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WO2012043248A1 - Film de résine polyoléfine multicouche pour feuille de protection arrière pour photopile - Google Patents

Film de résine polyoléfine multicouche pour feuille de protection arrière pour photopile Download PDF

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Publication number
WO2012043248A1
WO2012043248A1 PCT/JP2011/071073 JP2011071073W WO2012043248A1 WO 2012043248 A1 WO2012043248 A1 WO 2012043248A1 JP 2011071073 W JP2011071073 W JP 2011071073W WO 2012043248 A1 WO2012043248 A1 WO 2012043248A1
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Prior art keywords
layer
resin
film
weight
parts
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Ceased
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PCT/JP2011/071073
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English (en)
Japanese (ja)
Inventor
谷口幸司
中垣昇
奥山太
田中茂
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Toray Advanced Film Co Ltd
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Toray Advanced Film Co Ltd
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Priority to CN2011800451072A priority Critical patent/CN103119726A/zh
Priority to JP2011543011A priority patent/JP5732402B2/ja
Publication of WO2012043248A1 publication Critical patent/WO2012043248A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • 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 polyolefin resin multilayer film for solar cell back surface protection sheet. More specifically, in the solar cell manufacturing process, when heat-pressed in a glass laminating process or the like, the film is thinly deformed due to the influence of wiring members such as power collecting cells and current collecting electrodes called power generating cells and bus bars. Excellent heat resistance and concealment to the extent that it does not show through, and suitable for solar cell backside sheet materials that have high thermal adhesion to resins such as ethylene / vinyl acetate copolymer resins that are used as sealing materials for solar cells
  • the present invention relates to a polyolefin resin multilayer film.
  • Polyolefin-based resin films such as polyethylene and polypropylene have moderate strength and are excellent in transparency, heat sealability, moisture resistance, chemical resistance, low temperature impact strength, etc., foods, beverages, pharmaceuticals and medical products It is widely used as various packaging materials such as industrial materials and daily life materials.
  • a polyolefin resin film has been used as a member for a back surface protection sheet of a solar cell module for photovoltaic power generation because of its light weight, moisture resistance, and high withstand voltage characteristics. Therefore, various characteristics for improving the performance and long-term reliability of solar cell modules have been required.
  • the thermal adhesiveness with ethylene / vinyl acetate copolymer resin (hereinafter abbreviated as EVA), which is a sealing material for power generation cells, and the deformation due to the pressure during thermal bonding.
  • EVA ethylene / vinyl acetate copolymer resin
  • the contradictory property of heat resistance to suppress is required.
  • Patent Document 1 discloses a method in which a film obtained by adding a UV blocker or an antioxidant to a polyethylene resin having a density of 0.940 to 0.970 g / cm 3 is disclosed as a back sheet of a solar cell module.
  • a film obtained by adding a UV blocker or an antioxidant to a polyethylene resin having a density of 0.940 to 0.970 g / cm 3 is disclosed as a back sheet of a solar cell module.
  • the heat adhesion with EVA is excellent, the heat resistance is insufficient, and in the manufacturing process of the solar cell module, the film is partially deformed by the effect of heat and pressure during glass lamination.
  • the wiring becomes thin and the wiring such as the power generation cell and the bus bar is transparent, and the withstand voltage characteristic is lowered.
  • Patent Document 2 describes a solar cell module back surface protection sheet including a film sheet in which a polypropylene resin and a polyethylene resin are laminated for the purpose of improving penetration resistance due to solder protrusions of electrode portions of the solar cell.
  • the polypropylene resin and the polyethylene resin are simply laminated by coextrusion, they are easily peeled off at the laminated interface, and thus there are great restrictions when used as a solar cell module back surface protective sheet.
  • an object of the present invention is to solve the above-mentioned problems. That is, an object of the present invention is to form a thin film by deforming under the influence of a wiring member such as a bus bar when a solar cell module is subjected to thermocompression bonding in a glass laminating step or the like in a solar cell module manufacturing process as a solar cell back surface protective sheet. Excellent heat resistance and concealment to such an extent that wiring members such as busbars do not see through, have high thermal adhesive strength with resin such as EVA used as a sealing material for power generation cells, and adhesion between layers An object of the present invention is to provide a polyolefin-based resin multilayer film for a solar cell back surface protective sheet excellent in the above.
  • a polyolefin-based resin multilayer film for a solar cell back surface protective sheet is a film having a three-layer structure of A layer / B layer / C layer, and the A layer is 100 weight of polyethylene.
  • the layer B is composed of a resin composition in which 50 to 500 parts by weight of a polypropylene resin is mixed with the part, the layer B is composed of a polypropylene resin composition in which the addition amount of the coloring agent is 5 to 50% by weight, and the layer C Consists of a polyolefin resin multilayer film characterized by comprising a polypropylene resin composition.
  • the polyolefin-based resin multilayer film according to the present invention has excellent heat resistance to such an extent that the film does not become thin due to the influence of a wiring member such as a bus bar when heat-pressed in a glass laminating process or the like.
  • a wiring member such as a bus bar when heat-pressed in a glass laminating process or the like.
  • it can be suitably used for a solar cell back surface protective sheet material because it has a high thermal adhesive force with a resin such as EVA, which is used as, and is excellent in adhesion between layers.
  • examples of the polyethylene used in the layer A include high-pressure method low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and mixed resins thereof.
  • the linear low density polyethylene is a copolymer of ethylene and ⁇ -olefin (hereinafter abbreviated as LLDPE), and is a copolymer of ⁇ -olefin having 4 to 20 carbon atoms, preferably 4 to 8 carbon atoms.
  • LLDPE ⁇ -olefin
  • These ⁇ -olefins can be used alone or in combination.
  • 1-butene, 1-hexene, 1-octene and the like are preferably used from the viewpoint of polymerization productivity.
  • the melting point of LLDPE used in the present invention is preferably in the range of 110 to 130 ° C. It has excellent thermal adhesiveness with EVA when the melting point is 130 ° C. or lower, and maintains the partial discharge voltage without reducing the thickness of the sheet when thermally fused with EVA when it is 110 ° C. or higher. Is preferable.
  • the density of the LLDPE is preferably 0.90 g / cm 3 or more, but if the density is higher than 0.94 g / cm 3 , the dispersibility with the polypropylene resin is lowered, and a metal roll or rubber roll In the case of 0.94 g / cm 3 or less, the resin is likely to fall off and cause white powder.
