bonded by a heated roll group (thermal laminating method), adhesive
  • the coextrusion method is preferred in that the production process is short and the adhesion between the layers is good.
  • the manufacturing method by
  • the laminated sheet of the present invention is produced by a coextrusion method, first, a raw material for the P1 layer having a dried polybutylene terephthalate resin as a main constituent, a raw material for a P2 layer having an adhesive polyolefin resin as a main constituent, And three raw materials for P3 layer, the main component of which is polyolefin resin and polyolefin resin, heated to 240 ° C to 300 ° C, P2 layer and P3 layer to 180 ° C to 250 ° C under nitrogen flow Each is fed to an extruder and melted.
  • the P1 layer, the P2 layer and the P3 layer are joined and laminated in this order, and are coextruded from the T die into a sheet.
  • a multi-manifold die it is preferable to use a multi-manifold die from the viewpoint of suppressing lamination unevenness.
  • the laminated sheet of the present invention can be obtained by extruding the laminated sheet discharged from the T die by the above-described method onto a cooling body such as a casting drum and cooling and solidifying it.
  • the laminated sheet of the present invention obtained by the above-described method may be subjected to processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired.
  • processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired.
  • heat-treating the thermal dimensional stability of the laminated sheet of the present invention can be improved.
  • corona treatment or plasma treatment may be performed.
  • the solar cell backsheet of the present invention is composed of the laminated sheet of the present invention. That is, the laminated sheet of the present invention can be suitably used as a solar battery back sheet.
  • the solar cell of the present invention is characterized by using the solar cell backsheet of the present invention.
  • By using the laminated sheet of the present invention in a solar cell it becomes possible to increase the durability or reduce the thickness as compared with a conventional solar cell.
  • FIG. 1 A structural example of the solar cell of the present invention is shown in FIG.
  • a power generating element connected with a lead wire for taking out electricity (not shown in FIG. 1) is sealed with a transparent sealing material 2 such as EVA resin, and a transparent substrate 4 such as glass and the like.
  • the laminated sheet of the present invention is configured to be bonded as the solar battery backsheet 1
  • the configuration example of the solar battery of the present invention is not limited to this, and can be used for any configuration.
  • unit of this invention was shown in FIG. 1, it is also possible to use the composite sheet of the lamination sheet of this invention and another film according to the other required required characteristic.
  • a method of laminating with other films, etc. for example, a method of co-extrusion and processing into a sheet (co-extrusion method), a coating layer raw material is put into an extruder into a sheet made of a single film Then, melt extrusion and laminating while extruding from the die (melt laminating method), making each film separately, thermocompression bonding with heated rolls etc. (thermal laminating method), pasting through adhesive A method of bonding (adhesion method), a method of applying and drying a solution dissolved in a solvent (coating method), a method of combining these, and the like can be used.
  • the above-described solar cell backsheet 1 is installed on the back surface of the sealing material 2 in which the power generating element is sealed.
  • the solar cell backsheet of the present invention has an asymmetric configuration, and the P3 layer is disposed so as to be positioned on the sealing material 2 side, so that the adhesion with the sealing material can be further increased. This is preferable.
  • positioned so that P1 layer of the lamination sheet of this invention may be located in the opposite side to the sealing material 2 it becomes possible to improve the tolerance with respect to the ultraviolet rays etc. of the reflection from the ground, and high durability. It can be a solar cell or the thickness can be reduced.
  • the power generating element 3 converts light energy of sunlight into electric energy, and is based on crystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, dye enhancement Arbitrary elements such as a sensitive system can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost surface layer of the solar cell, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell of the present invention, the transparent substrate 4 having translucency can be made of any material as long as the above characteristics are satisfied. Examples thereof include glass, ethylene tetrafluoride-ethylene copolymer (ETFE), polyfluoride.
  • ETFE ethylene tetrafluoride-ethylene copolymer
  • Vinyl fluoride resin PVDF
  • PVDF polyvinylidene fluoride resin
  • TFE polytetrafluoroethylene resin
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • CFE polytrifluoroethylene chloride resin
  • Fluorinated resins such as polyvinylidene fluoride resins, polyolefin resins, acrylic resins, and mixtures thereof.
  • glass it is more preferable to use a tempered glass.
  • stretched the said resin uniaxially or biaxially from a viewpoint of mechanical strength is used preferably.
  • the sealing material 2 for sealing the power generating element covers the surface of the power generating element with resin and fixes it, protects the power generating element from the external environment, and has a light-transmitting base material for the purpose of electrical insulation.
  • a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used to adhere to the backsheet and the power generation element. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.
  • the solar battery back sheet using the laminated sheet of the present invention into the solar battery, it becomes possible to obtain a highly durable and / or thin solar battery compared to the conventional solar battery.
  • the solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.
  • the acetic acid permeability Pa (g / m 2 / day) in the backsheet of the present invention means the acetic acid permeability when acetic acid is in a saturated vapor pressure state (85 ° C.). And it is important for the back seat
  • the acetic acid permeability Pa of the backsheet of the present invention is 200 g / m 2 / day or more. Further, from the viewpoint of further suppressing power generation performance degradation, the acetic acid permeability Pa of the backsheet of the present invention is preferably 800 g / m 2 / day or more. On the other hand, the acetic acid permeability Pa is preferably as large as possible. However, considering that not only the expression (1) but also the expression (2) regarding the water vapor permeability Pw described later is satisfied at the same time, the acetic acid permeability Pa is 1500 g / m 2 / day. The following is preferable.
  • the water vapor transmission rate Pw (g / m 2 / day) in the backsheet of the present invention means the water vapor transmission rate in an environment of 40 ° C. and 90% RH.
  • the backsheet of the present invention has a water vapor transmission rate Pw of 2.5 g / in from the viewpoint of suppressing corrosion inside the solar cell module due to moisture, particularly discoloration due to corrosion of the collector electrode portion of the solar battery cell. It is important that it is not more than m 2 / day.
  • the water vapor transmission rate Pw is preferably as small as possible.
  • the water vapor transmission rate Pw is 0.5 g / m. 2 / day or more is preferable.
