WO2012057293A1 - Film feuilleté de polyphénylène-éther, feuille de cellule solaire et module de cellule solaire - Google Patents

Film feuilleté de polyphénylène-éther, feuille de cellule solaire et module de cellule solaire Download PDF

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Publication number
WO2012057293A1
WO2012057293A1 PCT/JP2011/074872 JP2011074872W WO2012057293A1 WO 2012057293 A1 WO2012057293 A1 WO 2012057293A1 JP 2011074872 W JP2011074872 W JP 2011074872W WO 2012057293 A1 WO2012057293 A1 WO 2012057293A1
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Prior art keywords
solar cell
polyphenylene ether
layer
laminated film
sheet
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PCT/JP2011/074872
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English (en)
Japanese (ja)
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夏樹 平
達哉 落合
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三菱樹脂株式会社
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Priority to JP2012540948A priority Critical patent/JPWO2012057293A1/ja
Publication of WO2012057293A1 publication Critical patent/WO2012057293A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • 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 polyphenylene ether-based laminated film having a laminated structure having at least an intermediate layer and surface layers on both sides thereof, and a solar cell sheet (solar cell laminated sheet) used for protecting a solar cell module using the same. And a solar cell module including the same.
  • the solar cell constitutes the central part of a photovoltaic power generation system that directly converts sunlight energy into electricity.
  • a plurality of solar cell elements are wired in series and in parallel as the structure, and various packaging is performed to protect the cells, thereby forming a unit.
  • a unit incorporated in this package is called a solar cell module, and the surface to which sunlight hits is generally covered with a transparent substrate (glass / translucent solar cell sheet; front sheet), and a thermoplastic (for example, ethylene- The gap is filled with a filler (sealing resin layer) made of a vinyl acetate copolymer), and the back surface is protected by a back surface sealing sheet (back sheet).
  • a transparent substrate glass / translucent solar cell sheet; front sheet
  • thermoplastic for example, ethylene-
  • the gap is filled with a filler (sealing resin layer) made of a vinyl acetate copolymer), and the back surface is protected by a back surface sealing sheet (back sheet).
  • the backsheet is also required to have sufficient durability, flame retardancy, dimensional stability, high mechanical strength, etc. in consideration of outdoor use. In addition, from the viewpoint of cleanliness and non-pollution, it is also required to reduce the environmental load. Furthermore, adhesion with a sealing resin layer and a junction box is also an important required characteristic. In particular, in order to effectively protect the power generation element in the sealing resin layer, adhesion with the sealing resin layer is very important.
  • polyphenylene ether is known as engineering plastics with excellent heat resistance, flame retardancy, dimensional stability, non-hygroscopicity, electrical properties, etc., but has difficulty in moldability. Blended with polystyrene with excellent processability. However, blending polystyrene inevitably reduces the flame retardancy of the polyphenylene ether, and therefore this system usually contains a flame retardant. However, when this polyphenylene ether is formed, particularly when a pigment or a flame retardant is added, there is a problem in that it is easy to generate scum and blisters and the appearance of the film is deteriorated.
  • Patent Document 1 discloses the coating of rolls and roll contamination during polyphenylene ether film formation. In this case, the film is formed of a single layer sheet having a large thickness (0.3 mm), and the thickness is small. No mention is made of the film formation of the two-type three-layer laminated sheet.
  • a first object is to use, as a main component, polyphenylene ether excellent in heat resistance, flame retardancy, dimensional stability, non-hygroscopicity, electrical characteristics, and the like. It has at least an intermediate layer and surface layers on both sides thereof, and the film-forming property is good, and when forming a film, it can prevent the occurrence of the surface layer portion, without polluting the roll,
  • the second object is to provide a polyphenylene ether-based laminated film having good durability, flame retardancy, dimensional stability and secondary processability, and the second object is to use the laminated film. It is providing the sheet
  • a third object is to provide a solar cell module including the solar cell sheet.
  • the intermediate layer is composed of a resin composition A containing polyphenylene ether and containing a pigment and / or a flame retardant, and the surface layers provided on both sides thereof both contain polyphenylene ether and contain the pigment and the flame retardant.
  • the present inventors have found that the first object can be achieved by a polyphenylene ether-based laminated film composed of a resin composition B substantially free of any of the above, and have completed the present invention. That is, the present invention is as follows.
  • a solar cell sheet obtained by laminating and integrating the solar cell sheet according to [8] or [9] and a sealing resin layer.
  • a solar cell module provided with the solar cell sheet according to any one of [8] to [10].
  • the main component is polyphenylene ether having excellent heat resistance, flame retardancy, dimensional stability, non-hygroscopicity, electrical properties, etc., and has at least an intermediate layer and surface layers on both sides thereof. It has good film-forming properties, and can prevent the occurrence of surface spots on the film, making it possible to produce long runs without contaminating the roll.
  • Durability, flame resistance, dimensions Polyphenylene ether-based laminated film having good stability and secondary processability, solar cell sheet used for protection of solar cell module using the same, and solar cell module comprising the solar cell sheet Can be provided.
