WO2012029465A1 - Feuille protectrice de surface avant pour photopile et module de photopile produit à l'aide de celle-ci - Google Patents

Feuille protectrice de surface avant pour photopile et module de photopile produit à l'aide de celle-ci Download PDF

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WO2012029465A1
WO2012029465A1 PCT/JP2011/067228 JP2011067228W WO2012029465A1 WO 2012029465 A1 WO2012029465 A1 WO 2012029465A1 JP 2011067228 W JP2011067228 W JP 2011067228W WO 2012029465 A1 WO2012029465 A1 WO 2012029465A1
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solar cell
protective sheet
layer
front protective
ethylene
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PCT/JP2011/067228
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English (en)
Japanese (ja)
Inventor
治 赤池
谷口　浩一郎
潤 西岡
亮太 山本
陽 宮下
綾　哲也
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三菱樹脂株式会社
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • 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 front protective sheet used as a front protective member for a cell for solar cells, and a laminate of the same and a sealing material, and more particularly, a solar cell comprising a resin layer having flexibility, moisture resistance and weather resistance.
  • Solar cell front protective sheet effective for weight reduction and durability improvement, and laminate of solar cell front protective sheet / encapsulant laminated with a sealing material effective for improving transparency and heat resistance
  • the present invention relates to a lightweight and highly durable solar cell using the solar cell front protective sheet or laminate.
  • a solar cell has a configuration in which solar cell cells are sealed between a front surface protective sheet and a back surface protective sheet from the light receiving surface side by a sealing film such as an ethylene-vinyl acetate copolymer, polyethylene, or polypropylene film.
  • a sealing film such as an ethylene-vinyl acetate copolymer, polyethylene, or polypropylene film.
  • Such a solar cell is usually manufactured by laminating a front protective sheet, a sealing film, a power generation element, a sealing film, and a back protective sheet in this order and bonding them together by heating and melting.
  • As a front protective sheet for solar cells it is required to have excellent durability against ultraviolet rays.
  • the sealing material has flexibility and impact resistance to protect the solar cell element, heat resistance when the solar cell module generates heat, and transparency to efficiently reach the solar cell element (all Light transmittance, etc.), durability, dimensional stability, flame retardancy, water vapor barrier properties, etc. are mainly required.
  • a glass plate is used as the surface-side protection member.
  • the glass plate is excellent in light resistance and moisture resistance, but has a drawback that it is heavy and weak against impact and easily cracked.
  • Patent Document 1 a transparent resin film is used for the front protective sheet to solve the problem of damage due to weight and impact, and the front protective sheet is combined with a resin film having good weather resistance and moisture resistance. Therefore, a solar cell front protective sheet effective for improving the durability of the solar cell has been proposed.
  • the front protective sheet for solar cells described in Patent Document 1 when the weather resistant layer and the moisture-proof layer are bonded to the front protective sheet using an adhesive, it is difficult to increase the thickness of the adhesive from the viewpoint of productivity. In some cases, the moisture-proof layer is damaged by falling objects on the light-receiving surface, thereby deteriorating the moisture-proof function.
  • the front protective sheet is made of an ethylene-vinyl acetate copolymer, which is generally used as a sealing material for solar electronics, as a film for laminating a weatherproof layer and a moisture-proof layer.
  • An adhesive is proposed (Patent Document 2).
  • Patent Document 2 A method for preventing deterioration of the moisture-proof function due to falling objects on the battery has been proposed (Patent Document 2).
  • Patent Document 2 when an ethylene-vinyl acetate copolymer is used, crosslinking is usually performed using a crosslinking agent such as an organic peroxide for the purpose of imparting heat resistance to the copolymer. Deterioration of appearance and deterioration of moisture-proof layer occur.
  • the ethylene-vinyl acetate copolymer contains an acetic acid, a crosslinking agent, a crosslinking aid, etc. generated by hydrolysis of the ethylene-vinyl acetate copolymer during long-term use.
  • the resin and the adhesive are deteriorated and peeling at the interface in the layer occurs.
  • ethylene-vinyl acetate copolymer is used for the sealing material, stress due to cross-linking shrinkage is generated above and below the moisture-proof layer in vacuum lamination for manufacturing solar cells, and the barrier property of the moisture-proof layer is significantly reduced. There was also a problem of letting it go.
  • a solar cell encapsulant made of an ⁇ -olefin polymer that does not require crosslinking and does not generate acetic acid (Patent Document 3), or a polymer made of at least one polyolefin copolymer and at least one crystalline polyolefin
  • a solar cell encapsulating material (Patent Document 4) comprising a blend or a polymer alloy is disclosed.
  • the above Patent Document 4 specifically describes a polymer blend of a low melting point ethylene-vinyl acetate copolymer and a high melting point ethylene-vinyl acetate copolymer (see Example 1), ethylene-methacrylic acid copolymer.
  • Polymer blends of coalesced and general purpose crystalline polyethylene (see Example 2) and polymer blends of ethylene-methyl acrylate copolymer and general purpose crystalline polypropylene (see Example 3) are disclosed.
  • the resin composition comprising a polymer mainly composed of propylene specifically used in Patent Document 3 has insufficient transparency (total light transmittance: 83.2% (see Examples). )))
  • total light transmittance 83.2% (see Examples).
  • each polymer blend used in Patent Document 4 is not necessarily excellent in transparency, and there is still a problem in balancing the flexibility, heat resistance and transparency.
  • the use of such a polymer for both the front protective sheet and the encapsulant leads to a significant deterioration in light transmittance, which seriously affects the performance of the solar cell.
  • an object of the present invention is to solve the above-mentioned conventional problems in a protective sheet used as a transparent protective member for a solar cell, and to prevent deterioration of a resin layer having a moisture-proof performance constituting a part of the sheet
  • a resin layer with a good balance between flexibility, heat resistance and transparency, it prevents deterioration of the moisture resistance of the front protective sheet due to falling objects, etc., and transparency and long-term high moisture resistance
  • the present inventors have obtained a resin layer containing an ethylene- ⁇ -olefin random copolymer having specific thermal characteristics and an ethylene- ⁇ -olefin block copolymer having specific thermal characteristics.
  • the weather-resistant layer (A) and the moisture-proof layer (B) are divided into an ethylene- ⁇ -olefin random copolymer (C-1) that satisfies the following condition (1) and an ethylene- ⁇ that satisfies the following condition (2): -A front protective sheet for solar cells, which is laminated through a flexible layer (C) containing an olefin block copolymer (C-2), and the front protective sheet for solar cells, An ethylene- ⁇ -olefin random copolymer (D-1) satisfying the condition (1) and an ethylene- ⁇ -olefin block copolymer (D-2) satisfying the condition (2) below are contained.
  • the present invention relates to a solar cell front protective sheet / sealing material laminate formed by laminating a sealing material (D).
  • a sealing material D
  • the heat of crystal fusion measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 0 to 70 J / g.
  • the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 ° C. or more, and the crystal melting heat amount is 5 to 70 J / g.
  • the present invention also relates to a solar cell module and a solar cell produced using the solar cell front protective sheet or solar cell front protective sheet / sealing material laminate of the present invention.