  • the ⁇ -olefin content in LLDPE is preferably 0.5 to 10 mol%, more preferably 2.0 to 8.0 mol%.
  • the density of LLDPE can be in the range of 0.90 g / cm 3 or more and 0.94 g / cm 3 or less.
  • the melt index at 190 ° C. (hereinafter abbreviated as MFR) of LLDPE used in the present invention is preferably 0.5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes. . If the MFR is smaller than 0.5 g / 10 min, lamination unevenness with other layers is likely to occur during film formation. On the other hand, if the MFR is larger than 10.0 g / 10 min, the handling property at the time of casting and the embrittlement due to the increase in crystallinity tend to occur.
  • LLLDPE used in the present invention can be produced by a conventional polymerization method using a multisite catalyst or a polymerization method using a single site catalyst (Kaminsky catalyst, metallocene catalyst).
  • High-pressure low-density polyethylene (hereinafter abbreviated as LDPE) can be produced by the same polymerization method using a conventional multi-site catalyst as that of LLDPE or a polymerization method using a single-site catalyst (Kaminsky catalyst, metallocene catalyst). it can.
  • the density of LDPE is preferably in the range of 0.90 to 0.93 g / cm 3 . It is preferable that the density is 0.90 g / cm 3 or more because excellent slipperiness of the film can be ensured and the film handleability during processing is improved. On the other hand, by setting it to 0.93 g / cm 3 or less, it is easy to express the effect of improving the dispersibility of polyethylene and polypropylene resin.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE and LDPE low density polyethylene
  • the A layer of the present invention it is necessary to mix 50 to 500 parts by weight of a polypropylene resin with respect to 100 parts by weight of polyethylene.
  • a polypropylene resin By mixing 50 to 500 parts by weight of a polypropylene resin, the heat resistance is improved and the adhesion with the B layer can be increased.
  • the amount of the polypropylene resin exceeds 500 parts by weight, the adhesion with EVA becomes insufficient, and when the amount is less than 50 parts by weight, the effect of improving the heat resistance and the adhesion between the B layers is lowered.
  • Heat resistance means that it can withstand a 130-170 ° C. glass laminate, etc., which is carried out in a processing step when used as a solar cell back surface protective sheet. More specifically, as described above, in the manufacturing process of the solar cell module incorporating wiring such as a bus bar, the resin constituting the solar cell back surface protection sheet is deformed by heat and pressure in the case of glass lamination or the like. It is important to maintain an initial thickness of 80% or more. By maintaining the initial thickness, it is possible to obtain a solar cell module excellent in design without causing a wiring member such as a bus bar to pass through. In addition, withstand voltage such as dielectric breakdown voltage and partial discharge voltage is a characteristic value of the resin and is proportional to the thickness of the film. Therefore, heat resistance is extremely important.
  • the content of the polypropylene resin is preferably in the range of 50 to 250 parts by weight, and more preferably 100 to 200 parts by weight.
  • the processing temperature is 150 to 170 ° C.
  • the content of the polypropylene resin is preferably in the range of 250 to 500 parts by weight, and more preferably in the range of 300 to 450 parts by weight.
  • polypropylene resin examples include homopolypropylene, ethylene / propylene random copolymer, and ethylene / propylene block copolymer. However, such as heat resistance, slipperiness, film handling property, and dispersibility with polyethylene, etc. To ethylene / propylene block copolymers and homopolypropylene are most preferred.
  • the ethylene content is preferably in the range of 1 to 15 mol%.
  • the ethylene content is less than 1 mol%, the dispersibility in LLDPE or LDPE or a mixed resin thereof is lowered, and the resin easily falls off during rubbing with a metal roll or a rubber roll, which causes generation of white powder.
  • the adhesive strength with EVA may be reduced.
  • the sheet thickness may be reduced and the partial discharge voltage may be lowered when thermally fused to EVA.
  • the MFR of the polypropylene resin at 230 ° C. is preferably in the range of 1.0 to 15 g / 10 min.
  • the MFR is smaller than 1.0 g / 10 min, the film width is lowered (necked down) than the discharge width of the die in the film forming step, and it is not preferable because stable production of the film becomes difficult.
  • MFR is larger than 15 g / 10min, since the crystallization speed increases and it becomes brittle, it is not preferable.
  • the melting point of the polypropylene resin is preferably in the range of 140 ° C. to 170 ° C. from the viewpoints of heat resistance, slipperiness, film handling properties, curl resistance, and thermal adhesion to EVA.
  • the melting point 140 ° C. or higher the A layer has excellent heat resistance, and when it is thermally fused to EVA as a back sheet for solar cells, the thickness of the sheet is reduced or the partial discharge voltage is reduced. Can be suppressed, which is preferable.
  • the melting point it is preferable for the melting point to be 170 ° C. or lower because an excellent adhesion with EVA can be secured.
  • the surface average roughness Ra of the layer A is preferably 0.10 to 0.30 ⁇ m because the film handling function during processing is satisfied.
  • inorganic or organic particles having an average particle diameter of 1 to 5 ⁇ m are added in an amount of 0.1 to 10% by weight based on the resin component of the layer A for the purpose of improving the handleability and slipperiness of the film. Also good.
  • inorganic particles for example, inorganic particles such as wet silica, dry silica, colloidal silica, aluminum silicate, and calcium carbonate, and organic particles such as crosslinked organic particles such as styrene, silicone, acrylic acid, and methacrylic acid are used. Can do.
  • use of inorganic particles of aluminum silicate is preferable from the viewpoint of dispersibility in the resin. If the average particle size is less than 1 ⁇ m, the effect of improving the slipperiness of the film is low, and if the average particle size is more than 5 ⁇ m, the particles may fall off the film and cause contamination and scratches, so care must be taken. .
  • an organic compound lubricant can be added to the A layer resin component.
  • the organic compound lubricant include stearamide and calcium stearate.
  • the B layer in the present invention comprises a polypropylene resin composition containing a colorant.
  • the polypropylene-based resin composition referred to here is composed of at least one resin selected from homopolypropylene, a random or block copolymer of ethylene and propylene, or a mixed resin of these resins and polyethylene. From the viewpoint of heat resistance, the polyethylene content is preferably less than 30% by weight of the total resin component.