  • a solar cell sheet obtained by laminating a gas barrier layer on the solar cell sheet and a solar cell sheet obtained by laminating and integrating the solar cell sheet and a sealing resin layer can be provided.
  • film is generally a thin flat product whose thickness is extremely small compared to length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (JIS K6900).
  • a “sheet” is a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width.
  • the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
  • the polyphenylene ether-based laminated film of the present invention (hereinafter sometimes simply referred to as “laminated film”) is a laminated film having at least an intermediate layer and surface layers on both sides thereof.
  • the intermediate layer is composed of the resin composition A containing polyphenylene ether and containing a pigment and / or a flame retardant, and the surface layers provided on both sides thereof both contain polyphenylene ether, and the pigment and the flame retardant Further, the resin composition B is substantially not included. That is, the polyphenylene ether-based laminated film of the present invention is a laminated film of at least two kinds and three layers.
  • the intermediate layer in the polyphenylene ether-based laminated film of the present invention is composed of a resin composition A containing polyphenylene ether and containing a pigment and / or a flame retardant.
  • polyphenylene ether is used as the main component of the resin composition A constituting the intermediate layer.
  • the “main component” represents the largest proportion of the resin composition A, and the lower limit is not particularly determined, but the polyphenylene ether is preferably 50% by mass or more, and 65% by mass. More preferably, it is more preferably 80% by mass or more. If it is this range, durability, a flame retardance, dimensional stability and high mechanical strength, high adhesiveness with a sealing resin layer, etc. can be achieved.
  • polyphenylene ether examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-) 6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6 -Dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenyle) ) Ether, poly (2,6-dichloro-1,4-phen
  • a copolymer obtained by grafting a styrene compound onto polyphenylene ether may be used.
  • the polyphenylene ether grafted with a styrene compound include a copolymer obtained by graft polymerization of styrene, ⁇ -methylstyrene, vinyltoluene, chlorostyrene and the like as the styrene compound to the polyphenylene ether.
  • the polyphenylene ether may be modified with a modifying agent having a polar group.
  • polar groups include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters, acid azides, sulfone groups, nitrile groups, cyano groups, isocyanate esters, amino groups, imide groups, hydroxyl groups, and epoxy groups.
  • the polyphenylene ether used for the intermediate layer and the surface layer described later preferably has a lower limit of the intrinsic viscosity of 0.2 dl / g or more determined from the viscosity measured in chloroform at 30 ° C. 0.3 dl / g or more is more preferable, and 0.4 dl / g or more is further preferable. If the value of the intrinsic viscosity is within this range, problems such as inferior heat resistance, flame retardancy, and mechanical strength are unlikely to occur.
  • the upper limit is preferably 0.8 dl / g or less, more preferably 0.7 dl / g or less, and further preferably 0.6 dl / g or less.
  • polyphenylene ethers having different intrinsic viscosities may be used in combination.
  • polyphenylene ethers are sold under the trade names “PPO646”, “PPO640”, and “PPO630” by SABIC Innovation Plastics and under the tradenames “S201A” and “S202” from Asahi Kasei Chemicals, respectively. Is possible.
  • the resin composition A serving as an intermediate layer and / or the resin composition B serving as a surface layer to be described later, the above-described polyphenylene ether, extrusion moldability, impact resistance, flame retardancy, adhesiveness
  • a styrene resin for the purpose of improving the physical properties such as, it is preferable to blend a styrene resin.
  • styrene resin include GPPS (general purpose polystyrene), HIPS (high impact polystyrene), ABS (acrylonitrile-butadiene-styrene), SEBS (hydrogenated styrene-butadiene-styrene block copolymer), SBS (styrene).
  • the content ratio of the polyphenylene ether and the styrene resin in the resin composition A is preferably 99: 1 to 60:40 by mass ratio, respectively. That is, the lower limit of the amount of the styrene resin to the total amount of the polyphenylene ether and the styrene resin is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less. If the content is within this range, the flame retardancy and heat resistance will not be excessively reduced.
  • the above-mentioned polyphenylene ether in the intermediate layer and the surface layer described later is used for the purpose of improving physical properties such as extrusion moldability, impact resistance, heat resistance, flame retardancy, and adhesiveness.
  • Other resin components can be appropriately blended as necessary within a range not impairing the effect.
  • resin components include, for example, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / ethyl acrylate copolymers, ethylene / glycidyl methacrylate copolymers.
  • Polymers ethylene resins such as ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, polyester resins such as polyester polyether elastomer and polyester polyester elastomer, polyamide resins And polyphenylene sulfide-based resin. These may be blended singly or in combination of two or more.
  • the resin composition A constituting the intermediate layer contains a coloring pigment and / or a flame retardant.
  • a coloring pigment include white pigments and black pigments.
  • white pigment For example, calcium carbonate, anatase type titanium oxide, rutile type titanium oxide, zinc oxide, lead carbonate, barium sulfate, basic lead carbonate, basic lead sulfate, basic silica Lead acid, zinc white, zinc sulfide, lithopone and the like can be used.