  • a front protection sheet for solar cells which has both transparency and long-term high moisture resistance and weather resistance, and is effective in reducing the weight and durability of solar cells, and the front protection sheet for solar cells
  • a sealing material laminate can be provided, and a lightweight, highly durable solar cell module and a solar cell using the solar cell front protective sheet or solar cell front protective sheet / sealing material laminate Can be provided.
  • the weather-resistant layer (A) in the present invention is a layer that is rich in flexibility, excellent in heat resistance, moisture resistance, and UV durability, and preferably highly transparent, and aims to maintain the solar cell front protective sheet and the surface appearance.
  • Used as The weather resistance of the weather resistant layer is preferably such that there is little decrease in mechanical properties and total light transmittance in a weather resistance test conducted according to JIS K7350, and mechanical properties and total light transmittance after 5000 hours have passed. Are preferable, and those having no decrease in mechanical properties and total light transmittance after 10000 hours are particularly preferable.
  • Examples of the material for the weathering layer (A) include polytetrafluoroethylene (PTFE), 4-fluorinated ethylene-perchloroalkoxy copolymer (PFA), and 4-fluorinated ethylene-6-fluorinated propylene copolymer.
  • PTFE polytetrafluoroethylene
  • PFA 4-fluorinated ethylene-perchloroalkoxy copolymer
  • HPC 4-fluorinated ethylene-6-fluorinated propylene copolymer
  • Fluoropolymer films such as (FEP), 2-ethylene-4-fluoroethylene copolymer (ETFE), poly-3-fluoroethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF),
  • FEP 2-ethylene-4-fluoroethylene copolymer
  • PCTFE poly-3-fluoroethylene chloride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • EFE 2-ethylene-4-fluoroethylene copolymer
  • FEP 4-fluoroethylene Ren-6-fluorinated propylene copolymer
  • said ultraviolet absorber the thing similar to the below-mentioned ultraviolet absorber which can be contained in a flexible layer can be used.
  • the said resin can also be used by 1 type, it can also be used in combination of 2 or more type.
  • the thickness of the weather resistant layer (A) is generally about 20 to 200 ⁇ m, preferably 30 to 120 ⁇ m, more preferably 40 to 80 ⁇ m from the viewpoint of ease of handling as a film and cost.
  • the moisture-proof layer (B) in the present invention is a resin layer that is used to prevent moisture, internal conductors due to permeation of water, rusting of electrodes, and the like, and is preferably a resin layer that is highly transparent and excellent in moisture resistance. Although there is no particular limitation, those having at least one inorganic oxide coating film on at least one surface of the base material layer are preferably used.
  • the base material layer is preferably a thermoplastic polymer film, and any material can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials.
  • polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefins, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), nylon 6 , Nylon 66, nylon 12, polyamide such as copolymer nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, polyvinyl Examples include butyral, polyarylate, fluororesin, acrylate resin, and biodegradable resin.
  • polyesters, polyamides, and polyolefins are preferable from the viewpoints of film properties and cost.
  • polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable from the viewpoint of film properties.
  • the base material layer is a known additive such as an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, An antioxidant etc. can be contained.
  • the thermoplastic polymer film as the base material layer is formed by using the above raw materials, but when used as a base material, it may be unstretched or stretched. Good. Moreover, you may laminate
  • Such a base material layer can be produced by a conventionally known method.
  • the raw material resin is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be oriented substantially amorphously. No unstretched film can be produced.
  • a multilayer die it is possible to produce a single layer film made of one kind of resin, a multilayer film made of one kind of resin, a multilayer film made of various kinds of resins, and the like.
  • the unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like.
  • a film stretched in at least a uniaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.
  • the draw ratio can be arbitrarily set, but the heat shrinkage at 150 ° C. is preferably 0.01 to 5%, more preferably 0.01 to 2%.
  • a biaxially stretched polyethylene naphthalate film, a polyethylene terephthalate and / or a coextruded biaxially stretched film of polyethylene naphthalate and other plastics are preferable.
  • anchor coating agent examples include solvent-based or water-soluble polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl-modified resins, vinyl alcohol resins, vinyl butyral resins, ethylene vinyl alcohol resins, nitrocellulose resins, oxazoline group-containing resins, carbodiimides.
  • a group-containing resin, a methylene group-containing resin, an epoxy group-containing resin, a modified styrene resin, a modified silicon resin, an alkyl titanate, or the like can be used alone or in combination of two or more.
  • silane coupling agents titanium coupling agents, light blocking agents, ultraviolet absorbers, stabilizers, lubricants, antiblocking agents, antioxidants, etc., or they are copolymerized with the above resins Things can be used.
  • the anchor coat layer As a method for forming the anchor coat layer, a known coating method is appropriately adopted. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Alternatively, the vapor deposition layer may be immersed in a resin solution. After coating, the solvent can be evaporated using a known drying method such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying. Moreover, in order to improve water resistance and durability, the crosslinking process by electron beam irradiation can also be performed. Further, the formation of the anchor coat layer may be a method performed in the middle of the base material layer production line (in-line) or a method performed after the base material layer is manufactured (off-line).
  • a known coating method is appropriately adopted. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air
  • a substrate in which a coating film of a metal such as aluminum is formed on the base material layer is known.
  • a metal such as aluminum is applied to a solar cell, current may leak. Therefore, an inorganic oxide coating film such as silica / alumina is preferably used.
  • any of a vapor deposition method and a coating method can be used, but a vapor deposition method is preferred 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).
  • Examples of the inorganic substance constituting the inorganic oxide coating film include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrogenated carbon, and the like, 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.
  • the thickness of the coating film is preferably 40 to 1000 nm, more preferably 80 to 800 nm, and still more preferably 160 to 600 nm from the viewpoint of stable moistureproof performance.
  • the thickness of the base material layer is generally about 5 to 100 ⁇ m, preferably 8 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
  • the thickness of the moisture-proof layer (A) is generally about 6 to 100 ⁇ m, preferably 9 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
  • the flexible layer (C) in the present invention is used between the weather-resistant layer (A) and the moisture-proof layer (B).
  • a resin layer made of an ethylene- ⁇ -olefin copolymer is used because it is highly transparent, rich in flexibility, and excellent in heat resistance and hydrolysis. It is possible to use a resin composition containing an ethylene- ⁇ -olefin random copolymer having specific thermal characteristics and an ethylene- ⁇ -olefin block copolymer having specific thermal characteristics. This is necessary from the viewpoint of expressing flexibility.
  • the ethylene- ⁇ -olefin random copolymer having specific thermal characteristics is an ethylene- ⁇ -olefin random copolymer (C-1) that satisfies the following condition (1), and has specific thermal characteristics.
  • the ethylene- ⁇ -olefin block copolymer possessed is an ethylene- ⁇ -olefin block copolymer (C-2) that satisfies the following condition (2).
  • the heat of crystal fusion measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 0 to 70 J / g.
  • the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 ° C. or more, and the crystal melting heat amount is 5 to 70 J / g.
  • the heat resistance of the front protective sheet for solar cells is the characteristics of the ethylene- ⁇ -olefin random copolymer (C-1) constituting the flexible layer (C) (crystal melting peak temperature, crystal melting heat, MFR, molecular weight, etc.) And ethylene- ⁇ -olefin block copolymer (C-2), which are affected by various properties (crystal melting peak temperature, crystal melting heat, MFR, molecular weight, etc.), especially ethylene- ⁇ -olefin block copolymer The crystal melting peak temperature of (C-2) is strongly affected.