  • the back sheet has a P4 layer.
  • the P4 layer means a layer in which one selected from the group consisting of a polyester resin, a polyamide resin, and a fluororesin is a main constituent component.
  • the layer which is one main component selected from the group consisting of a polyester resin, a polyamide resin, and a fluororesin is one layer selected from the group consisting of a polyester resin, a polyamide resin, and a fluororesin.
  • the polyester resin suitably used as the main component of the P4 layer in the present invention is a resin obtained by polycondensation of dicarboxylic acid and dialcohol. This polyester resin can be used alone or in combination with other resins.
  • dicarboxylic acid used for obtaining the polyester resin examples include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • dialcohol used for obtaining a polyester resin examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and the like.
  • polyester resin polyethylene terephthalate and / or polybutylene terephthalate are preferable from the viewpoints of price, water vapor permeability, strength, heat resistance, and the like.
  • the polyamide resin suitably used as the main component of the P4 layer in the present invention is 1) a ring-opening polymerization of a compound having a lactam skeleton, and 2) an amino acid component having an amino group and a carboxyl group in one molecule. Condensed ones, 3) polycondensed diamine components and dicarboxylic acid components, and those obtained by copolymerizing 1) to 3).
  • the polyamide resin can be used alone or in combination with other resins.
  • Examples of the compound having a lactam skeleton used in 1) include ⁇ -caprolactam (nylon 6 is obtained by ring-opening polymerization), ⁇ -undecanlactam (nylon 11 is obtained by ring-opening polymerization), and ⁇ -laurolactam. And lactam compounds such as (Nylon 12 is obtained by ring-opening polymerization).
  • amino acid component having an amino group and a carboxyl group in one molecule used in 2) examples include amino acids such as ⁇ -aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • the diamine component used in 3) includes tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 1,2,2,4-tetramethylhexamethylene diamine, 2,4,4-trimethyl.
  • dicarboxylic acid component used in 3 examples include adipic acid, peric acid, azelaic acid, sepacic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, Examples thereof include dicarboxylic acids such as naphthalenedicarboxylic acid and dimer acid.
  • polystyrene resin any one of a polymer of the component alone or a copolymer containing two or more components can be used in the present invention.
  • polycaproamide nylon 6
  • polyhexamethylene adipamide nylon 66
  • polyhexamethylene sebacamide nylon 610
  • polyhexa Methylene dodecanamide nylon 612
  • polyhexamethylene terephthalamide nylon 6T
  • polyhexamethylene isophthalamide nylon 6I
  • polyundecanamide nylon 11
  • polydodecanamide nylon 12
  • the polyamide resin suitably used as the main constituent component of the P4 layer is nylon 6, nylon 66, nylon 610, nylon 11, in terms of crystallinity, strength, heat resistance and rigidity. And at least one resin selected from the group consisting of nylon 12 and nylon 12.
  • the fluororesin suitably used as the main component of the P4 layer in the present invention is 1) a polymer obtained by substituting some or all of the hydrocarbon atoms with fluorine atoms, and 2) one hydrocarbon.
  • fluororesins examples include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, polychlorotrifluoroethylene, And ethylene / chlorotrifluoroethylene copolymer.
  • the fluororesin suitably used as the main component of the P4 layer in the backsheet of the present invention is polyvinyl fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene, four A fluorinated ethylene / hexafluoropropylene copolymer is particularly preferred.
  • the P4 layer is a layer mainly composed of one selected from the group consisting of a polyester resin, a polyamide resin, and a fluororesin, but the P4 layer is made of a polyamide resin or polybutylene terephthalate. It is particularly preferable to use the main component.
  • the P4 layer preferably contains 0.1% by mass to 30% by mass of inorganic particles in 100% by mass of all components of the P4 layer.
  • the content of the inorganic particles in the P4 layer is more preferably 2% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 20% by mass or less.
  • the inorganic particles are used for imparting necessary functions to the back sheet depending on the purpose.
  • handling properties may be lowered or durability may be lowered.
  • the content of the inorganic particles in the P4 layer is less than 0.1% by mass, the effect due to the inclusion of the inorganic particles is difficult to obtain, and yellowing may occur.
  • inorganic particles suitable for use in the P4 layer include inorganic particles having ultraviolet absorbing ability, particles having a large refractive index difference from polyester resins, polyamide resins, and fluororesins, conductive particles, and pigments. Thus, it is possible to impart ultraviolet resistance, optical properties such as light reflectivity and whiteness, antistatic properties and the like.
  • the particle means a particle having a primary particle diameter of 5 nm or more based on the diameter of a projected equivalent equivalent circle. Unless otherwise specified, in the present invention, the particle size means a primary particle size, and the particle means a primary particle.
  • the inorganic particles suitably used for the P4 layer of the present invention include, for example, gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, Metals such as nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, antimony, indium, yttrium, lanthanum, zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, oxidation Metal oxides such as lanthanum soot, zirconium oxide, aluminum oxide, silicon oxide, lithium fluoride, magnesium fluoride soot, aluminum fluoride soot, metal fluorides such as cryolite, metal phosphates such as calcium phosphate, carbonates such as calcium carbonate Salt, barium sulfate And sulfates such as talc, talc and
  • metal oxides such as titanium oxide, zinc oxide, and cerium oxide, which are inorganic particles having ultraviolet absorbing ability, are used as the inorganic particles in the P4 layer.
  • titanium oxide as the inorganic particles in the P4 layer in that high reflection characteristics can be imparted, and it is more preferable to use rutile type titanium oxide in terms of higher ultraviolet resistance.
  • the resin and inorganic particles are melt kneaded in advance using a vent type biaxial kneading extruder or tandem type extruder.
  • the method is preferred.
  • a high-concentration master pellet having a large amount of inorganic particles is prepared, mixed with the resin and diluted, and the predetermined P4 layer contains inorganic particles. It is preferable to set the ratio from the viewpoint of durability.