  • the rutile type is more preferable than the anatase type because it has less yellowing after being irradiated with light on the laminated film for a long time and is suitable for suppressing a change in color difference.
  • at least one inorganic fine particle selected from the group consisting of rutile type titanium oxide, barium sulfate, calcium carbonate and silicon dioxide is preferable from the viewpoint of stability and non-heavy metal compound, and barium sulfate and rutile type oxidation are preferable. Titanium is more preferable, and barium sulfate is more preferable.
  • Barium sulfate is a good white material that is physically and chemically stable and exhibits a reflectivity of 99% or more over almost the entire visible light region, and is a substance used as a white standard. Moreover, it is a material with high coloring property and concealment property, is efficiently whitened, and has a high light reflectivity effect as a solar cell backsheet.
  • the black pigment is not particularly limited, but carbon black, black iron oxide, and the like are used. Among them, carbon black is preferably used from the viewpoint of long-term stability. In order to develop other colors (blue, red, yellow, etc.), a dye or a pigment can be added. However, the addition of a pigment is preferable from the viewpoint of long-term stability.
  • This coloring pigment is blended in the resin composition A in an amount of usually 0.1 to 10% by mass, preferably 1 to 6% by mass, more preferably 2 to 4% by mass.
  • polyphenylene ether Since polyphenylene ether has an aromatic ring and oxygen atom in the unit skeleton, it easily forms a carbonized layer during combustion, and also has radical scavenging ability due to the presence of active hydrogen, and suppresses molecular chain breakage. Because of its easy characteristics, the resin is excellent in flame retardancy without causing dripping of the molten resin.
  • a halogen flame retardant such as brominated biphenyl ether, a metal hydroxide flame retardant such as magnesium hydroxide, an inorganic flame retardant such as a nitrogen compound, an antimony compound, etc.
  • the flame retardancy can be further improved by adding, it is preferable to add the following phosphorus flame retardant from the viewpoints of environmental load, imparting flame retardancy, and ensuring mechanical strength.
  • Phosphorus flame retardants include triphenyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl phenyl phosphate, xylenyl phosphate, resorcinol bis (diphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, triallyl phosphate, etc.
  • phosphoric acid ester flame retardants condensed phosphoric acid ester flame retardants such as aromatic condensed phosphoric acid esters, phosphazene compounds such as phosphonitrile phenyl ester, red phosphorus and the like.
  • the addition of the flame retardant is preferable because the heat resistance is not lowered excessively and the environment is not contaminated as a volatile gas during the melt processing.
  • it is 0.1 mass% or more, Preferably it is 1.0 mass% or more, More preferably, it is 3.0 mass% or more. If it is this range, since the effect which improves a flame retardance is acquired, it is suitable.
  • the laminated film of the present invention can be produced by extrusion using a two-kind three-layer multilayer T-die, but in this case, extrusion is performed at a relatively high temperature (220 ° C. to 300 ° C.). Therefore, heat resistance may be required for the component to be added.
  • An example of the heat resistance index is a weight reduction temperature by thermogravimetric analysis.
  • the 5% weight loss temperature when heated from normal temperature to 400 ° C. at an increase rate of 10 ° C./min in an inert gas atmosphere is preferably 150 ° C.
  • the phosphorus-based flame retardant volatilizes during molding and deteriorates the working environment, reduces the flame retardancy of the molded sheet, or promotes reaction with the base material during extrusion molding. Difficult to cause problems such as worsening the appearance.
  • the resin composition A constituting the intermediate layer of the laminated film of the present invention as long as the effects of the present invention are not impaired, other than the above-described coloring pigment and / or flame retardant, for example, heat resistance
  • inorganic fillers such as carbon filler, glass filler, talc, mica, etc., heat stabilizer, antioxidant, plasticizer (oil, low molecular weight polyethylene, epoxidized soybean oil) Polyethylene glycol, fatty acid esters, etc.), flame retardant aids for improving flame retardancy, weather resistance (light) improvers, nucleating agents, etc. may be added for improving durability.
  • the resin composition A constituting the above-described intermediate layer is formed by adding each of the above-described components to polyphenylene ether, but a commercially available product that has been mixed in advance may be purchased and used.
  • Commercially available polyphenylene ether-based resin compositions are trade names “Noryl PX9406”, “Noryl LTA1350” and “Noryl N300” from SABIC Innovation Plastics, and trade names “Zylon 540Z” and “Zylon 640Z” from Asahi Kasei Chemicals.
  • Zero 740Z is sold and available from Mitsubishi Engineering Plastics as "Iupiace LN91”, “Iupiace AN70”, “Iupiace AH90”, “Iupiace TX903B”, and "Remalloy BX528-A3".
  • a surface layer is provided on each side of the intermediate layer described above.
  • This surface layer is composed of a resin composition B that contains polyphenylene ether and substantially does not contain any pigment or flame retardant.
  • the resin composition B may contain a styrene resin.
  • the types of polyphenylene ether and styrene resin and the blending ratio thereof are as described in the description of the intermediate layer.