  • the temperature of a solar cell module rises to about 85 to 90 ° C. due to heat generated during power generation or radiant heat of sunlight, but the ethylene- ⁇ -olefin block copolymer (C— If the crystal melting peak temperature of 2) is 100 ° C. or higher, the heat resistance of the front protective sheet for solar cells can be ensured.
  • the upper limit temperature of the crystal melting peak temperature of the ethylene- ⁇ -olefin block copolymer (C-2) is 145 ° C., it can be sealed without excessively high temperature in the sealing step of the solar cell element. This is preferable because it is possible.
  • Types of ⁇ -olefins used in each of the ethylene- ⁇ -olefin random copolymer (C-1) and the ethylene- ⁇ -olefin block copolymer (C-2) constituting the flexible layer (C) in the present invention May be the same or different, but in the present invention, the same is the compatibility when mixed and the transparency of the front protective sheet, that is, the photoelectric conversion efficiency of the solar cell. Is preferable.
  • the total of (C-1) and (C-2) is 100 parts by mass.
  • the mixing (containing) mass ratio is in the above range because a flexible layer (C) having an excellent balance of flexibility, heat resistance, transparency and the like can be easily obtained.
  • the flexibility of the flexible layer (C) in the present invention may be appropriately adjusted in consideration of the shape, thickness, installation location, etc. of the applied solar cell.
  • the vibration frequency in dynamic viscoelasticity measurement is 10 Hz
  • the storage elastic modulus (E ′) at 20 ° C. is preferably 1 to 2000 MPa. From the viewpoint of protection of the solar cell element, the storage elastic modulus (E ′) is preferably lower.
  • the pressure is more preferably 3 to 1000 MPa, further preferably 5 to 500 MPa, and particularly preferably 10 to 100 MPa.
  • the heat resistance of the flexible layer (C) in the present invention is determined by various characteristics of the ethylene- ⁇ -olefin random copolymer (C-1) (crystal melting peak temperature, crystal melting heat amount, MFR, molecular weight, etc.) and ethylene- ⁇ - Although it is affected by various properties (crystal melting peak temperature, crystal melting heat, MFR, molecular weight, etc.) of the olefin block copolymer (C-2), in particular, ethylene- ⁇ -olefin block copolymer (C-2) The crystal melting peak temperature is strongly affected. As described above, if the crystal melting peak temperature of the ethylene- ⁇ -olefin block copolymer (C-2) in the flexible layer (C) is 100 ° C.
  • the heat resistance of the flexible layer (C) in the present invention is ensured. I can do it. And since a front surface protection sheet has the lowest heat resistance and elastic modulus of a flexible layer (C) in the layer which comprises a member, a flexible layer (C) determines the performance about the heat resistance of a front surface protection sheet.
  • the heat resistance of the flexible layer (C) is 0 mm between white plate glass having a thickness of 3 mm (size: length 75 mm, width 25 mm) and an aluminum plate having a thickness of 5 mm (size: length 120 mm, width 60 mm).
  • .5mm sheet-like flexible layer (C) is stacked, and a sample is laminated and pressed using a vacuum press machine at 150 ° C for 15 minutes, and the sample is inclined at 60 ° C in a 100 ° C constant temperature bath. Then, after observing the state after 500 hours, the case where the glass did not deviate from the initial reference position was evaluated as ⁇ , and the case where the glass deviated from the initial reference position or the sheet was melted was evaluated as x.
  • the total light transmittance of the flexible layer (C) in the present invention is not so much when applied to a type of solar cell to be applied, for example, an amorphous thin film silicon type or a portion that does not block sunlight reaching the solar electronic element. Although it may not be regarded as important, it is usually preferably 85% or more, more preferably 87% or more, taking into consideration the photoelectric conversion efficiency of the solar cell and handling properties when various members are superimposed, 90% % Or more is more preferable.
  • the flexibility, heat resistance and transparency of the flexible layer (C) in the present invention are likely to be contradictory characteristics. Specifically, if the crystallinity of the resin composition used for improving flexibility is excessively lowered, the heat resistance is lowered and becomes insufficient. On the other hand, if the crystallinity of the resin composition used for improving the heat resistance is excessively improved, the transparency is lowered and becomes insufficient.
  • the balance is used as an index of flexibility, the vibration frequency is 10 Hz in dynamic viscoelasticity measurement, the storage elastic modulus (E ′) at a temperature of 20 ° C., and the heating rate is 10 ° C. in differential scanning calorimetry as an index of heat resistance.
  • the total light transmittance is used as an index of crystal melting peak temperature and transparency measured in terms of / min, three indices are storage elastic modulus (E ′) of 1 to 2000 MPa, and crystal melting peak temperature is 100 ° C. or higher.
  • the total light transmittance is preferably 85% or more, the storage elastic modulus (E ′) is 5 to 500 MPa, the crystal melting peak temperature is 105 to 145 ° C., and the total light transmittance is more preferably 85% or more.
  • the storage elastic modulus (E ′) is 10 to 100 MPa, the crystal melting peak temperature is 110 to 145 ° C., and the total light transmittance is 87% or more.
  • the thickness of the flexible layer (C) is about 50 to 100 ⁇ m in order to suppress damage to the moisture-proof layer due to falling objects and deterioration of the moisture-proof function, and is preferably 150 to 750 ⁇ m, preferably 300 to 500 ⁇ m from the viewpoint of handling. Further preferred.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin random copolymer (C-1) used in the present invention is not particularly limited, but is usually MFR (JIS K7210, temperature: 190 ° C., load) 21.18N) is about 0.5 to 100 g / 10 min, preferably 2 to 50 g / 10 min, more preferably 3 to 30 g / 10 min.
  • the MFR may be selected in consideration of the formability when the sheet is formed.
  • the MFR is preferably a relatively low value, specifically about 0.5 to 5 g / 10 min from the handling property when the sheet is peeled off from the molding roll.
  • MFR is preferably 2 to 50 g / 10 min, more preferably 3 to 30 g / 10 min from the viewpoint of reducing the extrusion load and increasing the extrusion rate.
  • the ethylene- ⁇ -olefin random copolymer (C-1) used in the present invention has a heat of crystal melting of 0 to 70 J / g measured at a heating rate of 10 ° C./min in the condition (1) differential scanning calorimetry. It is important to satisfy, preferably 5 to 70 J / g, more preferably 10 to 65 J / g. If it is in this range, since the softness
  • general-purpose high-density polyethylene is about 170 to 220 J / g
  • low-density polyethylene resin LDPE
  • linear low-density polyethylene LLDPE
  • the crystal melting peak temperature of the ethylene- ⁇ -olefin random copolymer (C-1) used in the present invention is not particularly limited, but is usually less than 100 ° C., preferably 30 to 90. ° C.
  • crystal melting peak temperature general-purpose high-density polyethylene (HDPE) is about 130 to 145 ° C.
  • low-density polyethylene resin (LDPE) and linear low-density polyethylene (LLDPE) are 100 to 125. It is about °C. That is, with the ethylene- ⁇ -olefin random copolymer (C-1) used alone in the present invention, the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 ° C. or higher, In addition, it is difficult to achieve a crystal melting heat quantity of 5 to 70 J / g.