  • the P4 layer and the P6 layer of the backsheet of the present invention may have other additives (for example, a heat stabilizer, an ultraviolet absorber, Examples include weathering stabilizers, organic lubricants, pigments, dyes, fillers, antistatic agents, nucleating agents, etc.
  • a heat stabilizer for example, a heat stabilizer, an ultraviolet absorber
  • examples include weathering stabilizers, organic lubricants, pigments, dyes, fillers, antistatic agents, nucleating agents, etc.
  • the inorganic particles referred to in the present invention are not included in the additive herein. You may do it.
  • an ultraviolet absorber is selected as an additive and contained in the P4 layer and / or the P6 layer
  • the ultraviolet resistance of the backsheet of the present invention can be further improved.
  • an antistatic agent or the like is contained in the P4 layer and / or the P6 layer, an improvement in withstand voltage can be expected.
  • the P4 layer in the present invention is located on the surface layer of the back sheet from the viewpoint of flame retardancy.
  • the P4 layer being positioned on the surface means that the P4 layer is positioned on one outermost layer of the backsheet of the present invention.
  • the P5 layer is preferably located between the P4 layer and the P6 layer described later.
  • the P5 layer is a layer mainly composed of one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer.
  • the main constituent is one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer. It means that one selected from the group consisting of a crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer is contained more than 50% by mass and 100% by mass or less.
  • the P5 layer is preferably located between the P4 layer and the P6 layer.
  • the P4 layer is located on the surface layer, and when the P6 layer is located on the surface opposite to the P4 layer, It means that the P5 layer is located in the inner layer between these two layers.
  • the P5 layer preferably has a function of adhering to both the P4 layer and the P6 layer.
  • the low crystalline soft polymer that is one of the main components of the P5 layer preferably has a crystallinity of 50% or less and a melting point of 170 ° C. or less.
  • an acid-modified olefin, an unsaturated polyolefin, etc. Can be mentioned.
  • the acrylic adhesive that is one of the main components of the P5 layer include an ethylene-acrylic ester-maleic anhydride terpolymer.
  • the P5 layer is preferably composed of acid-modified polyolefin as a main constituent.
  • the acid-modified polyolefin include “Admer” (registered trademark) manufactured by Mitsui Chemicals, Inc. and “Modic” (registered trademark) manufactured by Mitsubishi Chemical Corporation.
  • the layer in which the olefin resin is the main constituent is designated as P6 layer.
  • the olefin resin used in the P6 layer include polyethylene, polypropylene, polybutene, polymethylpentene, polycycloolefin, polyhexene, polyoctene, polydecene, and polydodecene.
  • the olefin resin that is the main component of the P6 layer is preferably polyethylene or polypropylene.
  • These olefin resins may be mixed and copolymerized with other olefin components. For example, when an ethylene-propylene copolymer or an ethylene-propylene-butene copolymer is used, the melting point of the resin can be lowered.
  • an olefin resin is a main component means that 100 mass% of olefin resin is contained more than 50 mass% in 100 mass% of all the components of this layer.
  • the melting point (hereinafter also referred to as melting endothermic peak temperature) of the olefin resin that is the main component of the P6 layer in the present invention is preferably 120 ° C. or higher and 170 ° C. or lower. If the melting point of the olefin resin in the P6 layer is less than 120 ° C, the heat resistance may be inferior. On the other hand, when the melting point of the olefin resin in the P6 layer exceeds 170 ° C., the adhesiveness with the sealing material may be lowered.
  • the backsheet of the present invention preferably has a P4 layer and a P6 layer, the P6 layer contains inorganic particles, the P4 layer is located on the surface layer, and the P6 layer is located on the surface opposite to the P4 layer. Further, the back sheet of the present invention has a total thickness of Ta ( ⁇ m), a thickness of the P4 layer of T4 ( ⁇ m), a thickness of the P6 layer of T6 ( ⁇ m), and the content of inorganic particles in the P6 layer. It is more preferable that all of the formulas (3) to (5) are satisfied when M (mass%) is used.
  • T4 is obtained using only the P4 layer of the surface layer
  • T6 and M are obtained using only the P6 layer of the reverse surface layer
  • Formula (3) formulates the amount of inorganic particles per thickness, and in order to express the effect of inorganic particles, it is important to increase the concentration of inorganic particles as the thickness increases. Show. In Formula (3), when M / T6 is smaller than 0.05, the P6 layer is easily yellowed due to deterioration. If M / T6 is greater than 0.5, the adhesion to EVA may be reduced.
  • the P6 layer preferably contains inorganic particles.
  • the inorganic particles in the P6 layer are used for imparting necessary functions to the back sheet depending on the purpose.
  • the inorganic particles in the P6 layer the same inorganic particles as those mentioned as the inorganic particles used in the P4 layer can be used.
  • the inorganic particles in the P6 layer are obtained when a metal oxide such as titanium oxide, zinc oxide, cerium oxide or the like having ultraviolet absorbing ability is used. It is preferable in that it can exhibit the effect of reducing coloration due to deterioration of the back sheet over a long period of time by utilizing the ultraviolet resistance by the inorganic particles.
  • titanium oxide as inorganic particles in the P6 layer in that high reflection characteristics can be imparted, and it is more preferable to use rutile type titanium oxide in terms of higher ultraviolet resistance.
  • Formula (4) represents the range of the thickness of the entire back sheet.
  • Ta is smaller than 200 ⁇ m, heat resistance and water vapor permeability may be inferior.
  • Ta is larger than 500 ⁇ m, processability is poor and conveyance is difficult, so that process suitability may be poor, and a solar cell module that is required to be lightweight and save space may be too thick.
  • Formula (5) shows the ratio of the thickness of the P4 layer to the total thickness, and the heat resistance improves as the thickness of the P4 layer increases. Therefore, if the value of T4 / Ta is less than 0.3, the heat resistance May decrease. The durability increases as the value of T4 / Ta increases. However, since the P4 layer is often expensive in comparison with the P6 layer, it is preferably 0.5 or less from the viewpoint of reducing the product cost.
  • the thickness T5 ( ⁇ m) of the P5 layer is preferably 15 to 50 ⁇ m.