  • the ethylene content is 15 mol% or less.
  • a crystal nucleating agent can be added as necessary.
  • ⁇ -crystal nucleating agents are preferred, and specific examples include sorbitol-based and cyclopentadiene-based crystal nucleating agents.
  • the MFR at 230 ° C. of the polypropylene-based resin is preferably in the range of 1.0 to 15 g / 10 minutes from the viewpoint of lamination during coextrusion with the A layer and the C layer described later.
  • the MFR is smaller than 1.0 g / 10 min, the film melt-extruded from the die necks down in the film forming process, and the thickness unevenness in the width direction of the film deteriorates, making stable film formation difficult. Therefore, it is not preferable.
  • MFR is larger than 15 g / 10min, since the crystallization speed increases and it becomes brittle, it is not preferable.
  • Examples of the colorant used in the B layer of the present invention include inorganic and organic colorants such as titanium oxide, barium sulfate, carbon black, and phthalocyanine compounds.
  • inorganic and organic colorants such as titanium oxide, barium sulfate, carbon black, and phthalocyanine compounds.
  • titanium oxide particles are most preferable, and the rutile type, anatase type, brookite type, and the like are known as crystal types, and the rutile type is preferable because of excellent whiteness, weather resistance, and light reflectivity.
  • the titanium oxide used in the present invention may deteriorate the resin by photocatalysis, it is preferably surface-coated for the purpose of suppressing photocatalysis, and the composition is not limited, but silicon oxide Inorganic oxides such as alumina, zinc oxide and zinc oxide are preferred.
  • the coating method of the surface coating agent is not particularly limited, and titanium oxide particles obtained by a known method can be used.
  • a light stabilizer such as a hindered amine can be added to the resin.
  • a light stabilizer such as a hindered amine
  • the colorant particles used in the present invention preferably have an average particle size of 0.2 to 0.7 ⁇ m, and more preferably 0.25 to 0.35 ⁇ m for the purpose of increasing the reflectance of visible light.
  • the average particle size is smaller than 0.2 ⁇ m, the titanium oxide particles and the like are not preferable because the activity becomes high and causes deterioration of the resin. On the other hand, if the average particle diameter exceeds 0.7 ⁇ m, the dispersibility in the resin is deteriorated, and this may cause clogging of the filter used during film production, which is not preferable.
  • the amount of the colorant added to the B layer used in the present invention depends on the specific gravity, but must be in the range of 5 to 50% by weight, and more preferably in the range of 10 to 30% by weight. More preferred.
  • the addition amount is 5% by weight or more, sufficient whitening and light reflection effect can be obtained, and the wiring material such as a bus bar can be prevented from being transparent and can be excellent in design.
  • the upper limit is 50% by weight, whitening and concealment will not be improved even if added more than this, and the colorant will be sufficiently dispersed in the resin to ensure stable film formation. by.
  • the polypropylene resin in the B layer is homopolypropylene, ethylene. At least one resin selected from random or block copolymers of propylene and propylene, or a mixed resin of these resins and polyethylene, and the content of polyethylene should be less than 30% by weight of the total resin components It is preferable for maintaining the property.
  • the pelletizing method is generally a method of cutting the melted material after melt extrusion, but is not limited to this method.
  • the C layer in the present invention is composed of a polypropylene resin composition, and, like the B layer, one or more resins selected from polypropylene resins such as homopolypropylene, random or block copolymers of ethylene and propylene are used.
  • polypropylene resins such as homopolypropylene, random or block copolymers of ethylene and propylene are used.
  • the main component and the polypropylene resin is contained in an amount of 70% by weight or more, but it is homogenous from the viewpoints of heat resistance, slipperiness, film handling, scratch resistance, and curl resistance.
  • Most preferred is polypropylene alone.
  • the melting point of the polypropylene resin is preferably in the range of 150 ° C. to 170 ° C. from the viewpoints of heat resistance, slipperiness, film handling, scratch resistance, and curl resistance.
  • the melting point is 150 ° C. or more, which is excellent in heat resistance, and the thickness and thickness of the sheet are not reduced or the partial discharge voltage is not lowered by the temperature and pressure when thermally fused to EVA as a back sheet for solar cells.
  • the polypropylene resin preferably has an MFR at 230 ° C. in the range of 1.0 to 15 g / 10 min.
  • MFR is smaller than 1.0 g / 10 min, the necking down may occur in the film forming process, and stable production of the film may be difficult.
  • MFR is larger than 15 g / 10 minutes, the crystallization speed increases and it may become brittle.
  • a crystal nucleating agent can be added as necessary.
  • an ⁇ -crystal nucleating agent is preferable, and specific examples include sorbitol-based and cyclopentadiene-based crystal nucleating agents.
  • the addition amount of the crystal nucleating agent can be selected in the range of 0.1 to 3.0% by weight based on the resin.
  • a known antioxidant should be added to the A layer, B layer, and C layer from the viewpoint of preventing discoloration and maintaining strength.
  • Antioxidants include phenol-based, aromatic amine-based, thioether-based, phosphorus-based and the like, and it is preferable to use two or more types in combination in order to increase the effect with a small amount.
  • the combined use of phenol and phosphorus is preferred, and examples include phosphorus-phenol antioxidants.
  • this antioxidant it is preferable to add “Sumilizer GP” manufactured by Sumitomo Chemical because thermal stability and weather resistance during extrusion are improved.
  • the addition amount is preferably in the range of 0.05 to 0.35% by weight with respect to the resin of each layer. If the addition amount is less than 0.05% by weight, the effect is low, and if it exceeds 0.35% by weight, the dispersibility may deteriorate.
  • At least one of the A layer, the B layer, and the C layer in the present invention is described above from the viewpoint of preventing discoloration and improving weather resistance when used as a solar cell back surface protective sheet material.
  • other additives may be included.
  • the other additives include a light stabilizer, an ultraviolet absorber, and a heat stabilizer.
  • the light stabilizer one that captures active species at the start of photodegradation in the resin and prevents photooxidation can be used.
  • UV absorber As the above-mentioned ultraviolet absorber, it absorbs harmful ultraviolet rays in sunlight, converts them into innocuous heat energy in the molecule, and prevents the activation of active species that initiate photodegradation in the resin.