  • ethylene- ⁇ -olefin random copolymer (C-1) used in the present invention include trade names “Engage”, “Affinity” manufactured by Dow Chemical Co., Ltd., Mitsui Examples include trade names “TAFMER A”, “TAFMER P” manufactured by Kagaku Co., Ltd., and “kernel” manufactured by Nippon Polyethylene Co., Ltd.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin block copolymer (C-2) used in the present invention is not particularly limited, but is usually MFR (JIS K7210, temperature: 190 ° C., load) : 21.18N) is about 0.5 to 100 g / 10 min, more preferably 1 to 50 g / 10 min, still more preferably 1 to 30 g / 10 min, and particularly preferably 1 to 10 g / 10 min.
  • the ethylene- ⁇ -olefin block copolymer (C-2) used in the present invention has a crystal melting peak temperature of 100 ° C. or higher measured at a heating rate of 10 ° C./min in differential scanning calorimetry, It is important that the heat of fusion satisfies 5 to 70 J / g (condition (2)).
  • the crystal melting peak temperature is preferably 105 ° C. or higher, more preferably 110 ° C. or higher, and the upper limit is usually 145 ° C.
  • the heat of crystal melting is preferably 10 to 60 J / g, more preferably 15 to 55 J / g.
  • the block structure of the ethylene- ⁇ -olefin block copolymer (C-2) used in the present invention is not particularly limited as long as the above-described condition (2) is satisfied, but flexibility, heat resistance, Two or more, preferably three or more segments or blocks having different comonomer contents, crystallinity, density, crystal melting peak temperature (melting point Tm), or glass transition temperature (Tg) from the viewpoint of balancing such as transparency
  • a multi-block structure containing Specific examples include a completely symmetric block, an asymmetric block, and a tapered block structure (a structure in which the ratio of the block structure gradually increases in the main chain).
  • 2005/090425 (WO2005 / 090425), International Publication No. 2005/090426 (WO2005 / 090426), and International Publication No.2005. / 090427 pamphlet (WO2005 / 090427) or the like can be employed.
  • the ethylene- ⁇ -olefin block copolymer having the multi-block structure will be described in detail below.
  • the ethylene- ⁇ -olefin block copolymer having a multiblock structure can be suitably used in the present invention, and an ethylene-octene multiblock copolymer having 1-octene as a copolymerization component as an ⁇ -olefin is preferable.
  • As the block copolymer an almost non-crystalline soft segment copolymerized with a large amount of octene component (about 15 to 20 mol%) with respect to ethylene and a small amount of octene component (about 2 mol% with respect to ethylene).
  • a multiblock copolymer having two or more highly crystalline hard segments each having a copolymerized crystal melting peak temperature of 110 to 145 ° C. is preferred.
  • chain length and ratio of these soft segments and hard segments By controlling the chain length and ratio of these soft segments and hard segments, both flexibility and heat resistance can be achieved.
  • trade name “Infuse” manufactured by Dow Chemical Co., Ltd. may be mentioned.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin block copolymer (C-2) used in the present invention is not particularly limited, but usually MFR (JIS K7210, temperature: 190 ° C., load) : 21.18N) is about 0.5 to 100 g / 10 min, more preferably 1 to 50 g / 10 min, still more preferably 1 to 30 g / 10 min, and particularly preferably 1 to 10 g / 10 min.
  • the MFR may be selected in consideration of the formability when the sheet is formed. Specifically, when calendering a sheet, the MFR is preferably relatively low, specifically about 0.5 to 5 g / 10 min from the handling property when the sheet is peeled off from the molding roll, In the case of extrusion molding using a T die, an MFR of 1 to 30 g / 10 min is preferably used from the viewpoint of reducing the extrusion load and increasing the extrusion amount. Further, from the viewpoint of adhesion and ease of wraparound when sealing the solar cell element (cell), an MFR of 3 to 50 g / 10 min is preferably used.
  • the contents of the ethylene- ⁇ -olefin random copolymer (C-1) and the ethylene- ⁇ -olefin block copolymer (C-2) in the flexible layer (C) are flexibility, heat resistance, From the viewpoint of having an excellent balance such as transparency, it is preferably 50 to 99% by mass, 1 to 50% by mass, more preferably 60 to 98% by mass, 2 to 40% by mass, respectively. Preferably, they are 70 to 97% by mass and 3 to 30% by mass.
  • the front protective sheet for a solar cell of the present invention is formed by laminating the above-mentioned weather resistant layer (A) and moisture-proof layer (B) via a flexible layer (C).
  • the protective sheet / encapsulant laminate is formed by laminating the encapsulant (D) on the solar cell front protective sheet.
  • the encapsulant (D) is used to encapsulate the solar cell element and, like the flexible layer (B), an ethylene- ⁇ -olefin random copolymer (D-) that satisfies the following condition (1): 1) and an ethylene- ⁇ -olefin block copolymer (D-2) satisfying the following condition (2).
  • the heat of crystal fusion measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 0 to 70 J / g.
  • the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 ° C. or more, and the crystal melting heat amount is 5 to 70 J / g.
  • the ethylene- ⁇ -olefin random copolymer (D-1) satisfying the condition (1) the ethylene- ⁇ -olefin random copolymer (C-1) used for the front protective sheet is used.
  • the same ethylene- ⁇ -olefin block copolymer (D-2) that satisfies the condition (2) can be used as the ethylene-
  • the types of olefins may be the same or different, but in the present invention, the same olefin is compatible when mixed and the transparency of the front protective sheet, that is, the solar cell. It is preferable because photoelectric conversion efficiency is improved.
  • the flexible layer (C ) can contain other similar resins or additives.
  • Properties of the obtained sealing material such as storage elastic modulus, heat resistance, total light transmittance, and the relationship thereof are the same as those of the layer (C).
  • the sealing material (D) those having the same composition and properties as the flexible layer (C) are preferable from the viewpoint of preventing the moisture-proof performance from being lowered when a solar cell module described later is produced.
  • the thickness of the sealing material (D) is not particularly limited, but is usually about 0.05 to 1 mm, preferably 0.1 to 0.7 mm, more preferably 0.3 to 0.5 mm. It is used in the form of a sheet.
  • the solar cell front protective sheet and solar cell front protective sheet / sealing material laminate according to the present invention have various physical properties (flexibility, heat resistance, transparency, adhesiveness, etc.) without departing from the gist of the present invention. ),
  • the above-mentioned ethylene- ⁇ -olefin random copolymer (C-1) or (D-1) or ethylene- ⁇ -olefin block copolymer (C-) Resins other than 2) or (D-2) can be mixed.
  • the resin examples include other polyolefin resins and various elastomers (olefin-based, styrene-based, etc.), polar groups such as carboxyl groups, amino groups, imide groups, hydroxyl groups, epoxy groups, oxazoline groups, thiol groups, silanol groups, and the like. And a resin modified with a tackifier resin.
  • the tackifying resin examples include petroleum resins, terpene resins, coumarone-indene resins, rosin resins, and hydrogenated derivatives thereof.
  • the petroleum resin includes cyclopentadiene or an alicyclic petroleum resin derived from a dimer thereof and an aromatic petroleum resin derived from a C 9 component
  • the terpene resin includes terpene resin and terpene derived from ⁇ -pinene.
  • -Phenol resin, and examples of rosin resins include rosin resins such as gum rosin and wood rosin, and esterified rosin resins modified with glycerin, pentaerythritol, and the like.