  • the thickness T5 ( ⁇ m) of each P5 layer is preferably 15 to 50 ⁇ m.
  • T5 is smaller than 15 ⁇ m, the adhesion with the P4 layer or the P6 layer is lowered, and delamination may occur.
  • T5 is larger than 50 ⁇ m, the flame retardancy is likely to deteriorate when the combustibility of the backsheet is confirmed.
  • T5 is more preferably 20 ⁇ m or more and 40 ⁇ m or less.
  • delamination refers to what peels at the interface such as between the P4 layer and the P5 layer and between the P5 layer and the P6 layer.
  • the laminated structure of the back sheet in the present invention is a structure in which at least the P4 layer is located on the surface layer, and the P6 layer is located on the surface opposite to the P4 layer.
  • the P6 layer being positioned on the reverse surface layer of the P4 layer means that the P4 layer is positioned on one outermost layer of the backsheet and therefore the P6 layer is positioned on the other outermost layer.
  • the layer configuration (layer order) of the backsheet of the present invention is preferably P4 layer / P5 layer / P6 layer.
  • Examples of the method of laminating the P4 layer, the P5 layer, and the P6 layer in the backsheet of the present invention include, for example, a polyamide resin for the P4 layer or a raw material mainly comprising polybutylene terephthalate, and a low crystalline softness for the P5 layer.
  • a raw material mainly composed of one selected from the group consisting of a polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer, and a raw material mainly composed of an olefin resin for the P6 layer are separately extruded.
  • a sheet manufactured by a manufacturing method including a step of feeding a P4 layer, a P5 layer, and a P6 layer after being melted together, laminating them in this order, and extruding them into a sheet form from a T die.
  • a method of laminating a coating layer raw material into an extruder and laminating while extruding and extruding from a die (melt laminating method), producing each sheet separately,
  • a method of thermocompression bonding with a heated group of rolls thermocompression bonding with a heated group of rolls (thermal lamination method), a method of bonding via an adhesive (adhesion method), a method of applying and drying a solution dissolved in a solvent (coating method), and A method combining these can be used.
  • the coextrusion method is preferred in that the production process is short and the adhesion between the layers is good.
  • the manufacturing method by a coextrusion method is explained in full detail.
  • the backsheet of the present invention is produced by the coextrusion method, first, a dried polyamide resin for P4 layer or a raw material mainly comprising polybutylene terephthalate, a low crystalline soft polymer for P5 layer, an acrylic adhesive And a raw material mainly composed of one selected from the group consisting of ethylene vinyl acetate copolymer and a raw material mainly composed of an olefin resin for P6 layer under a nitrogen stream, a raw material for P4 layer
  • the raw material for P5 layer and the raw material for P6 layer are fed to three extruders heated to 180 ° C or higher and 250 ° C or lower, respectively, and melted.
  • the P4 layer, the P5 layer and the P6 layer are joined and laminated in this order, and are coextruded from the T die into a sheet.
  • a multi-manifold die it is preferable to use a multi-manifold die from the viewpoint of suppressing lamination unevenness.
  • the back sheet discharged from the T die by the above method is extruded onto a cooling body such as a casting drum and solidified by cooling, whereby the back sheet of the present invention can be obtained.
  • the back sheet of the present invention obtained by the above-described method may be subjected to processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired.
  • processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired.
  • heat-treating the thermal dimensional stability of the backsheet of the present invention can be improved.
  • corona treatment or plasma treatment may be performed.
  • the solar cell module of the present invention has the back sheet for solar cell of the present invention.
  • the back sheet of the present invention By using the back sheet of the present invention in a solar cell module, it is possible to maintain power generation characteristics for a long period of time compared to a conventional solar cell module.
  • a configuration example of the solar cell module of the present invention is shown in FIG. In FIG. 1, a solar cell connected with a lead wire for taking out electricity (not shown in FIG. 1) is sealed with a transparent sealing material 2 such as EVA resin, and a transparent substrate 4 such as glass.
  • the solar cell backsheet 1 of the present invention is bonded together, and the configuration example of the solar cell module of the present invention is not limited to this and can be used for any configuration.
  • the above-described solar cell backsheet 1 is installed on the back surface of the sealing material 2 that seals the solar cells.
  • the solar cell backsheet of the present invention has an asymmetric configuration, and the P6 layer is disposed so as to be positioned on the sealing material 2 side, so that the adhesion with the sealing material can be further increased. This is preferable.
  • seat of this invention may be located in the opposite side to the sealing material 2, it becomes possible to raise the tolerance with respect to the ultraviolet-ray of reflection from the ground, etc., and highly durable. It can be a solar cell module or the thickness can be reduced.
  • the solar battery cell 3 converts light energy of sunlight into electric energy, and is made of polycrystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, Arbitrary elements, such as a dye sensitizing system, can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost layer of the solar cell module, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell module of the present invention, the transparent substrate 4 having translucency can use any material as long as it satisfies the above characteristics.
  • Examples thereof include glass, ethylenetetrafluoroethylene (ETFE), and polyvinyl fluoride (PVF). ), Fluorinated resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (TFE), tetrafluoroethylene-hexafluoropropylene (FEP), polytrifluoroethylene chloride (CTFE), polyvinylidene fluoride, Preferred examples include olefin resins, acrylic resins, and mixtures thereof. In the case of glass, it is more preferable to use a tempered glass. Moreover, when using the resin-made translucent base material, what extended
  • PVDF polyvinylidene fluoride
  • TFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene
  • CTFE polytrifluoroethylene chloride
  • the surface is subjected to corona treatment, plasma treatment, ozone treatment, and easy adhesion treatment. Done.
  • the sealing material 2 for sealing the solar battery cell covers and fixes the unevenness of the surface of the solar battery cell with a resin, protects the solar battery cell from the external environment, and has a light transmitting property in addition to the purpose of electrical insulation. Therefore, a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.
  • EVA ethylene-vinyl acetate copolymer
  • EMA ethylene-methyl acrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMA ethylene-methacrylic acid copolymer
  • Ionomer resins polyvin
  • the solar cell module of the present invention is not limited to outdoor use and indoor use, such as a solar power generation system and a power source for small electronic components, and can be suitably used for various uses.