  • heat stabilizer examples include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus Acids, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) penta
  • phosphorus heat stabilizers such as erythritol diphosphite
  • lactone heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Can do. Moreover, these can also use 1 type or 2 types or more. Among these, it is preferable to use a phosphorus heat stabilizer and a lactone heat stabilizer
  • the content of the mixture of the ultraviolet absorber, heat stabilizer and the like is preferably in the range of 0.01 to 10.0% by weight with respect to the resin composition of each layer.
  • a flame retardant can be added to the film of the present invention as necessary. It does not specifically limit as a flame retardant. Well-known techniques, such as an organic flame retardant and an inorganic flame retardant, are applicable. Examples of organic flame retardants include those containing at least one chlorine atom or bromine atom in the molecule, such as chlorinated paraffin, chlorinated polyethylene, hexachloroendomethylenetetrahydrophthalic acid, perchloropentacyclodecane, and tetrachlorophthalic anhydride.
  • inorganic flame retardants include inorganic hydroxide salts such as aluminum hydroxide and magnesium hydroxide, phosphorus oxides such as ammonium phosphate and zinc phosphate, red phosphorus, antimony trioxide and expanded graphite. .
  • the blending amount of the organic flame retardant and the inorganic flame retardant alone or in a mixture is preferably in the range of 5 to 30% by weight with respect to the resin of each layer. If the addition amount is less than 5% by weight, there is no effect of addition, and if it exceeds 30% by weight, dispersibility may be deteriorated or coloring with a flame retardant may occur.
  • the thickness of the film of the present invention varies depending on the structure of the solar cell used, the thickness is preferably in the range of 10 to 200 ⁇ m, and more preferably in the range of 20 to 150 ⁇ m from the viewpoint of film production and lamination with other substrates.
  • the film of the present invention is composed of A layer / B layer / C layer, and the lamination ratio is not particularly limited, but the range of A layer and C layer is 5 to 20%, and B layer is 90 to 60%. Preferably there is.
  • a resin containing a large amount of particles in the die at the time of manufacture by sandwiching the B layer containing the colorant between the A layer and the C layer by using the A layer / B layer / C layer.
  • the adhesion of the decomposed product can be suppressed, and quality problems such as process contamination and film scratches caused by dropping the decomposed product can be avoided.
  • Young's modulus of the film of the present invention is preferably in the range of 300 to 1000 MPa from the viewpoint of winding properties during film formation and handling properties during secondary processing such as lamination.
  • the layer A is configured to be on the incident surface side of the solar cell.
  • EVA which is a filler used on the incident surface side, and the A layer, excellent thermal adhesiveness can be obtained.
  • an easy adhesion treatment on the C layer for the purpose of improving the adhesiveness of the adhesive with other materials.
  • the easy adhesion treatment include methods such as corona discharge treatment, plasma treatment, and chemical treatment.
  • a low-cost corona discharge treatment is particularly preferable.
  • the wetting tension at this time is preferably in the range of 35 to 55 mN / m.
  • the film of the present invention can be used by being laminated with other base materials by a method such as adhesive or heat fusion.
  • base materials include aluminum foil, paper, and a thermoplastic resin film.
  • Thermoplastic resins include polyesters such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, styrene resins such as polystyrene and acrylonitrile / styrene copolymer, polycarbonate , Polyamide, polyether, polyurethane, polyphenylene sulfide, polyester amide, polyether ester, polyvinyl chloride, polymethacrylic acid ester, modified polyphenylene ether, polyarylate, polysulfone, polyether imide, polyamide imide, polyimide and the main components thereof Or a mixture of these resins.
  • the light reflectance at 560 nm on the layer A surface side of the solar cell back surface protective sheet obtained by laminating the film of the present invention and the PET film is preferably 85% or more, more preferably 90% or more.
  • the power generation efficiency of the solar cell is preferably increased.
  • a resin used for the layer A a resin mixture is used in which 50 to 500 parts by weight of a polypropylene resin is mixed with 100 parts by weight of LLDPE having a melting point of 110 ° C. to 130 ° C.
  • a resin used for the B layer a polypropylene resin having a melting point in the range of 140 ° C. to 170 ° C., a coloring agent, 5 to 50% by weight of rutile type titanium oxide, and “Sumilizer GP” as an antioxidant 0 A resin mixture mixed in the range of 0.05 to 0.35% by weight is used.
  • a resin used for the layer C a polypropylene resin having a melting point of 150 to 170 ° C. was used. Each of the resins prepared in this way is supplied to a single-screw melt extruder and melted in the range of 220 to 280 ° C., respectively. After removing foreign substances and coarse inorganic particles through a filter installed in the middle of the polymer tube, a multi-manifold type T die or a feed block installed on top of the T die is used for A layer / B layer / C layer type. Three-kind three-layer lamination is performed, and the unstretched film is obtained by discharging from a T die onto a rotating metal roll with the C layer side facing the metal roll surface.
  • the surface temperature of the rotating metal roll is preferably controlled to 20 to 60 ° C., because the C layer does not stick to the metal roll and the crystallinity is improved.
  • the C layer of the film of the present invention thus obtained is subjected to corona discharge treatment in air or in one or more atmospheres of nitrogen gas and carbon dioxide gas for bonding to other substrates, and the surface wetting tension. Is wound up to 35 mN / m or more.
  • the polyolefin-based resin multilayer film of the present invention can be suitably used for a solar cell back surface protective sheet.
  • a solar cell back surface protective sheet for example, a hydrolysis-resistant PET film (Toray Industries, Inc .: “Lumirror” X10S) having a thickness of 25 to 250 ⁇ m and a polyolefin multilayer laminated film of the present invention are used with a known adhesive. It can be used as a dry laminate.
  • each layer in the case of a laminated film is as follows: the laminated film is embedded in an epoxy resin, the film cross section is cut out with a microtome, and the cross section is magnified 200 times with a polarizing microscope (Nikon Corporation, ECLIPSE E400 POL). The thickness ratio of each layer was determined.
  • the melting point of the resin used is increased by heating from 20 ° C. to 10 ° C./minute using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60). The highest peak temperature of the peak was taken as the melting point.
  • Peel strength is 70 N / 15 mm or more +: Peel strength is less than 70 N / 15 mm, 40 N / 15 mm or more ⁇ : Peel strength is less than 40 N / 15 mm -: Peeled at the lamination interface of the polyolefin resin multilayer film.