  • the tackifying resin can be obtained with various softening temperatures mainly depending on the molecular weight, but when mixed with the copolymer (C-1) and copolymer (C-2) described above, Aliphatic ring having a softening temperature of 100 to 150 ° C., preferably 120 to 140 ° C., in view of compatibility, color tone and thermal stability when mixed with polymer (D-1) and copolymer (D-2) Particularly preferred are hydrogenated derivatives of formula petroleum resins.
  • a flexible layer In (C) or the sealing material (D) when a resin other than the above-mentioned copolymer (C-1) or copolymer (C-2), or a resin other than copolymer (D-1) or copolymer (D-2) is mixed, a flexible layer In (C) or the sealing material (D), when the resin composition is usually 100 parts by mass, it is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.
  • additives can be added to the solar cell front protective sheet and the solar cell front protective sheet / sealing material laminate of the present invention as necessary.
  • the additive include a silane coupling agent, an antioxidant, an ultraviolet absorber, a weathering stabilizer, a light diffusing agent, a nucleating agent, a pigment (for example, a white pigment), a flame retardant, and a discoloration preventing agent.
  • a silane coupling agent, an antioxidant, an ultraviolet absorber, and a weathering stabilizer is added for reasons described later.
  • a crosslinking agent and / or a crosslinking aid may be blended.
  • silane coupling agents include compounds having a hydrolyzable group such as an alkoxy group together with an unsaturated group such as a vinyl group, an acryloxy group or a methacryloxy group, an amino group or an epoxy group.
  • Specific examples of the silane coupling agent include N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyltriethoxy.
  • Examples thereof include silane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane.
  • ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane are preferably used because of good adhesiveness and little discoloration such as yellowing.
  • the amount of the silane coupling agent added is usually about 0.1 to 5% by mass in the solar cell front protective sheet or in each resin layer constituting the solar cell front protective sheet / sealing material laminate. It is preferable to add 0.2 to 3% by mass.
  • a coupling agent such as an organic titanate compound can be effectively used.
  • antioxidant various commercial 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.
  • monophenols include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-tert-butyl-4-ethylphenol.
  • bisphenols examples 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, triphenol (vitamin E) and the like.
  • 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 effect of the antioxidant, thermal stability, economy and the like, and it is more preferable to use a combination of both.
  • the addition amount of the antioxidant is usually about 0.1 to 1% by mass in the front protective sheet for solar cells or in each resin layer constituting the front protective sheet / sealant laminate for solar cells. 0.2 to 0.5% by mass is preferably added.
  • UV absorber various commercially available products can be applied, and various types such as benzophenone-based, benzotriazole-based, triazine-based, and salicylic acid ester-based materials can be exemplified.
  • benzophenone ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n.
  • benzotriazole ultraviolet absorber examples include hydroxyphenyl-substituted benzotriazole compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butylphenyl).
  • Benzotriazole 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, etc. be able to.
  • triazine ultraviolet absorbers examples include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( Examples include 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol.
  • salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
  • the addition amount of the ultraviolet absorber is usually about 0.01 to 2.0% by mass in the front protective sheet for solar cells or in each resin layer constituting the front protective sheet / sealant laminate for solar cells. It is preferable to add 0.05 to 0.5% by mass.
  • Hindered amine light stabilizers are preferably used as the weather stabilizer for imparting weather resistance in addition to the above ultraviolet absorbers.
  • a hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with an ultraviolet absorber.
  • hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ 2, 2,6,6-tetramethyl-4-piperidyl ⁇ imino ⁇ ], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3 , 5-Di-tert-4 Hydroxybenzyl) -2-
  • the amount of the hindered amine light stabilizer added is usually 0.01 to 0.5 in the solar cell front protective sheet or in each resin layer constituting the solar cell front protective sheet / sealing material laminate. It is about mass%, and it is preferable to add 0.05 to 0.3 mass%.
  • the weathering layer (A), moisture-proof layer (B), flexible layer (C) and sealing material (D) used in the present invention known methods such as a single screw extruder and a multi-screw extruder are used. It has melt mixing equipment such as a Banbury mixer and a kneader, and can adopt an extrusion casting method using a T-die or a calendar method, and is not particularly limited. From the viewpoint of properties and the like, an extrusion casting method using a T die is preferably used.
  • 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 130 to 300 ° C., preferably 150 to 250 ° C.
  • Various additives such as silane coupling agents, antioxidants, UV absorbers, and weathering stabilizers may be dry blended with the resin in advance and then supplied to the hopper.
  • the master batch may be supplied after being prepared, or a master batch in which only the additive is previously concentrated in the resin may be prepared and supplied.
  • the thickness of the front protective sheet for solar cells of the present invention is not particularly limited, but is usually about 0.05 to 1 mm, preferably 0.1 to 0.7 mm.
  • the front protective sheet for a solar cell of the present invention is formed by removing the film-formed weatherable layer (A), moisture-proof layer (B) and flexible layer (C) with a vacuum laminator at a temperature of 120 to 150 ° C. according to a conventional method. It can be produced by heat-pressure bonding with a gas time of 2 to 15 minutes, a press pressure of 0.5 to 1 atm, and a press time of 8 to 45 minutes.
  • the thickness of the front protective sheet / sealing material laminate is not particularly limited, but is usually about 0.12 to 2.3 mm, preferably about 0.3 to 1.6 mm. Preferably, it is used in the form of a sheet of about 0.60 to 1.2 mm.
  • the front protective sheet / sealing material laminate is prepared by subjecting the above-mentioned weathered layer (A), flexible layer (B), moisture-proof layer (C) and sealing material (D) to a temperature by a vacuum laminator according to a conventional method. It can be produced by heat and pressure bonding at 120 to 170 ° C., a degassing time of 2 to 15 minutes, a pressing pressure of 0.5 to 1 atm, and a pressing time of 8 to 45 minutes.
  • the front protective sheet of the present invention has the weather resistant layer (A) as its surface side and the moisture proof layer (B) as its inner surface side, that is, from the front surface (upper part), the weather resistant layer (A ), Flexible layer (C), and moisture-proof layer (B) are preferably arranged in this order, and the front protective sheet / sealing material laminate is formed from the front surface (upper part), the weather resistant layer (A), and the flexible layer (C).
  • the moisture-proof layer (B) and the sealing material (D) are preferably arranged in this order.
  • the example of the front protective sheet for a solar cell shown in FIG. 1 is obtained by laminating a weather-resistant layer 1 and a moisture-proof layer 2 via a flexible layer 3 and bonding them together.
  • the solar cell front protective sheet / sealing material laminate of the present invention is laminated with a sheet-like sealing material (D) after forming a weather-resistant layer (A), a flexible layer (C) and a moisture-proof layer (B).
  • the example of the solar cell front protective sheet / sealing material laminate shown in FIG. 2 is obtained by laminating a weather-resistant layer 1, a flexible layer 3, a moisture-proof layer 2, and a sealing resin layer 4.
  • the solar cell front protective sheet / sealing material laminate according to the present invention has the above-described configuration.
  • the moisture-proof layer (B) is provided as described above.
  • positioning between a flexible layer (C) and a sheet-like sealing material (D) it becomes possible to achieve a high light transmittance and to reduce a moisture-proof fall remarkably.