  • the P1 layer, P3 layer, P4 layer, and P6 layer are each cut or peeled off from the laminated sheet (back sheet) to separate the P1 layer, P3 layer, P4 layer, and P6 layer. The content of particles was calculated.
  • ⁇ Tcg Tc ⁇ Tg
  • ⁇ Tcg Tc ⁇ Tg
  • breaking strength When the breaking strength is 80 MPa or more: S When the breaking strength is 40 MPa or more and less than 80 MPa: A When the breaking strength is 30 MPa or more and less than 40 MPa: B When the breaking strength is 20 MPa or more and less than 30 MPa: C When the breaking strength is less than 20 MPa: D S to C pass, and S is the best among them.
  • breaking elongation E0 was measured according to the said (4) term, and elongation retention was computed by the following formula using the obtained breaking elongation E0 and E1.
  • ⁇ Elongation retention (%) (E1 / E0) ⁇ 100
  • the obtained elongation retention was determined as follows. When the elongation retention is 50% or more: S When the elongation retention is 40% or more and less than 50%: A When the elongation retention is 30% or more and less than 40%: B When the elongation retention is 20% or more and less than 30%: C When the elongation retention is less than 20%: D S to C pass, and S is the best among them.
  • breaking elongation E0 was measured according to the said (4) term, and elongation retention was computed by the following formula using the obtained breaking elongation E0 and E1.
  • ⁇ Elongation retention (%) (E1 / E0) ⁇ 100
  • the obtained elongation retention was determined as follows. When the elongation retention is 50% or more: S When the elongation retention is 40% or more and less than 50%: A When the elongation retention is 30% or more and less than 40%: B When the elongation retention is 20% or more and less than 30%: C When the elongation retention is less than 20%: D S to C pass, and S is the best among them.
  • the b values before and after the irradiation were determined by measuring the b values before and after the P1 layer and calculating the average value.
  • the difference (b value after irradiation to b value before irradiation) was defined as a color tone change ⁇ b1 after ultraviolet irradiation.
  • the obtained color tone change ( ⁇ b1) was determined as follows.
  • the b values before and after the irradiation were determined by measuring the b values before and after the P3 layer and calculating the average value.
  • the difference (b value after irradiation from b value after irradiation) was defined as a color tone change ⁇ b2 after ultraviolet irradiation.
  • the obtained color tone change ( ⁇ b2) was determined as follows.
  • the adhesion with the sealing material was determined as follows.
  • peel strength is 50 N / 10 mm or more:
  • S When the peel strength is 40 N / 10 mm or more and less than 50 N / 10 mm:
  • A When peel strength is 30N / 10mm or more and less than 40N / 10mm:
  • B When the peel strength is 20 N / 10 mm or more and less than 30 N / 10 mm:
  • C When peel strength is less than 20 N / 10 mm: D S to C pass, and S is the best among them.
  • the interlayer adhesion was evaluated from the delamination strength after treatment at 85 ° C and 85% RH for 1000 hours.
  • the delamination strength the strength at the time of peeling in the T shape measured according to JIS K6854-3 (1999) was used.
  • the interlayer was defined as an interlayer capable of interfacial separation such as between the P1 layer and the P2 layer and between the P2 layer and the P3 layer.
  • the test piece width of the delamination strength test was 15 mm, and two test pieces were prepared. The test piece was changed in place and measured at three locations, and the average value of the obtained measurement values was taken as the delamination strength.
  • the interlayer adhesion was determined as follows.
  • peel strength When peel strength is 10N / 15mm or more: S When the peel strength is 6 N / 15 mm or more and less than 10 N / 15 mm: A When peel strength is 3N / 15mm or more and less than 6N / 15mm: B When peel strength is 1N / 15mm or more and less than 3N / 15mm: C When peel strength is less than 1 N / 15 mm: D S to C pass, and S is the best among them.
  • FIG. 2 shows a cross-sectional view and FIG. 3 shows a top view of the jig 11 used for measuring acetic acid permeability.
  • the jig 11 is made of stainless steel and has a 65 cm 2 circular opening, and a jig lower part which is a container containing acetic acid having the same shape as the jig 7 on the upper surface of the container.
  • the acetic acid stock solution 9 is put into the lower part 8 of the jig.
  • the laminated sheet to be measured, the back sheet 1, has a mesh 10 made of stainless steel with a wire diameter of 0.29 mm and a mesh size of 0.98 mm between the jig lower part 8 and the jig upper part 7 on the jig upper part 7 side.
  • the jig upper part 7 and the jig lower part 8 were fixed with screws so as to prevent acetic acid vapor from escaping and sandwiched together with an O-ring set on the jig lower part 8.
  • the mass W1 at room temperature after the jig 11 prepared with the back sheet 1 and the acetic acid stock solution 9 satisfying the measurement area of 65 cm 2 was left at 85 ° C. for 1 hour in that state was measured.
  • the P6 layer yellowed backsheet was cut into the shape of a measurement piece (3 cm ⁇ 3 cm), and then subjected to treatment at 120 ° C. for 72 hours in a hot air oven PV (H) -212 manufactured by Espec Corp.
  • PV (H) -212 manufactured by Espec Corp.
  • the sample measurement diameter was set to 30 mm ⁇ , the b value on the P6 layer side was measured, and the average value was calculated to obtain the difference between the b values before and after the treatment.
  • ⁇ b was obtained by subtracting the b value before processing from the b value after processing, and the following determination was performed.
  • S When the color change ⁇ b is 3 or more and less than 5: A When the color change ⁇ b is 5 or more and less than 8: B When color change ⁇ b is 8 or more and 10 or less: C When the color change ⁇ b exceeds 10, D.
  • the partial discharge voltage of the back sheet was determined using a partial discharge tester KPD2050 (manufactured by Kikusui Electronics Co., Ltd.).
  • the test conditions are as follows.