  • Example 1 As a resin used for the layer A, a melting point of 127 ° C., a density of 0.940 g / cm 3 , an MLD of 5.0 g / 10 minutes, LLDPE of 80 parts by weight, a melting point of 112 ° C., a density of 0.912 g / cm 3 , and an MFR of 4.0 g / 10 20 parts by weight of LDPE (total 100 parts by weight of polyethylene), and a polypropylene resin, an ethylene / propylene random copolymer having a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 mol / 10 min.
  • the resin used for the B layer is a titanium oxide master batch with respect to 100 parts by weight of homopolypropylene (hereinafter abbreviated as H-PP) having a melting point of 160 ° C., a density of 0.90 g / cm 3 , and an MFR of 7 g / 10 min.
  • H-PP homopolypropylene
  • a resin mixture mixed with 30 parts by weight of A was used.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight.
  • an ethylene / propylene block copolymer resin (hereinafter referred to as B-PP) having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4.0 g / 10 min, and an ethylene content of 7 mol%. (Abbreviated) was used.
  • the corona discharge treatment was performed on the C side of the multilayer film, and the film was wound up with a surface wetting tension of 40 mN / m.
  • the laminated film was aged at a temperature of 40 ° C. for 72 hours to promote the curing reaction of the adhesive layer, and used as the solar cell back surface protective sheet of the present invention.
  • Table 1 shows the overall evaluation results including heat resistance of the Enomoto film that was thermally bonded to EVA. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Example 2 As the resin used in the A layer, melting point 112 ° C., relative LDPE100 parts of density 0.912g / cm 3, MFR4g / 10 min, melting point 0.99 ° C., density 0.900g / cm 3, MFR7g / 10 min, ethylene content A resin mixture of 150 parts by weight of EPC in an amount of 4 mol% was used.
  • the resin used for layer B has a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 min, an ethylene content of 4 mol%, and 100 parts by weight of EPC with a melting point of 160 ° C. and a density of 0.900 g. / cm 3, MFR4g / 10 min, B-PP100 parts of ethylene content 7 mol%, and a resin mixture obtained by mixing the titanium oxide master batch A20 parts.
  • the addition amount of titanium oxide, which is a coloring agent, is 5.5% by weight.
  • the resin used for the C layer has a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, an ethylene content of 7 mol%, and 100 parts by weight of B-PP with a melting point of 162 ° C. and a density of 0.900 g / A resin mixture in which 100 parts by weight of H-PP of cm 3 and MFR of 7 g / 10 min was mixed was used.
  • Example 3 As the resin used in the A layer, melting point 127 ° C., relative LLDPE70 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE A resin mixture prepared by mixing 30 parts by weight (total 100 parts by weight of polyethylene) and 200 parts by weight of EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 mol / 10 min. Using.
  • the melting point is 160 ° C.
  • the density is 0.90 g / cm 3
  • the MFR is 4 g / 10 minutes
  • the ethylene content is 7 mol%.
  • the resin mixture which mixed was used.
  • the addition amount of titanium oxide as a coloring agent is 19.5% by weight.
  • EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 minutes, and an ethylene content of 4 mol% was used.
  • CC layer of the multilayer film was subjected to corona discharge treatment and wound up with a surface wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • the certified film cleared all the necessary requirements of the present invention as shown in Table 1.
  • Example 4 As the resin used in the A layer, melting point 127 ° C., relative LLDPE97 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE A resin mixture of 3 parts by weight (total 100 parts by weight of polyethylene) and 50 parts by weight of H-PP with a melting point of 164 ° C. and a density of 0.900 g / cm 3 and an MFR of 3 g / 10 min was used as the polypropylene resin.
  • the resin used for layer B a resin mixture in which 100 parts by weight of titanium oxide master batch A is mixed with 100 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 and MFR of 7 g / 10 minutes is used. It was.
  • the addition amount of titanium oxide as a coloring agent is 30.0% by weight.
  • H-PP having a melting point of 162 ° C., a density of 0.900 g / cm 3 and an MFR of 7 g / 10 min was used.
  • CC layer of the multilayer film was subjected to corona discharge treatment and wound up with a surface wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. As shown in Table 1, this film cleared all the necessary requirements of the present invention.
  • the resin used for the A layer has a melting point of 127 ° C., a density of 0.940 g / cm 3 , and 100 parts by weight of LLDPE with an MFR of 5 g / 10 min.
  • titanium oxide master batch A As the resin used for layer B, 300 parts by weight of titanium oxide master batch A is mixed with 100 parts by weight of EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , MFR of 7 g / 10 minutes, and an ethylene content of 4 mol%. The resin mixture used was used. The addition amount of titanium oxide as a coloring agent is 45.0% by weight.
  • the resin used for the C layer has a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / 10 with respect to 100 parts by weight of H-PP having a melting point of 162 ° C., a density of 0.900 g / cm 3 and an MFR of 7 g / 10 min.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m of% / 70% / 20% was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. As shown in Table 1, this film cleared all the necessary requirements of the present invention.
  • Example 6 As a resin used for the layer A, a melting point of 131 ° C., a density of 0.956 g / cm 3 , an MFR of 4 g / 10 minutes, HDPE of 100 parts by weight, a polypropylene resin, a melting point of 164 ° C., a density of 0.900 g / cm 3 , MFR 3 g / A resin mixture of 50 parts by weight of H-PP for 10 minutes was used.
  • a resin used for the layer A a melting point of 131 ° C., a density of 0.956 g / cm 3 , an MFR of 4 g / 10 minutes, HDPE of 100 parts by weight, a polypropylene resin, a melting point of 164 ° C., a density of 0.900 g / cm 3 , MFR 3 g / A resin mixture of 50 parts by weight of H-PP for 10 minutes was used.
  • a resin mixture in which 25 parts by weight of a titanium oxide master batch A is mixed with 100 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 and an MFR of 7 g / 10 minutes is used. It was.
  • the addition amount of titanium oxide as a coloring agent is 12.0% by weight.
  • B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% was used.
  • the certified film cleared all the necessary requirements of the present invention as shown in Table 1. However, since LDPE or HDPE having a higher melting point than LLDPE was formulated for the A layer, the adhesion between the A layer and EVA after the glass laminate test was slightly inferior.