  • polyphenylene ether has a range that does not impair the effects of the present invention for the purpose of improving physical properties such as extrusion moldability, impact resistance, heat resistance, flame retardancy, and adhesiveness.
  • other resin components can be appropriately blended.
  • Other resin components are as described in the description of the intermediate layer.
  • the surface layer contains a pigment and / or a flame retardant
  • the surface layer part is likely to cause scumming and blisters, the film appearance is deteriorated, and a long run due to roll contamination is caused. It is easy to form a film. Moreover, the secondary processability of the obtained laminated film also deteriorates.
  • the fact that the resin composition B constituting the surface layer contains substantially no pigment and flame retardant means that the content of the pigment and the content of the flame retardant in the resin composition B are respectively It indicates 0.1% by mass or less.
  • the pigment and the flame retardant are as described in the description of the intermediate layer.
  • the resin composition B constituting the surface layer can contain an antioxidant.
  • the resin composition A constituting the intermediate layer can also contain an antioxidant.
  • the antioxidant various commercially available products can be applied, and various types such as monophenol type, bisphenol type, polymer type phenol type, sulfur type and phosphite type can be exemplified. Examples of monophenols include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-tert-butyl-4-ethylphenol.
  • Bisphenols include 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [ ⁇ 1,1-dimethyl- 2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl ⁇ 2,4,9,10-tetraoxaspiro] 5,5-undecane.
  • Examples of the high molecular phenolic group include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-bidoxybenzyl) benzene, tetrakis- ⁇ methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ⁇ methane, bis ⁇ (3,3′-bis-4′-hydroxy-3′-tert-butylphenyl) butyric acid ⁇ glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4 '-Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, 2- ⁇ 1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl ⁇
  • sulfur-based compounds examples include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiopropionate.
  • phosphites include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, Crick neopentanetetrayl bis (octadecyl phosphite), tris (mono and / or di) phenyl phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10 pho
  • phenol-based and phosphite-based antioxidants are preferably used in view of the effects of antioxidants, thermal stability, economy, etc., and using both in combination as an antioxidant with respect to the added amount It is more preferable because the effect can be enhanced.
  • the addition amount of the antioxidant is usually 0.1% by mass or more, preferably 0.2% by mass or more, and 1% by mass or less, preferably 100% by mass of the resin composition A or the resin composition B. Is preferably added in the range of 0.5% by mass or less.
  • the polyphenylene ether-based laminated film of the present invention preferably has a thickness of 10 to 500 ⁇ m, more preferably 20 to 200 ⁇ m, from the viewpoint of flame retardancy and economy. Further, the thickness ratio of the surface layer / intermediate layer / surface layer described above is 0.01 to from the viewpoint of the balance of improving the formability without impairing the essence of the film performance while bearing the essence of the film performance in the intermediate layer. It is preferably 2 / 9.98 to 6 / 0.01 to 2, more preferably 0.1 to 2 / 9.9 to 6 / 0.1 to 2, and 0.15 to 2/9. 7 to 6 / 0.15 to 2 is more preferable, and 0.5 to 1/9 to 8 / 0.5 to 1 is particularly preferable.
  • the polyphenylene ether-based laminated film of the present invention is produced, for example, by using an extruder equipped with a two-layer three-layer multi-layer T-die and extruding with a barrel temperature of 220 to 300 ° C. and a base temperature of 290 ° C. be able to. Specifically, while carrying out nitrogen purge, raw materials (resin composition A, resin composition B) are charged, the molten raw material is extruded from a T-die die, cooled and solidified with a cast roll, and the speed of the cast roll Is adjusted to produce a polyphenylene ether-based laminated film having a predetermined thickness and having a two-kind / three-layer structure.
  • the solar cell sheet of the present invention includes first to third solar cell sheets.
  • seat for solar cells is a sheet
  • the first solar cell sheet is a sheet used for constituting a solar cell module, and particularly includes a front or back surface sealing sheet (front sheet or back sheet), a substrate sheet, and the like, and particularly as a back sheet. It is a solar cell sheet that can be suitably used.
  • an easy adhesion layer, a light reflective colored layer, a hard coat layer, or the like may be provided on the surface.
  • the second solar cell sheet is a solar cell sheet obtained by further laminating a gas barrier layer on the first solar cell sheet described above.
  • Gas barrier layer As a gas barrier layer in the 2nd sheet
  • a metal thin film such as an aluminum foil or a thermoplastic polymer can be used as the gas barrier layer, and any material that can be used for ordinary packaging materials can be used without any particular limitation.
  • polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefin, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 66, polyamide such as nylon 12, copolymer nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (partially saponified product, EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate , Polyvinyl butyral, polyarylate, acrylate resin and the like.
  • polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene
  • amorphous polyolefins such as cyclic polyolefin
  • polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate
  • polyester, polyamide, and polyolefin are preferable from the viewpoint of film properties.
  • polyethylene terephthalate and polyethylene naphthalate are more preferable from the viewpoint of film strength.
  • polyethylene naphthalate is preferable in terms of weather resistance and hydrolysis resistance.