  • the output voltage application pattern on the output sheet is a pattern in which the first stage simply increases the voltage from 0 V to a predetermined test voltage, the second stage is a pattern that maintains a predetermined test voltage, and the third stage is a predetermined test A pattern composed of three stages of patterns in which the voltage is simply dropped from 0 to 0 V is selected.
  • the frequency is 50 Hz.
  • the test voltage is 1 kV.
  • the first stage time T1 is 10 sec
  • the second stage time T2 is 2 sec
  • the third stage time T3 is 10 sec.
  • the counting method on the pulse count sheet is “+” (plus), and the detection level is 50%.
  • the charge amount in the range sheet is set to 1,000 pc.
  • the pulse count is 100,000.
  • the start voltage is 1.0 pc and the extinction voltage is 1.0 pc.
  • the measurement was carried out at 10 arbitrary positions in the film plane, and the average value was defined as the partial discharge voltage V0. Further, the measurement was performed using a measurement sample left overnight in a room at 23 ° C. and 65% RH.
  • partial discharge voltage is 1,050 V or more: S When the partial discharge voltage is 950 V or more and less than 1,050 V: A When partial discharge voltage is 700V or more and less than 950V: B When the partial discharge voltage is 300V or more and less than 700V: C When partial discharge voltage is less than 300V: D.
  • Adhesion with sealing material (135 ° C vacuum lamination) Based on JIS K6854 (1994), the adhesion between the EVA sheet (sealing material) and the P6 layer of the back sheet was evaluated from the peel strength.
  • the test specimen is a 500 ⁇ m thick EVA sheet manufactured by Sanvic Co., Ltd. and a corona-treated Example and Comparative Example back sheet on a 3 mm thick semi-tempered glass, and a commercially available glass laminator is used. Then, after evacuation, press-treated for 15 minutes with a load of 29.4 N / cm 2 under a heating condition of 135 ° C. was used.
  • the width of the test piece for the peel strength test was 10 mm, two test pieces were prepared, and each test piece was measured at three locations with different locations, and the average value of the obtained measured values was taken as the peel strength value. From the obtained peel strength, the adhesiveness of the sealing material was determined as follows. In the case of a backsheet not having the P6 layer, the evaluation is performed in the same manner.
  • peel strength When peel strength is 50 N / 10 mm or more: S When the peel strength is 40 N / 10 mm or more and less than 50 N / 10 mm: A When peel strength is 30N / 10mm or more and less than 40N / 10mm: B When the peel strength is 20 N / 10 mm or more and less than 30 N / 10 mm: C When peel strength is less than 20 N / 10 mm: D.
  • the P1 layer is scraped from the rigid amorphous amount laminated sheet, and subjected to differential scanning calorimetry (DSC) and temperature modulation DSC method with the following apparatus and conditions. 65, no. 11 (2009) P.I.
  • the amount of rigid amorphous was calculated using the method 428.
  • ⁇ DSC method> Apparatus: DSC Q1000 manufactured by TA Instruments Atmosphere: Nitrogen flow (50 mL / min) Temperature / calorie calibration: High purity indium Temperature range: 0-250 ° C Temperature increase rate: 10 ° C / min Sample weight: 10mg Sample container: Aluminum standard container ⁇ Temperature modulation DSC method> Apparatus: DSC Q1000 manufactured by TA Instruments Atmosphere: Nitrogen flow (50 mL / min) Temperature / calorie calibration: High purity indium specific heat calibration: Sapphire temperature range: 0-300 ° C Temperature increase rate: 2 ° C / min Sample weight: 5mg Sample container: Aluminum standard container Note that the rigid amorphous amount: ⁇ ra (%) was calculated by the following formula.
  • the particle size distribution is obtained by laser analysis / scattering method for the remaining components, and the average particle size is determined by 50% of the integrated value in the particle size distribution. It was.
  • the particle size distribution referred to here is “Laser diffraction / scattering particle size distribution analyzer LS series” (Beckman Coulter, Inc.), Mayumi Toyoda, “Measuring particle size distribution” (Beckman Coulter, Inc., Particle Properties Division, Academic Team) Sought in accordance with The measurement solution was prepared so that inorganic particles were added to pure water and dispersed with a homogenizer for 1 minute, so that the display of the concentration adjustment window of the apparatus was 45 to 55%.
  • Polybutylene terephthalate resin “Trecon” (registered trademark) 1200M (manufactured by Toray Industries, Inc.) as the polybutylene terephthalate resin (PBT) constituting the P1 layer in Examples 1 to 26, 57 to 72, and Comparative Example 1 Using.
  • Example 25 “Noblen” (registered trademark) FLX80E4 manufactured by Sumitomo Chemical Co., Ltd. was used as PP1. Acid Modified Polyolefin “Modic” (registered trademark) P553A manufactured by Mitsubishi Chemical Corporation was used as Resin 1 as the resin constituting the P2 layer in Examples 1 to 26 and 57 to 72. Polyolefin Elastomer For Example 24, “Notio” (registered trademark) PN2060 manufactured by Mitsui Chemicals, Inc. was used as the elastomer 1 as the polyolefin elastomer.
  • Inorganic particles Examples 1-5, 7-26, 57-72, P1 layer of Comparative Example 1 and Examples 1-9, 11-26, Inorganic particles of P3 layer of Comparative Example 2 use titanium dioxide It was.
  • the titanium dioxide of the P1 layer has a desired concentration of a masterbatch prepared in a ratio of 50% by mass / 50% by mass of the resin and titanium dioxide used as main components of the P1 layer in each example and comparative example.
  • a master batch prepared by adding 30% by mass / 70% by mass of the resin and titanium dioxide used as the main constituent components of the P3 layer for each example and comparative example was added to a desired concentration. .
  • End-capping agent used for the P1 layer of Examples 1, 3 to 25, 57 to 72 and Comparative Example 1 was P-400 manufactured by Rhein Chemie.
  • Example 26 “Carbodilite” (registered trademark) HMV-15CA manufactured by Nisshinbo Chemical Co., Ltd. was used.
  • Crystal nucleating agent Sodium montanate was used as the crystal nucleating agent for the P1 layer of Examples 61 to 63.