  • the solar cell front protective sheet and the solar cell front protective sheet / sealing material laminate in the present invention preferably both have high transparency, and the total light transmittance is the type of solar cell to be applied, for example, amorphous.
  • the total light transmittance is the type of solar cell to be applied, for example, amorphous.
  • it is preferably 84% or more, and more preferably 85% or more.
  • the total light transmittance can be measured according to JIS K7105 as described later.
  • the configuration of the front protective sheet in particular, flexibility, heat resistance and transparency are well balanced.
  • the flexible layer (C) on the outer side (front surface) of the moisture-proof layer (B)
  • the structure of the front protective sheet / sealing material laminate in particular, the flexible layer (C) is used as the moisture-proof layer (B).
  • a moisture-proof layer (B) between the flexible layer (C) and the sealing material (D) it is possible to prevent deterioration of the moisture-proof layer by ensuring the flexibility of the front protective sheet.
  • long-term high moisture resistance and weather resistance can be achieved.
  • the moisture-proof performance is evaluated according to the conditions of JIS Z0222 “Moisture permeability test method for moisture-proof packaging containers” and JIS Z0208 “Moisture permeability test method for moisture-proof packaging materials (cup method)”, and specifically evaluated by the method described below. Can do.
  • the solar cell module can be manufactured by fixing the solar cell element together with the back sheet using the front protective sheet for solar cells or the front protective sheet / sealing material laminate of the present invention.
  • various types can be exemplified.
  • the solar cell front protective sheet of the present invention preferably, the solar cell front protective sheet of the present invention and the sealing are used.
  • a solar cell module manufactured using a stopper, a solar cell element, and a lower protective material is mentioned. Specifically, an upper protective material (front protective sheet for solar cell of the present invention) / sealing material ( Sealing resin layer) / solar cell element / sealing material (sealing resin layer) / lower protective material (see FIG.
  • the front surface protection sheet / sealing material laminate of the present invention when using the front surface protection sheet / sealing material laminate of the present invention, preferably, the front surface protection sheet / sealing material layered body for solar cells, the solar cell element, and the lower protection material of the present invention are used.
  • the solar cell module produced by the above method can be used.
  • a structure see FIG.
  • the solar cell front protective sheet / sealing material laminate of the present invention is formed on the solar cell element formed on the inner peripheral surface of the lower protective material
  • an amorphous solar cell element produced by sputtering or the like on a fluororesin-based transparent protective material Such as forming a sealant and lower protective material Or the like can be mentioned the formation.
  • Examples of solar cell elements include single crystal silicon type, polycrystalline silicon type, amorphous silicon type, III-V group and II-VI group compound semiconductor types such as gallium-arsenic, copper-indium-selenium, cadmium-tellurium, Examples include a dye sensitizing type and an organic thin film type.
  • each member which comprises the solar cell module produced using the front surface protection sheet for solar cells of this invention or a front surface protection sheet and a sealing material laminated body although it does not specifically limit,
  • a sealing material For example, an ethylene-vinyl acetate copolymer may be mentioned, but it is preferable to use the sealing material (D).
  • the sealing material is preferably subjected to surface treatment such as corona treatment on at least one surface thereof from the viewpoint of ensuring adhesion to the front protective sheet.
  • the lower protective material is a single layer or multilayer sheet such as a metal or various thermoplastic resin layers, for example, a metal such as tin, aluminum or stainless steel, an inorganic material such as glass, a polyester, an inorganic vapor deposition polyester, a fluorine-containing resin. And a single-layer or multilayer protective material such as polyolefin.
  • the surface of the upper and / or lower protective material can be subjected to a known surface treatment such as a primer treatment or a corona treatment in order to improve the adhesion to the sealing material or other members.
  • the solar cell front protective sheet 10 As shown in FIG. 3, the solar cell front protective sheet 10, the sealing resin layer 12A, the solar cell elements 14A and 14B, the sealing resin layer 12B, and the back sheet 16 are laminated in order from the sunlight receiving side. Further, a junction box 18 (a terminal box for connecting wiring for taking out the electricity generated from the solar cell element) is bonded to the lower surface of the back sheet 16. 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 back sheet 16 and connected to the junction box 18.
  • a known manufacturing method can be applied, and is not particularly limited, but generally, a front protective sheet, a sealing resin layer, a solar cell element, a sealing resin layer, a lower part It has the process of laminating
  • the solar cell module produced by using the front protective sheet for solar cells or the front protective sheet / sealing material laminate of the present invention is a small solar cell typified by a mobile device depending on the type of solar cell applied and the module shape. It can be applied to various uses regardless of whether it is indoors or outdoors, such as batteries and large solar cells installed on the roof or rooftop.
  • this solar cell protective sheet, encapsulant, power generation element, encapsulant, and back surface protective sheet are removed at a temperature of 120 to 150 ° C. with a vacuum laminator according to a conventional method.
  • Manufacture can be easily performed by heat-pressure bonding with a gas time of 2 to 15 minutes, a press pressure of 0.5 to 1 atm, and a press time of 8 to 45 minutes.
  • Crystal melting peak temperature (Tm) (Physical property measurement)
  • Tm Crystal melting peak temperature
  • a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name “Pyris1 DSC”, according to JIS K7121 about 10 mg of the sample was heated from ⁇ 40 ° C. to 200 ° C. at a heating rate of 10 ° C./min.
  • the temperature was lowered to ⁇ 40 ° C. at a cooling rate of 10 ° C./min, and again from the thermogram measured when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min ( Tm) (° C.) was determined.
  • each flexible layer, and the moisture-proof layer are stacked between two pieces of white plate glass (size: length 75 mm, width 25 mm) having a thickness of 3 mm, and 150 ° C. for 15 minutes using a vacuum press machine.
  • a sample that was laminated and pressed under the above conditions was prepared, the total light transmittance was measured according to JIS K7105, the value was described, and the results evaluated according to the following criteria were also shown.
  • ( ⁇ ) Total light transmittance is 90% or more
  • ⁇ ) Total light transmittance is 85% or more and less than 90%
  • ⁇ Total light transmittance is less than 85% or clearly cloudy (not measured) )
  • a flexible layer is layered between two pieces of 3 mm thick white sheet glass (size: length 75 mm, width 25 mm), and a sample that is laminated and pressed using a vacuum press machine at 150 ° C. for 15 minutes is prepared.
  • the sample was installed at an inclination of 60 degrees in a constant temperature bath at 100 ° C., the state after 500 hours was observed, and evaluated according to the following criteria.
  • ⁇ The glass did not deviate from the initial reference position
  • ⁇ The glass deviated from the initial reference position or the sheet melted
  • Moisture-proof performance is evaluated by the following method according to the conditions of JIS Z0222 “Test method for moisture permeability of moisture-proof packaging containers” and JIS Z0208 “Test method for moisture permeability of amount of moisture-proof packaging material (cup method)”. be able to. Using two laminated films or laminates each having a moisture permeable area of 10.0 cm x 10.0 cm square, a bag containing about 20 g of anhydrous calcium chloride as a hygroscopic agent and sealed on all sides is produced.