  • Examples of the inorganic substance constituting the inorganic thin film layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrogenated carbon, etc., or oxides, carbides, nitrides, or mixtures thereof.
  • Diamond-like carbon mainly composed of silicon oxide, aluminum oxide, and hydrogenated carbon is preferable.
  • silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide are preferable in that high gas barrier properties can be stably maintained.
  • any of a vapor deposition method and a coating method can be used, but a vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained.
  • This vapor deposition method includes methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of physical vapor deposition include vacuum deposition, ion plating, and sputtering, and chemical vapor deposition includes plasma CVD using plasma and a catalyst that thermally decomposes a material gas using a heated catalyst body. Examples include chemical vapor deposition (Cat-CVD).
  • the material gas that can be used for chemical vapor deposition is preferably composed of at least one gas.
  • a rare gas such as ammonia, nitrogen, oxygen, hydrogen or argon as the second source gas for the first source gas containing silicon.
  • the first source gas containing silicon includes monosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane.
  • the source gas may be liquid or gas at room temperature, and the liquid source can be vaporized by a source vaporizer and supplied into the apparatus. In the catalytic chemical vapor deposition method, monosilane gas is preferable from the viewpoint of deterioration of the heated catalyst body, reactivity, and reaction rate.
  • the thickness of the gas barrier layer thus formed is usually about 5 to 500 ⁇ m, preferably 10 to 400 ⁇ m, more preferably 25 to 300 ⁇ m, from the viewpoint of performance and economy as a gas barrier layer.
  • the second solar cell sheet is a sheet used for constituting a solar cell module, and particularly includes a front or back surface sealing sheet (front sheet or back sheet), a substrate sheet, and the like, and particularly as a back sheet. It is a solar cell sheet that can be suitably used. In addition to the second solar cell sheet, an easy adhesion layer, a light reflective colored layer, a hard coat layer, or the like may be provided on the gas barrier layer.
  • the third solar cell sheet is a solar cell sheet formed by laminating and integrating the first or second solar cell sheet and the sealing resin layer.
  • the sealing resin layer of the layers constituting the third solar cell sheet is not particularly limited, but is preferably made of a resin composition containing a polyolefin resin or a modified polyolefin resin as a main component. Specific polyolefin resins and modified polyolefin resins are exemplified below, but these resins may be used alone or in combination of two or more.
  • the sealing resin layer may be a single layer or a laminate of two or more layers as long as each is a layer composed of a resin composition mainly composed of a polyolefin resin or a modified polyolefin resin. .
  • polyolefin resin The type of the polyolefin resin is not particularly limited, but is preferably at least one resin selected from the group consisting of a polyethylene polymer, a polypropylene polymer, and a cyclic olefin polymer.
  • polyethylene polymer The type of polyethylene polymer is not particularly limited, and specifically, ultra-low density polyethylene, low density polyethylene, linear low density polyethylene (ethylene- ⁇ -olefin copolymer), medium density polyethylene, High density polyethylene, ultra high density polyethylene, etc. are mentioned.
  • linear low density polyethylene ethylene- ⁇ -olefin copolymer
  • linear low density polyethylene has low crystallinity and excellent transparency and flexibility, which impedes the power generation characteristics of the solar cell element and causes excessive stress to the solar cell element.
  • the ethylene- ⁇ -olefin copolymer may be a random copolymer or a block copolymer.
  • the type of ⁇ -olefin copolymerized with ethylene is not particularly limited, but usually an ⁇ -olefin having 3 to 20 carbon atoms is preferably used.
  • Examples of the ⁇ -olefin copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 3-methyl-butene. -1,4-methyl-pentene-1 and the like.
  • propylene, 1-butene, 1-hexene, and 1-octene are preferably used as the ⁇ -olefin copolymerized with ethylene from the viewpoints of industrial availability, various characteristics, and economical efficiency. It is done.
  • the ⁇ -olefin copolymerized with ethylene may be used alone or in combination of two or more.
  • the content of ⁇ -olefin copolymerized with ethylene is not particularly limited, but is usually 2 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually It is 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.
  • the method for producing the polyethylene polymer is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst can be employed.
  • a known polymerization method using a known olefin polymerization catalyst can be employed.
  • the ethylene- ⁇ -olefin copolymer used as the sealing resin layer is preferably a relatively soft resin, and has a low molecular weight component from the standpoint of ease of granulation after pelletization and prevention of blocking of raw material pellets.
  • a polymerization method using a single site catalyst capable of polymerizing a raw material with a small molecular weight distribution and a small molecular weight distribution is suitable.
  • polyethylene-based polymer used for the sealing resin layer examples include trade names “Hizex”, “Neozex”, “Ultzex” manufactured by Prime Polymer Co., Ltd., Japan. Trade names “Novatec HD”, “Novatech LD”, “Novatech LL”, trade names “Engage”, “Affinity”, “Infinity” manufactured by Dow Chemical Co., Ltd. "Fuse”, Mitsui Chemicals' brand names "TAFMER A”, “TAFMER P", Nippon Polyethylene's brand name "Kernel”, etc. It can be illustrated.