  • Example 7 The film of Example 1 was melted using a uniaxial melt extruder at 260 ° C., and then pelletized to obtain a recovered raw material.
  • the resin used for the B layer 50 parts by weight of the recovered raw material with respect to 100 parts by weight of EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 minutes, and an ethylene content of 4 mol%, titanium oxide A resin mixture in which 21 parts by weight of master batch A was mixed was used. The addition amount of titanium oxide as a coloring agent is 13.8% by weight.
  • the polyolefin resin multilayer film of the same formulation and the same composition as Example 1 was obtained. The film was made into a solar cell back surface protective sheet by the same method as in Example 1. As shown in Table 1, this film cleared all the necessary requirements of the present invention.
  • the resin used for layer B has a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 min, an ethylene content of 4 mol%, and 100 parts by weight of EPC with a melting point of 112 ° C. and a density of 0.912 g /
  • a resin mixture prepared by mixing 50 parts by weight of LDPE with cm 3 and MFR 4 g / 10 min and 21 parts by weight of titanium oxide master batch A was used.
  • the addition amount of titanium oxide as a coloring agent is 7.4% by weight.
  • the polyolefin resin multilayer film of the same formulation and the same composition as Example 1 was obtained. The film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • Example 9 The resin used for the A layer has a melting point of 127 ° C., a density of 0.940 g / cm 3 , and 100 parts by weight of LLDPE with an MFR of 5 g / 10 min.
  • a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / A resin mixture in which 350 parts by weight of EPC having an ethylene content of 4 mol% for 10 minutes was mixed was used.
  • the polyolefin resin multilayer film of the same formulation as Example 1 and the same composition was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. As shown in Table 1, this film cleared all the necessary requirements of the present invention.
  • the resin used for the A layer has a melting point of 127 ° C., a density of 0.940 g / cm 3 , and 100 parts by weight of LLDPE with an MFR of 5 g / 10 min.
  • a polypropylene resin a melting point of 160 ° C., a density of 0.900 g / cm 3 , and an MFR of 4 g / A resin mixture in which 500 parts by weight of B-PP having an ethylene content of 7 mol% was mixed for 10 minutes was used.
  • the polyolefin resin multilayer film of the same formulation as Example 1 and the same composition was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. As shown in Table 1, this film cleared all the necessary requirements of the present invention.
  • Example 11 As resin used for the A layer, benzotriazole-based UV absorber master batch A100 parts by weight with respect to 100 parts by weight of EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / 10 min. The resin mixture which mixed was used. The addition amount of the benzotriazole ultraviolet absorber is 5.0% by weight.
  • the resin used for layer B includes a titanium oxide masterbatch A, 30 parts by weight, and a benzotriazole-based ultraviolet absorber for 35 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.90 g / cm 3 , and an MFR of 7 g / 10 minutes.
  • a resin mixture in which 65 parts by weight of master batch B was mixed was used.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight
  • the addition amount of benzotriazole-based ultraviolet absorber is 5.0% by weight.
  • B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% was used.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m was obtained.
  • Corona discharge treatment was performed on one side of the C layer of the multilayer film, and the surface was wound with a wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • This film was thermally bonded to EVA, and the comprehensive evaluation results including heat resistance are shown in Table 1. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Example 12 As the resin used in the A layer, melting point 127 ° C., relative LLDPE70 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE 20 parts by weight and, as a polypropylene resin, a resin in which melting point 150 ° C., density 0.900 g / cm 3 , MFR 7 g / 10 min ethylene content 4 mol% EPC 100 parts by weight, nano zinc oxide master batch A 10 parts by weight A mixture was used. The amount of nano zinc oxide added is 0.5% by weight.
  • the resin used for layer B includes a melting point of 160 ° C., a density of 0.90 g / cm 3 , an MFR of 7 g / 10 min of H-PP of 2.5 parts by weight, a titanium oxide master batch A of 30 parts by weight, and a hindered amine UV absorption.
  • the addition amount of titanium oxide, which is a coloring agent, is 13.8% by weight
  • the addition amount of the benzotriazole ultraviolet absorber is 5.0% by weight
  • the addition amount of the hindered amine light stabilizer is 2.5% by weight.
  • a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and B-PP were used.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m was obtained.
  • Corona discharge treatment was performed on one side of the C layer of the multilayer film, and the surface was wound with a wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • This film was thermally bonded to EVA, and the comprehensive evaluation results including heat resistance are shown in Table 1. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Example 13 As the resin used in the A layer, melting point 127 ° C., relative LLDPE20 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE 20 parts by weight, hindered amine ultraviolet absorber master batch A 10 parts by weight, nano zinc oxide master batch A 50 parts by weight, and polypropylene resin, melting point 150 ° C., density 0.900 g / cm 3 , MFR 7 g / 10 min ethylene content A resin mixture obtained by mixing 100 parts by weight of 4 mol% EPC was used. The amount of hindered amine light stabilizer added was 0.5% by weight, and the amount of nano zinc oxide added was 2.5% by weight.
  • the resin used for the layer B a melting point of 160 ° C., a density 0.90 g / cm 3, relative to MFR7g / 10 min H-PP61 parts, the titanium oxide master batch A30 parts, hindered amine light stabilizer master A resin mixture in which 6.5 parts by weight of batch B and 32.5 parts by weight of nano zinc oxide master batch B were mixed was used.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight
  • the addition amount of a hindered amine light stabilizer is 0.5% by weight
  • the addition amount of nano zinc oxide is 2.5% by weight.
  • B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% was used.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m was obtained.
  • Corona discharge treatment was performed on one side of the C layer of the multilayer film, and the surface was wound with a wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • This film was thermally bonded to EVA, and the comprehensive evaluation results including heat resistance are shown in Table 1. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Example 14 As the resin used in the A layer, melting point 127 ° C., relative LLDPE70 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE 20 parts by weight, a hindered amine light stabilizer master batch A10 parts, and a polypropylene-based resin, melting point 0.99 ° C., the EPC100 parts of density 0.900g / cm 3, MFR7g / 10 min ethylene content 4 mol% mixture The resin mixture used was used. The amount of hindered amine light stabilizer added is 0.5% by weight.
  • the resin used for layer B is 30 parts by weight of titanium oxide masterbatch A, hindered amine light stable, with a melting point of 160 ° C., density of 0.90 g / cm 3 , and MFR of 7 g / 10 min.