  • ⁇ Inorganic particles (3 ⁇ m to 20 ⁇ m) As the inorganic particles of 3 ⁇ m or more and 20 ⁇ m or less of the P3 layer of Examples 64-72, talc having an average particle diameter of 5 ⁇ m was used.
  • Examples 1 to 26, 61 to 72 Using the extruder 1, the extruder 2 and the extruder 3, the raw materials shown in Table 1 and Table 5 are supplied to each extruder so as to have a desired blending ratio, and then the layer melt-extruded from the extruder 1 is P1. Layers, Extruder 2 is P2 layer, Extruder 3 is P3 layer, P1 layer / P2 layer / P3 layer are laminated in order of multi-manifold, and the resin discharged from the die is 25 ° C. A laminated sheet was obtained by cooling and solidifying on a cast drum. The thicknesses shown in Tables 1 and 5 were obtained for the P1, P2, and P3 layers. The evaluation shown in Table 2 and Table 6 was implemented about the obtained lamination sheet. As a result, as shown in Tables 2 and 6, the examples were found to be excellent laminated sheets.
  • Example 24 contained an elastomer in the P2 layer, the interlayer adhesion was extremely excellent.
  • Example 57 A laminated sheet was prepared in the same manner as in Example 1 except that the cast drum temperature was changed to 15 ° C. (Example 57), 20 ° C. (Example 58), 40 ° C. (Example 59), and 50 ° C. (Example 60), respectively. did.
  • the evaluation shown in Table 6 was implemented about the obtained lamination sheet. As a result, as shown in Table 6, it was found that the examples were excellent laminated sheets.
  • a laminated sheet capable of achieving both heat and moisture resistance, heat resistance, and adhesion between the sealing material and the laminated sheet using a conventional polybutylene terephthalate resin.
  • Such laminated sheets are suitable for use in applications where importance is placed on wet heat resistance, resistance to ultraviolet rays, and light reflectivity, including solar cell backsheets, liquid crystal display reflectors, automotive materials, and building materials. can do.
  • a laminated sheet that can be suitably used as a solar battery backsheet, and a method for producing the laminated sheet can be provided.
  • Example 27 to 56 Comparative Example 5
  • Polyamide resin Nylon 6 resin “Amilan” registered trademark
  • CM1021T manufactured by Toray Industries, Inc.
  • PA6 polyamide resin constituting the P4 layer in Examples 27, 34 to 39, 41 to 49 and Comparative Examples 4 and 5 Tm; 225 ° C.
  • Polyethylene terephthalate As polyethylene terephthalate (PET) constituting the P4 layer in Example 28, a film of 25 ⁇ m “Lumirror” (registered trademark) S10 (manufactured by Toray Industries, Inc.) was used.
  • Polyvinyl fluoride As the polyvinyl fluoride (PVF) constituting the P4 layer in Example 30, a 38 ⁇ m “Tedra” (registered trademark) (manufactured by Dupont) film was used.
  • Ethylenetetrafluoroethylene As ethylenetetrafluoroethylene (ETFE) constituting the P4 layer in Example 31, a film of 50 ⁇ m “Toyoflon” (registered trademark) EL (manufactured by Toray Film Processing Co., Ltd.) was used.
  • -Tetrafluoroethylene-propylene hexafluoride As the tetrafluoroethylene-hexafluoropropylene (FEP) constituting the P4 layer in Example 32, 25 ⁇ m "Toyoflon” (registered trademark) FL (Toray Film Processing Co., Ltd.) Manufactured film).
  • Example 46 “Evolue” (registered trademark) SP2530 manufactured by Sumitomo Chemical Co., Ltd. was used as LLDPE1.
  • Example 47 “Evolue” (registered trademark) SP2540 manufactured by Sumitomo Chemical Co., Ltd. was used as LLDPE2.
  • Example 48 1% ethylene copolymer polypropylene was used as EPC1.
  • Example 49 “Noblen” (registered trademark) FLX80E4 manufactured by Sumitomo Chemical Co., Ltd. was used as PP1. Acid Modified Olefin “Modic” (registered trademark) P553A manufactured by Mitsubishi Chemical Corporation was used as Resin 1 as the resin constituting the P5 layer in Examples 34 to 39, 41 to 54, and Comparative Example 5. -Ethylene vinyl acetate copolymer "Modic” (registered trademark) A515 manufactured by Mitsubishi Chemical Corporation was used as the resin 2 as the resin constituting the P5 layer in Example 55. Acrylic Adhesive “Bond First” (registered trademark) 7L manufactured by Sumitomo Chemical Co., Ltd.
  • Example 27 was used as the resin 3 as the resin constituting the P5 layer in Example 56.
  • Inorganic particles Examples 27, 29, 34 to 39, 41 to 54, inorganic particles used in the P4 layer of Comparative Example 5 and the P6 layer of Examples 27 to 54 and Comparative Example 5 have an average particle size of 0.25 ⁇ m. Titanium dioxide was used.
  • the titanium dioxide of the P4 layer has a desired concentration of the resin used as the main component of the P4 layer and the resin obtained by mastering titanium dioxide at a ratio of 50% by mass / 50% by mass for each example and comparative example.
  • the titanium dioxide of P6 layer was added so that the resin used as the main component of P6 layer for each Example and Comparative Example and the resin mastered at a ratio of 30% by mass / 70% by mass of titanium dioxide to a desired concentration. .
  • Examples 27 and 29 use the extruder 4 and the extruder 6 to supply the raw materials shown in Table 3-1 to each extruder so as to have a desired blending ratio.
  • the layers melt-extruded from the extruder 4 are P4 layers
  • the extruder 6 is P6 layers
  • the layers are joined together in a multi-manifold so that they are laminated in the order of P4 layers / P6 layers, and the resin discharged from the die is cast.
  • a back sheet was obtained by cooling and solidifying on a drum.
  • Examples 28, 30 to 33, and Comparative Example 3 were used for adhesion between the respective layers by the dry laminating method so as to have the desired configurations shown in Tables 3-1 and 3-2. Lamination was performed using a polyurethane adhesive as an adhesive.