  • Moisture retention (barrier stability) Laminated weather-proof layer, flexible layer, moisture-proof layer and sealing resin layer using a vacuum laminator LM-30x30 manufactured by NPC Corporation at 150 ° C for 15 minutes and laminated the front protective sheet sealing material An article was made. Then, the water vapor transmission rate of the produced front protective sheet sealing material laminate and the water vapor transmission rate of the moisture-proof layer of the following constituent film (2) were respectively measured according to the above-mentioned JIS Z0208 “Moisture permeability test method for moisture-proof packaging material amount (cup method ) "And evaluated moisture-proof performance. With respect to the moisture proof performance of the moisture proof layer of the following constituent film (2), the degree of decrease in the moisture proof performance of the obtained laminate was evaluated as ⁇ , within 50%, ⁇ over 50% and 100%, and x over 100%.
  • the resin composition constituting the sheet is 80 parts by mass of ( ⁇ -1) and an ethylene-octene block copolymer (manufactured by Dow Chemical Co., Ltd., trade name: Infuse D9507.15, Octene content: 16.4 mol% (44 mass%), MFR: 5, Tm: 123 ° C., ⁇ Hm: 21 J / g) (hereinafter abbreviated as ⁇ -2) 20 mass parts
  • ⁇ -2 ethylene-octene block copolymer
  • ( ⁇ -1) is an ethylene-propylene-hexene ternary random copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name: Kernel KJ640T, propylene content: 7.4 mol% (10 wt%), hexene content: 4.4 mol% (10 wt%), MFR: 30, Tm: 53 ° C., ⁇ Hm: 58 J / g
  • the flexible layer 3 having a thickness of 0.5 mm was obtained in the same manner as the flexible layer 1 except that the thickness was changed to (hereinafter abbreviated as ⁇ -2).
  • the resin composition constituting the sheet is an ethylene-octene random copolymer (manufactured by Prime Polymer Co., Ltd.), a general-purpose crystalline polyethylene resin. , Trade name: Moretech 0238CN, Octene content: 1 mol% (4 mass%), MFR: 2.1, Tm: 121 ° C., ⁇ Hm: 127 J / g (hereinafter abbreviated as P-1) Except for the above, a flexible layer 5 having a thickness of 0.5 mm was obtained in the same manner as the flexible layer 1.
  • Flexible layer 9 A flexible layer 9 was obtained in the same manner as the flexible layer 1 except that ⁇ -1 and ⁇ -1 in the preparation of the flexible layer 1 were used and the thickness of the sheet was changed to 0.3 mm. The results of measuring the thickness, composition, total light transmittance, heat resistance and flexibility (storage modulus) of each of the obtained flexible layers 1 to 9 are summarized in Table 1 below.
  • Example 1 The prepared weather-resistant layer, flexible layer 1 and moisture-proof layer were laminated by a conventional method at 150 ° C. for 15 minutes using a vacuum laminator LM-30x30 manufactured by NPC Co., Ltd. to prepare a front protective sheet 1. Then, the total light transmittance was measured by the method similar to the flexible layer shown above using the produced front surface protection sheet 1, and the result is shown in Table 2. Furthermore, when moisture resistance was measured by the following method, the value was 0.24 g / (m 2 ⁇ day).
  • Example 2 The weatherproof layer, the flexible layer 2 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce the front protective sheet 2 and the total light transmittance was measured in the same manner. The results are shown in Table 2. Moreover, when moisture-proof property was measured like Example 1, the value was 0.24 g / (m ⁇ 2 > * day).
  • Example 3 The weatherproof layer, the flexible layer 3 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce the front protective sheet 3 and the total light transmittance was measured. The results are shown in Table 2. Moreover, when moisture-proof property was measured like Example 1, the value was 0.21 g / (m ⁇ 2 > * day).
  • Comparative Example 1 The weather resistant layer, the flexible layer 4 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce the front protective sheet 4 and the total light transmittance was measured. The results are shown in Table 2.
  • Comparative Example 2 The weather-resistant layer, the flexible layer 5 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce the front protective sheet 5 and the total light transmittance was measured. The results are shown in Table 2.
  • Comparative Example 3 The weatherproof layer, the flexible layer 6 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to prepare the front protective sheet 6 and the total light transmittance was measured. The results are shown in Table 2.
  • Comparative Example 4 The weatherproof layer, the flexible layer 7 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce a front protective sheet 7 and the total light transmittance was measured. The results are shown in Table 2.
  • Comparative Example 5 The weather-resistant layer, the flexible layer 8 and the moisture-proof layer were laminated by vacuum lamination in the same manner as in Example 1 to produce the front protective sheet 8 and the total light transmittance was measured. The results are shown in Table 2.
  • the front protective sheet of the present invention obtained as described above has both high moisture resistance and weather resistance and is excellent in transparency.
  • the flexible layers 1 to 3 used in the front protective sheet of the present invention have a good balance between flexibility, heat resistance and transparency required for protecting the moisture-proof layer. As shown, it had a sufficient thickness. Therefore, the front protective sheets of Examples 1 to 3 produced using the flexible layers 1 to 3 have not only high moisture resistance and weather resistance, but also excellent transparency. It can withstand use under high temperature and inclined conditions, and can be protected from impact from falling objects. On the other hand, the flexible layers 4 and 8 are inferior in heat resistance, and when used under high temperature / inclined conditions, it has been revealed that the flexible layers 4 and 8 are deviated from the reference value or the sheet is melted.
  • the flexible layer cannot fulfill its role, and it is considered that the moisture-proof layer is not sufficiently protected. That is, it is not preferable as a material for a solar cell member that is expected to be used under high temperature and inclined conditions.
  • the flexible layers 5 to 7 were inferior in flexibility (storage modulus), indicating that the moisture-proof layer was insufficiently protected. Therefore, also in the front protective sheets of Comparative Examples 2 to 4 produced using the flexible layers 5 to 7, it is considered that the flexible layer cannot fulfill its role and the moisture-proof layer is not sufficiently protected.
  • Example 4 The above-prepared weathering layer, flexible layer 1, moisture-proof layer and flexible layer 1 are laminated in this order by a conventional method at 150 ° C. for 15 minutes using a vacuum laminating machine LM-30x30 manufactured by NPC Corporation. A sheet sealing material laminate 1 was produced. Then, using the produced front protective sheet sealing material laminate 1, the total light transmittance and moisture proof retention were measured by the above methods. The results are shown in Table 3.
  • “ETFE” means ETFE made by Asahi Glass and “BF” means Tech Barrier LX made by Mitsubishi Plastics.
  • Example 5 The weather-resistant layer, the flexible layer 2, the moisture-proof layer and the flexible layer 2 are laminated by vacuum lamination in the same manner as in Example 4 to produce the front protective sheet sealing material laminate 2, and the total light transmittance and moisture-proof retaining property are similarly obtained. Was measured. The results are shown in Table 3.
  • Example 6 The weather-resistant layer, the flexible layer 3, the moisture-proof layer, and the flexible layer 3 are laminated by vacuum lamination in the same manner as in Example 4 to produce the front protective sheet sealing material laminate 3 in the same manner. Was measured. The results are shown in Table 3.
  • Example 7 The weather-resistant layer, the flexible layer 9, the moisture-proof layer and the flexible layer 9 are laminated by vacuum lamination in the same manner as in Example 4 to produce the front protective sheet sealing material laminate 4, and the total light transmittance and moisture-proof retaining property are similarly obtained. Was measured. The results are shown in Table 3.