  • a resin mixture in which 6.5 parts by weight of the agent master batch B was mixed was used.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight, and the addition amount of hindered amine light stabilizer is 0.5% by weight.
  • B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% was used.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m was obtained.
  • Corona discharge treatment was performed on one side of the C layer of the multilayer film, and the surface was wound with a wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • This film was thermally bonded to EVA, and the comprehensive evaluation results including heat resistance are shown in Table 1. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Example 15 As the resin used in the A layer, melting point 127 ° C., relative LLDPE60 parts of density 0.940g / cm 3, MFR5g / 10 min, melting point 112 ° C., a density 0.912g / cm 3, MFR4g / 10 min LDPE 20 parts by weight, a hindered amine-based master batch master batch A10 parts, benzotriazole-based ultraviolet absorber masterbatch A10 parts, and a polypropylene-based resin, melting point 0.99 ° C., density 0.900g / cm 3, MFR7g / 10 min ethylene A resin mixture in which 100 parts by weight of EPC having a content of 4 mol% was mixed was used. The amount of hindered amine light stabilizer added is 0.5% by weight, and the amount of benzotriazole UV absorber added is 0.5% by weight.
  • the resin used for the B layer 30 parts by weight of titanium oxide master batch A, hindered amine light stabilizer master with respect to 87 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.90 g / cm 3 and MFR of 7 g / 10 min.
  • a resin mixture obtained by mixing 6.5 parts by weight of batch B and 6.5 parts by weight of benzotriazole-based UV absorber master batch B was used.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight
  • the addition amount of a hindered amine light stabilizer is 0.5% by weight
  • the addition amount of a benzotriazole ultraviolet absorber is 0.5% by weight.
  • B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol% was used.
  • a polyolefin resin multilayer film having a film thickness of 150 ⁇ m was obtained.
  • Corona discharge treatment was performed on one side of the C layer of the multilayer film, and the surface was wound with a wetting tension of 40 mN / m.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • This film was thermally bonded to EVA, and the comprehensive evaluation results including heat resistance are shown in Table 1. As is clear from the table, the film of the present invention cleared all the requirements necessary for a solar cell back surface protective sheet.
  • Comparative Example 1 As a resin used for the A layer and the C layer, a melting point of 150 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / 10 with respect to 100 parts by weight of LLDPE having a melting point of 127 ° C., a density of 0.940 g / cm 3 and an MFR of 5 g / 10 min. A resin mixture of 20 parts by weight of EPC having an ethylene content of 4 mol% was used.
  • the resin used for the layer B a melting point of 116 ° C., relative LDPE100 parts of density 0.912g / cm 3, MFR4g / 10 min, a resin mixture of titanium oxide master batch B30 parts.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight.
  • Each of the resins prepared as described above is supplied to a single-screw melt extruder, melt extruded at 260 ° C., extruded onto a casting drum maintained at 30 ° C., and cooled at 25 ° C. from the non-drum surface side.
  • Was sprayed and solidified by cooling to obtain a polyolefin resin multilayer film having a thickness constitution ratio of each layer of A layer / B layer / C layer 10% / 80% / 10% and a film thickness of 150 ⁇ m.
  • One layer A of the multilayer film was subjected to corona discharge treatment and wound up with a surface wetting tension of 40 mN / m.
  • Corona-treated surface of the sample film obtained in the present invention and a biaxially stretched polyester film (“Lumirror” X10S 125 ⁇ m manufactured by Toray Industries Inc.) are used as a two-component curing type adhesive (LX-903 / KL- manufactured by Dainippon Ink and Chemicals, Inc.) 75 8/1) was applied at a solid coating thickness of 6 ⁇ m and dried to prepare a laminate.
  • the laminated film was aged at a temperature of 40 ° C. for 72 hours to promote the curing reaction of the adhesive layer and foaming in the adhesive layer, thereby obtaining the solar cell back surface protective sheet of the present invention.
  • This film has a low content of the A layer polypropylene resin, the portion corresponding to the C layer is made of a resin mainly composed of polyethylene, and since the B layer is LDPE, the heat resistance is inferior and the thickness change is 20%. As described above, two or more pieces of copper plate were observed.
  • Table 2 The results of each comparative example are shown in Table 2.
  • Comparative Example 2 The A layer had the same formulation as Comparative Example 1.
  • the resin used for layer B was a resin mixture in which 30 parts by weight of titanium oxide master batch A was mixed with 100 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , and MFR of 7 g / 10 minutes. .
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight.
  • a resin used for the C layer resin a melting point of 127 ° C., a density of 0.940 g / cm 3 , an MFR of 5 g / 10 minutes, LLDPE of 100 parts by weight, a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 7 g / 10 minutes, ethylene
  • a resin mixture in which 50 parts by weight of EPC having a content of 4 mol% was mixed was used.
  • A-layer / B-layer / C-layer 10% / A polyolefin resin multilayer film having a film thickness of 70 ⁇ m / 20% and a thickness of 150 ⁇ m was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1.
  • this film did not show copper plate shedding in the heat resistance test, it was excellent in adhesiveness with EVA, but with a B layer mainly composed of polypropylene and 20 parts by weight of polypropylene resin and less polyethylene. Peeling easily occurred at the interface of the main A layer.
  • Comparative Example 3 As a resin used for the A layer, EPC having a melting point of 150 ° C., a density of 0.900 g / cm 3 , an MFR of 5 g / 10 min, and an ethylene content of 4 mol% was used.
  • the resin used for the B layer was the same as the B layer of Comparative Example 2.
  • H-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , and an MFR of 7 g / 10 min was used.
  • the amount of the polypropylene resin added to the A layer was as large as 550 parts by weight, so that the film peeled at the interface between the A layer and EVA, and sufficient adhesive strength was not obtained.
  • the resin composition of the B layer a resin mixture in which 3 parts by weight of titanium oxide master batch A was mixed with 100 parts by weight of H-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , and MFR of 7 g / 10 minutes was used. .
  • the back side of the solar cell was protected in the same manner as in Example 1, using B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 min, and an ethylene content of 7 mol%. A sheet was obtained.
  • the addition amount of titanium oxide as a coloring agent is 1.7% by weight.