  • Polypropylene polymer The type of the polypropylene polymer is not particularly limited, and specific examples include a propylene homopolymer, a propylene copolymer, a reactor type polypropylene thermoplastic elastomer, and a mixture thereof. It is done.
  • a copolymer of propylene a random copolymer (random polypropylene) of propylene and ethylene or other ⁇ -olefin, or a block copolymer (block polypropylene), a block copolymer or a graft copolymer containing a rubber component Etc.
  • the other ⁇ -olefin copolymerizable with propylene is preferably one having 4 to 12 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene and the like, and one or a mixture of two or more thereof are used.
  • the content of ⁇ -olefin copolymerized with propylene is not particularly limited, but is usually 2 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually It is 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.
  • polypropylene used in the sealing resin layer examples include trade names “Novatech PP” and “Wintech” manufactured by Nippon Polypro Co., Ltd., and “Prime Polypro” and “Prime” manufactured by Prime Polymer Co., Ltd. Examples include TPO "and trade name” Nobren "manufactured by Sumitomo Chemical Co., Ltd.
  • the type of the cyclic olefin polymer is not particularly limited, and specifically, a cyclic olefin polymer obtained by ring-opening polymerization of one or more cyclic olefins, a hydride thereof, and a linear chain. And a block copolymer of a linear ⁇ -olefin and a cyclic olefin, and a random copolymer of a linear ⁇ -olefin and a cyclic olefin.
  • the type of the cyclic olefin constituting the cyclic olefin polymer is not particularly limited, but bicyclohept-2-ene (2-norbornene) and its derivatives such as norbornene, 6-methylnorbornene, 6-ethyl Norbornene, 6-n-butylnorbornene, 5-propylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclo-3-dodecene and its derivatives
  • the type of linear ⁇ -olefin copolymerized with the cyclic olefin is not particularly limited, but usually a linear ⁇ -olefin having 2 to 20 carbon atoms is preferably used.
  • Examples of the linear ⁇ -olefin copolymerized with the cyclic olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. Etc.
  • ethylene is preferably used as the linear ⁇ -olefin copolymerized with the cyclic olefin from the viewpoints of industrial availability, various characteristics, economy, and the like.
  • the linear ⁇ -olefin copolymerized with the cyclic olefin may be used alone or in combination of two or more.
  • the content of the cyclic olefin copolymerized with the linear ⁇ -olefin is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more. And, it is usually 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less.
  • the content of the cyclic olefin is increased, the heat resistance, the barrier property and the transparency can be improved, and when the content is decreased, the flexibility is improved, which is preferable. If the content of the cyclic olefin is within this range, it is preferable because the crystallinity is reduced by the copolymerization component, transparency is exhibited, and problems such as blocking of raw material pellets hardly occur.
  • cyclic olefin-based polymer used in the sealing resin layer include a product name “APEL” manufactured by Mitsui Chemicals, Inc., and a product name “TOPAS (TOPAS) manufactured by Topas Advanced Polymers Co., Ltd. ) ”, Trade names“ ZEONOR ”and“ ZEONEX ”manufactured by Nippon Zeon Co., Ltd. can be exemplified.
  • Modified polyolefin resin The type of the modified polyolefin resin constituting the sealing resin layer in the present invention is not particularly limited, but EVA (ethylene-vinyl acetate copolymer), EVOH (ethylene-vinyl alcohol copolymer), E- MMA (ethylene-methyl methacrylate copolymer), E-EAA (ethylene-ethyl acrylate copolymer), E-GMA (ethylene-glycidyl methacrylate copolymer), ionomer resin (ionic crosslinkable ethylene-methacrylic acid copolymer) It is preferably at least one resin selected from the group consisting of a polymer, an ion crosslinkable ethylene-acrylic acid copolymer), a silane crosslinkable polyolefin, and a maleic anhydride graft copolymer.
  • EVA ethylene-vinyl acetate copolymer
  • EVOH ethylene-vinyl alcohol copolymer
  • E- MMA
  • the content of various monomers that modify the modified polyolefin resin is not particularly limited, but is usually 0.5 mol% or more, preferably 1 mol% or more, more preferably 2 mol% or more. And, it is usually 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.
  • modified polyolefin resin used in the sealing resin layer examples include EVA (ethylene-vinyl acetate copolymer), trade name “Novatech EVA” manufactured by Nippon Polyethylene Co., Ltd., Mitsui DuPont Polychemical The product name “EVAFLEX” manufactured by Nihon Kayaku Co., Ltd., the “NUC” series manufactured by Nihon Unicar Co., Ltd., and the EVOH (ethylene-vinyl alcohol copolymer) product name manufactured by Nippon Synthetic Chemical Co., Ltd.
  • EVA ethylene-vinyl acetate copolymer
  • trade name “Novatech EVA” manufactured by Nippon Polyethylene Co., Ltd. Mitsui DuPont Polychemical
  • EVAFLEX manufactured by Nihon Kayaku Co., Ltd.