  • the EPBC 1 used in Examples 28 and 30 to 33 is a resin in which raw materials are supplied to the extruder 6 in advance so as to obtain a desired blending ratio, and then melt extruded from the extruder 6 and discharged from the die. A single layer sheet obtained by cooling and solidifying on a cast drum was used.
  • Example 39 raw materials were supplied to the extruder 6 so as to obtain a desired blending ratio, and then the resin melt-extruded from the extruder 6 and discharged from the die was cooled and solidified on a cast drum. A layer sheet was used.
  • the flux “HOZAN H722” was applied to the front and back silver electrodes of the solar cell “Qcells Q6LPT-G2” with a dispenser, and the wiring was cut to a length of 155 mm on the front and back silver electrodes.
  • the material “Hitachi Cable Co., Ltd. copper foil SSA-SPS0.2 ⁇ 1.5 (20)” 10 mm away from one end of the cell on the surface side is the end of the wiring material, and the back side is symmetrical with the surface side. Then, the soldering iron was brought into contact with the soldering iron from the back side of the cell using a soldering iron, and the front and back sides were simultaneously soldered to produce one cell string.
  • the thicknesses of the P4 layer, the P5 layer, and the P6 layer, the acetic acid permeability Pa, and the water vapor permeability Pw were as shown in Tables 3-1 and 3-2. Further, the evaluation shown in Tables 4-1 and 4-2 was performed on the obtained back sheet and the solar cell module using the back sheet. As a result, as shown in Tables 4-1 and 4-2, the examples were found to be excellent backsheets. In Comparative Example 5, since Pw was larger than 2.5, the color of the cell collector electrode was inferior.
  • a polyurethane adhesive is used as an adhesive, a 125 ⁇ m white polyethylene terephthalate film “Lumirror” E20F (manufactured by Toray Industries, Inc.), and an inorganic compound vapor deposition layer made of aluminum oxide.
  • Pa 10 g / 24 hr / m 2
  • Pw 0.2 g / 24 hr / m 2
  • a solar cell module was produced using this back sheet, and the maximum output retention rate was compared to about 85 hours at 85 ° C. and 85% RH 5000 hours. As a result, the maximum output retention rate was 10%, and Pa was smaller than 200. Was inferior.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une feuille stratifiée ayant : une couche ayant une résine de poly(téréphtalate de butylène) comme composant principal (couche P1) ; et une couche ayant une résine de polyoléfine comme composant principal (couche P3). Une feuille arrière de cellule solaire, caractérisée en ce que la perméabilité à l'acide acétique (Pa) (g/m2/jour) à 85°C et la perméabilité à la vapeur d'eau (Pw) (g/m2/jour) à 40°C, 90 % d'humidité relative (RH) satisfont les relations (1) 200 ≤ Pa et (2) Pw ≤ 2,5. L'invention concerne une feuille stratifiée ayant une meilleure résistance à la chaleur humide et une capacité améliorée à obtenir à la fois une résistance à la chaleur et une performance d'adhésion par rapport à un élément d'étanchéité comparé avec une feuille stratifiée classique dans laquelle une résine de poly(téréphtalate de butylène) est utilisée, et un procédé de fabrication de la feuille stratifiée. L'invention concerne également une feuille arrière de module de cellule solaire qui est peu coûteuse et qui est apte à prévenir la décoloration de l'électrode collectrice d'une cellule solaire tout en maintenant les caractéristiques de production d'énergie du module de cellule solaire pendant une longue période, et un procédé de fabrication de la feuille arrière de module de cellule solaire.
PCT/JP2013/082533 2012-12-10 2013-12-04 Feuille stratifiée et son procédé de fabrication, feuille arrière de cellule solaire, module de cellule solaire et procédé de fabrication de feuille arrière de cellule solaire WO2014091973A1 (fr)

Priority Applications (3)

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KR1020157013902A KR20150095635A (ko) 2012-12-10 2013-12-04 적층 시트 및 그의 제조 방법, 및 태양 전지용 백시트, 태양 전지 모듈 및 태양 전지용 백시트의 제조 방법
JP2014508619A JP6287829B2 (ja) 2012-12-10 2013-12-04 積層シート及びその製造方法、並びに太陽電池用バックシート、太陽電池モジュール及び太陽電池用バックシートの製造方法
CN201380064004.XA CN104822528B (zh) 2012-12-10 2013-12-04 层叠片材及其制造方法、以及太阳能电池用背板、太阳能电池组件和太阳能电池用背板的制造方法

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JP2012-269009 2012-12-10
JP2012269009 2012-12-10
JP2012272025 2012-12-13
JP2012-272025 2012-12-13

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CN (1) CN104822528B (fr)
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WO2017213864A1 (fr) * 2016-06-10 2017-12-14 Soliculture, Inc. Matériau à base de copolyester amorphe dans un module photovoltaïque
WO2019185842A1 (fr) * 2018-03-28 2019-10-03 Dsm Ip Assets B.V. Feuille de support comprenant du polybutylène téréphtalate
JP2020072159A (ja) * 2018-10-30 2020-05-07 大日本印刷株式会社 太陽電池モジュール用の透明保護シート

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CN109742295B (zh) * 2018-12-28 2022-09-09 界首市天鸿新材料股份有限公司 一种干法锂电池隔膜及其制备方法
TWI707773B (zh) * 2019-10-15 2020-10-21 南亞塑膠工業股份有限公司 用於太陽能電池的背板及其製法

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WO2017213864A1 (fr) * 2016-06-10 2017-12-14 Soliculture, Inc. Matériau à base de copolyester amorphe dans un module photovoltaïque
WO2019185842A1 (fr) * 2018-03-28 2019-10-03 Dsm Ip Assets B.V. Feuille de support comprenant du polybutylène téréphtalate
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TW201429717A (zh) 2014-08-01
KR20150095635A (ko) 2015-08-21
JPWO2014091973A1 (ja) 2017-01-12
JP6287829B2 (ja) 2018-03-07
TWI604951B (zh) 2017-11-11
CN104822528A (zh) 2015-08-05

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