  • the Enomoto film was judged to be unfavorable because the copper plate was transparent before the heat resistance test because the titanium oxide concentration was low.
  • Comparative Example 6 a solar cell back surface protective sheet of the same formulation and the same manufacturing method was obtained except that the titanium oxide master batch A of the B layer was 600 parts by weight. The addition amount of titanium oxide as a coloring agent is 51.4% by weight.
  • Tsubakimoto film had a high concentration of titanium oxide in the film production process, agglomerates occurred frequently, and the agglomerates were clogged in the die, so that the film could not be collected.
  • the A layer had the same formulation as in Example 1.
  • a resin mixture of 30 parts by weight of titanium oxide master batch B was used with respect to 100 parts by weight of LDPE having a melting point of 116 ° C., a density of 0.912 g / cm 3 , and MFR of 4 g / 10 minutes.
  • the addition amount of titanium oxide as a coloring agent is 13.8% by weight.
  • the C layer had the same formulation as Comparative Example 5.
  • A-layer / B-layer / C-layer 10% /
  • a polyolefin resin multilayer film having a film thickness of 70 ⁇ m / 20% and a thickness of 150 ⁇ m was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. In this film, the see-through of the copper plate occurred in the heat resistance test. Further, peeling was observed at the interface between the B layer and the C layer.
  • the A layer and B layer had the same formulation as in Example 1.
  • the resin used for the layer C a melting point of 116 ° C., using a density 0.912g / cm 3, MFR4g / 10 min LDPE.
  • a polyolefin resin multilayer film having a film thickness of 70 ⁇ m / 20% and a thickness of 150 ⁇ m was obtained.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. In this film, peeling at the interface between the B layer and the C layer was observed in the adhesion test with EVA.
  • the B layer had the same formulation as in Example 1.
  • the C layer used was B-PP having a melting point of 160 ° C., a density of 0.900 g / cm 3 , an MFR of 4 g / 10 minutes, and an ethylene content of 7 mol%.
  • the film was made into a solar cell back surface protective sheet by the same method as in Example 1. This film had low adhesion between the A layer and EVA in the adhesion test with EVA.

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Abstract

L'invention porte sur un film de résine polyoléfine multicouche pour des feuilles de protection arrière pour des photopiles qui a une configuration à trois couches composée de couche A/couche B/couche C, caractérisé en ce que la couche A comprend une composition de résine comprenant 100 parties en poids de polyéthylène et 50-500 parties en poids d'une résine de polypropylène, la couche B comprend une composition de résine de polypropylène contenant un colorant ajouté à hauteur de 5-50 % en poids et la couche C comprend une composition de résine de polypropylène. Le film de résine polyoléfine multicouche a une excellente résistance thermique au point que le film, lorsqu'il est chauffé et collé à la presse dans, par exemple, une étape de stratification à du verre, n'est pas aminci sous l'influence d'un élément de câblage tel qu'une barre omnibus. Le film a une force d'adhésion élevée après collage thermique à des résines qui sont employées comme matériaux de scellement pour des cellules de production d'énergie électrique, telles que des résines de copolymère d'éthylène/acétate de vinyle, il a une excellente cohésion interlaminaire et il est approprié pour être utilisé comme matériau pour des feuilles de protection arrière pour des photopiles.
PCT/JP2011/071073 2010-09-29 2011-09-15 Film de résine polyoléfine multicouche pour feuille de protection arrière pour photopile Ceased WO2012043248A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2011800451072A CN103119726A (zh) 2010-09-29 2011-09-15 太阳能电池背面保护片材用聚烯烃类树脂多层膜
JP2011543011A JP5732402B2 (ja) 2010-09-29 2011-09-15 太陽電池裏面保護シート用ポリオレフィン系樹脂多層フィルム

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JP2010-218606 2010-09-29
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JP2012171310A (ja) * 2011-02-24 2012-09-10 Toray Advanced Film Co Ltd ポリオレフィン系樹脂多層フィルム
WO2013051403A1 (fr) * 2011-10-05 2013-04-11 東レフィルム加工株式会社 Feuille de protection arrière destinée à un module de cellule solaire et module de cellule solaire utilisant celle-ci
WO2014021003A1 (fr) * 2012-07-30 2014-02-06 東レ株式会社 Feuille stratifiée et son procédé de fabrication
WO2015008614A1 (fr) * 2013-07-17 2015-01-22 東レフィルム加工株式会社 Feuille de protection arrière pour module de cellule solaire
JP2018536081A (ja) * 2015-10-28 2018-12-06 ボレアリス エージー 層要素用ポリプロピレン組成物

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CN104842616B (zh) * 2015-04-10 2017-08-08 苏州中来光伏新材股份有限公司 一种光伏太阳能电池复合背板和制备方法及其组件
CN109964320B (zh) * 2016-11-11 2024-03-05 赢润太阳能解决方案有限公司 包含面向背面封装剂的基于聚烯烃的功能层的背板
CN107501785A (zh) * 2017-08-16 2017-12-22 合肥卓立雅工程材料科技有限公司 一种防辐射阻燃型pvc高分子防水卷材及其制备方法
KR20250016475A (ko) * 2018-05-24 2025-02-03 다이니폰 인사츠 가부시키가이샤 자발광형 표시체용 또는 직하형 백라이트용의 밀봉재 시트, 자발광형 표시체, 직하형 백라이트

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Publication number Priority date Publication date Assignee Title
JP2012171310A (ja) * 2011-02-24 2012-09-10 Toray Advanced Film Co Ltd ポリオレフィン系樹脂多層フィルム
WO2013051403A1 (fr) * 2011-10-05 2013-04-11 東レフィルム加工株式会社 Feuille de protection arrière destinée à un module de cellule solaire et module de cellule solaire utilisant celle-ci
WO2014021003A1 (fr) * 2012-07-30 2014-02-06 東レ株式会社 Feuille stratifiée et son procédé de fabrication
WO2015008614A1 (fr) * 2013-07-17 2015-01-22 東レフィルム加工株式会社 Feuille de protection arrière pour module de cellule solaire
JP2018536081A (ja) * 2015-10-28 2018-12-06 ボレアリス エージー 層要素用ポリプロピレン組成物
US10934422B2 (en) 2015-10-28 2021-03-02 Borealis Ag Polypropylene compositions for a layer element

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