  • Comparative Example 6 A weather-resistant layer, a flexible layer 4, a moisture-proof layer, and a flexible layer 4 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminated product 5, and similarly, the total light transmittance and moisture-proof retaining property. Was measured. The results are shown in Table 3.
  • Comparative Example 7 A weather-resistant layer, a flexible layer 5, a moisture-proof layer, and a flexible layer 5 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminated product 6, and similarly, the total light transmittance and moisture-proof retaining property. Was measured. The results are shown in Table 3.
  • Comparative Example 8 A weather-resistant layer, a flexible layer 6, a moisture-proof layer, and a flexible layer 6 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminate 7 and similarly, the total light transmittance and moisture-proof retention was measured. The results are shown in Table 3.
  • Comparative Example 9 The weather-resistant layer, the flexible layer 7, the moisture-proof layer, and the flexible layer 7 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminate 8 and similarly, the total light transmittance and moisture-proof retention. Was measured. The results are shown in Table 3.
  • Comparative Example 10 A weather-resistant layer, a flexible layer 8, a moisture-proof layer, and a flexible layer 8 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminate 9 and similarly, the total light transmittance and moisture-proof retention property. Was measured. The results are shown in Table 3.
  • Comparative Example 11 The weather-resistant layer, the flexible layer 7, the moisture-proof layer, and the flexible layer 1 are laminated by vacuum lamination in the same manner as in Example 4 to produce the front protective sheet sealing material laminate 10, and the total light transmittance and moisture-proof retaining property are similarly obtained. Was measured. The results are shown in Table 3.
  • Comparative Example 12 A weather-resistant layer, a flexible layer 8, a moisture-proof layer, and a flexible layer 1 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminate 11, and similarly, the total light transmittance and moisture-proof retention. Was measured. The results are shown in Table 3.
  • Reference example 1 The weather-resistant layer, the flexible layer 1, the moisture-proof layer, and the flexible layer 7 are laminated by vacuum lamination in the same manner as in Example 4 to produce a front protective sheet sealing material laminate 12 and similarly, the total light transmittance and moisture-proof retention. Was measured. The results are shown in Table 3.
  • front protective sheet sealing material laminates 1 to 4 of the present invention were both excellent in moisture resistance and weather resistance and excellent in transparency.
  • the flexible layers 1 to 3 and 9 used in the front protective sheet sealing material laminate of the present invention have the flexibility, heat resistance and transparency necessary for protecting the moisture-proof layer.
  • the film had a sufficient thickness and a good balance. Therefore, the front protective sheet encapsulant laminates of Examples 4 to 7 produced using the flexible layers 1 to 3 and 9 have both high moisture resistance and weather resistance, and are not only excellent in transparency,
  • the moisture-proof layer can withstand long-term use under high-temperature / inclined conditions, and can be protected from impact from falling objects.
  • the flexible layers 4 and 8 are inferior in heat resistance, and when used under high temperature / tilting conditions, it has been revealed that the flexible layers 4 and 8 are displaced from the reference position or the sheet is melted.
  • the flexible layer cannot fulfill its role, and the moisture-proof layer is not sufficiently protected. That is, it is not preferable as a material for a solar cell member that is expected to be used under high temperature and inclined conditions. Further, it was shown that the flexible layers 5 to 7 were inferior in flexibility (storage modulus) and the moisture-proof layer was not sufficiently protected. Accordingly, even in the front protective sheet sealing material laminate manufactured using the flexible layers 5 to 7, the flexible layer cannot fulfill its role, and the moisture-proof layer is not sufficiently protected.

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Abstract

L'invention porte sur une feuille protectrice de surface avant pour une photopile et sur un stratifié de feuille protectrice de surface avant-matériau d'étanchéité pour une photopile, chacun comprenant une couche de résine ayant un bon équilibre entre la flexibilité et la résistance thermique ou la transparence, ce qui empêche de cette manière la détérioration de la performance de protection contre l'humidité de la feuille protectrice de surface avant provoquée par un objet tombant ou similaire, tout en ayant une transparence, une résistance à l'humidité de longue durée et une résistance aux intempéries de longue durée élevée en même temps. La feuille protectrice de surface avant pour une photopile et le stratifié de feuille protectrice de surface avant-matériau d'étanchéité pour une photopile sont efficaces pour la réduction du poids et l'amélioration de la durabilité d'une photopile. De façon spécifique, l'invention porte sur : une feuille protectrice de surface avant pour une photopile qui est obtenue par stratification d'une couche résistante aux intempéries (A) et d'une couche de protection contre l'humidité (B), une couche flexible (C) étant intercalée entre celles-ci, ladite couche flexible (C) contenant un copolymère statistique d'éthylène-α-oléfine (C-1) qui a une enthalpie de fusion cristalline de 0-70 J/g déterminée par calorimétrie différentielle à balayage à une vitesse de chauffage de 10°C/minute et un copolymère séquencé d'éthylène-α-oléfine (C2) qui a une température de pic de fusion cristalline supérieure ou égale à 100°C et une enthalpie de fusion cristalline de 5-70 J/g déterminée par calorimétrie différentielle à balayage à une vitesse de chauffage de 10°C par minute ; et un stratifié de feuille protectrice de surface avant-matériau d'étanchéité pour une photopile, qui est obtenu par stratification d'un matériau d'étanchéité spécifique (D) sur la feuille protectrice de surface avant pour une photopile.
PCT/JP2011/067228 2010-08-31 2011-07-28 Feuille protectrice de surface avant pour photopile et module de photopile produit à l'aide de celle-ci WO2012029465A1 (fr)

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JP2010195084 2010-08-31
JP2010-195084 2010-08-31
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025357A (ja) * 1996-07-12 1998-01-27 Dainippon Printing Co Ltd 透明複合フィルム
JP2000174298A (ja) * 1998-12-07 2000-06-23 Bridgestone Corp 太陽電池用カバー材、封止膜及び太陽電池
JP2010504646A (ja) * 2006-09-20 2010-02-12 ダウ グローバル テクノロジーズ インコーポレイティド エチレンマルチブロックコポリマーを含む電子装置モジュール
WO2010042335A1 (fr) * 2008-10-09 2010-04-15 Dow Global Technologies Inc. Film de polyoléfine contenant une couche adhésive améliorée pour applications d’airbag
JP2011040735A (ja) * 2009-07-17 2011-02-24 Mitsubishi Plastics Inc 太陽電池封止材及びそれを用いて作製された太陽電池モジュール

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025357A (ja) * 1996-07-12 1998-01-27 Dainippon Printing Co Ltd 透明複合フィルム
JP2000174298A (ja) * 1998-12-07 2000-06-23 Bridgestone Corp 太陽電池用カバー材、封止膜及び太陽電池
JP2010504646A (ja) * 2006-09-20 2010-02-12 ダウ グローバル テクノロジーズ インコーポレイティド エチレンマルチブロックコポリマーを含む電子装置モジュール
WO2010042335A1 (fr) * 2008-10-09 2010-04-15 Dow Global Technologies Inc. Film de polyoléfine contenant une couche adhésive améliorée pour applications d’airbag
JP2011040735A (ja) * 2009-07-17 2011-02-24 Mitsubishi Plastics Inc 太陽電池封止材及びそれを用いて作製された太陽電池モジュール

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