  • NUC Nihon Unicar Co., Ltd.
  • EVOH ethylene-vinyl alcohol copolymer
  • silane crosslinkable polyolefin trade name “Rychlon” manufactured by Mitsubishi Chemical Corporation can be exemplified, and as a maleic anhydride graft copolymer, “Admer” manufactured by Mitsui Chemicals, Inc. can be exemplified.
  • the resin composition constituting the encapsulating resin layer is described above for the purpose of further improving various physical properties (flexibility, heat resistance, transparency, adhesiveness, etc.), molding processability, and economical efficiency as necessary.
  • Resins other than polyolefin resins and modified polyolefin resins can be mixed.
  • the resin include other polyolefin resins and various elastomers (olefin-based, styrene-based, etc.), modified with polar groups such as carboxyl group, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, and thiol group.
  • Resin and tackifying resin include other polyolefin resins and various elastomers (olefin-based, styrene-based, etc.), modified with polar groups such as carboxyl group, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, and thiol group.
  • additives can be added to the resin composition constituting the sealing resin layer as necessary.
  • the additive include radical generators (crosslinking agents / crosslinking aids), silane coupling agents, antioxidants, ultraviolet absorbers, weathering stabilizers, light diffusing agents, nucleating agents, pigments (for example, white pigments) ), Flame retardants, discoloration inhibitors and the like.
  • it is preferable that at least one additive selected from a radical generator, a silane coupling agent, an antioxidant, an ultraviolet absorber, and a weathering stabilizer is added.
  • the thickness of the sealing resin layer is not particularly limited, but is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and about 1000 ⁇ m (1.0 mm) or less, preferably 700 ⁇ m or less. Preferably, it may be 500 ⁇ m or less. Since the third solar cell sheet has a laminated structure of a flexible sealing resin layer and a rigid first or second solar cell sheet, the handling property is reduced even if the thickness is thin.
  • the sealing resin layer may be thinned according to the type and configuration of the solar cell to be applied and in view of economy.
  • an extrusion casting method using a T die is preferably used from the viewpoints of handling properties and productivity.
  • the molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film forming properties of the resin composition to be used, but is generally 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, More preferably, the temperature is 140 ° C.
  • a radical generator or a silane coupling agent is added. In such a case, it is preferable to lower the molding temperature in order to suppress an increase in resin pressure and a fish eye accompanying the crosslinking reaction.
  • the solar cell sheet of the present invention has a surface such as scratch resistance and antifouling on the surface that is the outermost surface when formed as a solar cell module, that is, on the surface opposite to the surface in contact with the sealing resin layer.
  • a known hard coat treatment or antifouling treatment may be performed.
  • the solar cell module of the present invention is provided with any one of the first to third solar cell sheets described above. Specifically, as shown in FIG. 1, the transparent substrate 10, the sealing resin layer 12A, the solar cell elements 14A and 14B, the sealing resin layer 12B, and the solar cell sheet of the present invention (in order from the sunlight receiving side) In this case, a back sheet 16 is laminated, and a junction box 18 (a terminal box for connecting wiring for taking out electricity generated from the solar cell element) is bonded to the lower surface of the solar cell sheet 16. Being done.
  • the solar cell elements 14A and 14B are connected by a wiring 20 in order to conduct the generated current to the outside.
  • the wiring 20 is taken out through a through hole (not shown) provided in the solar cell sheet 16 and connected to the junction box 18. Since the solar cell module deteriorates when moisture enters the inside, when attaching accessories such as a junction box, ensure sufficient sealing so that outside air does not enter the inside of the solar cell module. Although it is necessary, according to the solar cell sheet of the present invention, since it can be bonded only by heat treatment, it is possible to easily and reliably prevent the intrusion of outside air.
  • the transparent substrate glass or a single-layer or multilayer plastic sheet such as acrylic resin, polycarbonate, polyester, fluorine-containing resin is used.
  • plastic for the purpose of providing gas barrier properties, an inorganic thin film is formed in the same manner as the gas barrier film constituting the solar cell sheet, or heat resistance, weather resistance, mechanical strength, chargeability, dimensions
  • a crosslinking agent, an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent, a reinforcing fiber, a flame retardant, a preservative, and the like are added.
  • a film can be laminated
  • the thickness of the transparent substrate can be appropriately set in view of strength, gas barrier properties, durability, and the like.
  • the sealing resin layer it is as having demonstrated with the sheet
  • the solar cell element is arranged and wired between the sealing resin layers.
  • Examples thereof include a single crystal silicon type, a polycrystalline silicon type, an amorphous silicon type, various compound semiconductor types, a dye sensitized type, and an organic thin film type.
  • the solar cell module does not specifically limit as a manufacturing method of the solar cell module at the time of using the sheet
  • a transparent substrate, a sealing resin layer, a solar cell element, a sealing resin layer It has the process of laminating
  • the solar cell module can be suitably used for various applications regardless of small size, large size, indoors, and outdoors due to the excellent durability, flame retardancy, dimensional stability and high mechanical strength of the solar cell sheet.
  • Preparation Example 1 Preparation of Resin Composition 1 Polystyrene ether (PPE) resin [trade name “PPO646” manufactured by SABIC Innovation Plastics Co., Ltd.] 90 parts by mass, styrene resin [Asahi Kasei Co., Ltd. trade name “Tuftec H1051] 10 mass” Part, a phosphorus-based flame retardant as a flame retardant [trade name “PX200” manufactured by Daihachi Chemical Industry Co., Ltd.] 7.5 parts by mass, and 3 parts by mass of carbon black as a pigment, and melt-kneaded at 300 ° C. to prepare a raw material A Was prepared.
  • PPE Polystyrene ether
  • Preparation Example 2 Preparation of Resin Composition 2 To 90 parts by mass of PPE resin (supra), 10 parts by mass of a styrene resin (supra) was added and melt-kneaded at 300 ° C. to prepare resin composition 2.
  • Preparation Example 3 Preparation of Resin Composition 3 To 90 parts by mass of PPE resin (supra), 10 parts by mass of a styrene resin (supra) and 7.5 parts by mass of a phosphorus-based flame retardant (supra) are added as a flame retardant.
  • the resin composition 3 was prepared by melt-kneading at 300 ° C.
  • Preparation Example 4 Preparation of Resin Composition 4 To 90 parts by mass of PPE resin (supra), 10 parts by mass of a styrene resin (supra) and 3 parts by mass of carbon black as a pigment were added, and melt-kneaded at 300 ° C. Resin composition 4 was prepared.
  • Preparation Example 5 Preparation of Resin Composition 5 To 90 parts by mass of PPE resin (supra), 10 parts by mass of styrene resin (supra) and 6.5 parts by mass of titanium oxide as a pigment are added, and melt kneaded at 300 ° C. Thus, a resin composition 5 was prepared.
  • Preparation Example 6 Preparation of Resin Composition 6 To 90 parts by mass of PPE resin (supra), 10 parts by mass of styrene resin (supra), and 7.5 parts by mass of a phosphorus flame retardant (supra) as a flame retardant and pigment As a result, 6.5 parts by mass of titanium oxide was added and melt-kneaded at 300 ° C. to prepare a resin composition 6.
  • Table 1 shows compounding components in the resin compositions 1 to 6 prepared in the above Preparation Examples 1 to 6.
  • Examples 1 to 5 and Comparative Examples 1 to 4 As a test lab machine, a 50mm ⁇ , 35mm ⁇ extruder equipped with two kinds of three-layer multilayer T-die was used. A 50 ⁇ m two-type three-layer laminated sheet or a single-layer sheet was formed. Specifically, while carrying out nitrogen purge to the extruder, each raw material is charged, the molten raw material is extruded from a T-die die, cooled and solidified by a cast roll, and the speed of the cast roll is adjusted to be predetermined. A two-type three-layer laminated sheet or a single-layer sheet having a thickness of 50 ⁇ m was formed. The evaluation results for each sheet are shown in Table 2.
  • the polyphenylene ether-based laminated film of the present invention is suitable as a solar cell sheet used for protecting a solar cell module.

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Abstract

L'invention concerne un film feuilleté qui a, au moins, une couche intermédiaire et des couches de surface sur les deux côtés de celle-ci. Ladite couche intermédiaire comprend une composition de résine (A) qui contient du polyphénylène éther et qui contient également un pigment et/ou un retardateur de flamme. Chacune des couches de surface disposées sur les deux côtés de la couche intermédiaire comprend une composition de résine (B) qui contient du polyphénylène éther et qui ne contient pratiquement pas de pigments ou de retardateurs de flamme.
PCT/JP2011/074872 2010-10-28 2011-10-27 Film feuilleté de polyphénylène-éther, feuille de cellule solaire et module de cellule solaire WO2012057293A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09147812A (ja) * 1995-11-22 1997-06-06 Asahi Chem Ind Co Ltd 多層構造を有する密閉型二次電池用電槽
JP2007296686A (ja) * 2006-04-28 2007-11-15 Kaneka Corp 多層押出発泡積層シートおよびそれを用いた自動車内装材
JP2009241266A (ja) * 2008-03-28 2009-10-22 Sekisui Plastics Co Ltd 自動車内装材用積層シート、自動車内装材及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62149728A (ja) * 1985-08-27 1987-07-03 Matsushita Electric Works Ltd 金属箔張積層板の製法
JPS62235335A (ja) * 1986-04-04 1987-10-15 Matsushita Electric Works Ltd 金属箔張積層板の製法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09147812A (ja) * 1995-11-22 1997-06-06 Asahi Chem Ind Co Ltd 多層構造を有する密閉型二次電池用電槽
JP2007296686A (ja) * 2006-04-28 2007-11-15 Kaneka Corp 多層押出発泡積層シートおよびそれを用いた自動車内装材
JP2009241266A (ja) * 2008-03-28 2009-10-22 Sekisui Plastics Co Ltd 自動車内装材用積層シート、自動車内装材及びその製造方法

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