WO2016125882A1 - Photovoltaic module - Google Patents

Photovoltaic module Download PDF

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Publication number
WO2016125882A1
WO2016125882A1 PCT/JP2016/053464 JP2016053464W WO2016125882A1 WO 2016125882 A1 WO2016125882 A1 WO 2016125882A1 JP 2016053464 W JP2016053464 W JP 2016053464W WO 2016125882 A1 WO2016125882 A1 WO 2016125882A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
layer
resin
adhesive layer
film
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PCT/JP2016/053464
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French (fr)
Japanese (ja)
Inventor
史陽 石村
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長州産業株式会社
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Publication of WO2016125882A1 publication Critical patent/WO2016125882A1/en

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    • 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
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • 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
    • H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0745—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; 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 photovoltaic module.
  • photovoltaic module there is a type having a heterojunction photovoltaic element.
  • the heterojunction type photovoltaic device includes a first amorphous semiconductor film and a first conductive type second amorphous system on one surface side of a first conductive type (mainly n-type) crystalline semiconductor substrate.
  • a semiconductor film, a first translucent electrode film, and a first electrode are provided in this order.
  • the first amorphous semiconductor film is an intrinsic amorphous semiconductor film, or the first conductivity type amorphous system having an impurity concentration lower than that of the second amorphous semiconductor film. It is a semiconductor film.
  • the photovoltaic element has an intrinsic amorphous semiconductor film, a second conductive type (mainly p-type) amorphous semiconductor film, and a second light-transmitting electrode on the other surface side of the crystalline semiconductor substrate.
  • the membrane and the second electrode are provided in this order.
  • the photovoltaic module is bonded to one surface of the photovoltaic element via the first adhesive layer and a plurality of first fine wirings bonded and fixed to the first electrode on one surface of the photovoltaic element by the first adhesive layer. And a first resin film sandwiching a plurality of first fine wirings between one surface of the photovoltaic device, a translucent substrate, and between the translucent substrate and the first resin film And a filled first sealing layer. Further, the photovoltaic module includes a plurality of second fine wirings bonded and fixed to the second electrode on the other surface of the photovoltaic element by the second adhesive layer, and the other of the photovoltaic elements via the second adhesive layer.
  • a second resin film bonded to the surface and sandwiching a plurality of second fine wirings between the other surface of the photovoltaic element, a back sheet or a second translucent substrate, and a back sheet or first And a second sealing layer filled between the translucent substrate 2 and the second resin film.
  • Patent Document 1 describes an epoxy adhesive, an acrylic adhesive, a rubber adhesive, a silicon adhesive, and a polyvinyl ether adhesive as materials for the first adhesive layer.
  • the heterojunction photovoltaic device has an amorphous semiconductor film on both surfaces of a crystalline semiconductor substrate.
  • the amorphous semiconductor film is vulnerable to moisture and sodium. For this reason, when a material having an insufficient barrier property against moisture or sodium is used as the material of the sealing layer, the amorphous semiconductor film is deteriorated.
  • the material of the 1st contact bonding layer described in patent document 1 has very weak tolerance with respect to an ultraviolet-ray. For this reason, when using such a material, generally, the first adhesive layer is protected by including an ultraviolet absorber in the first sealing layer. However, when the first sealing layer contains an ultraviolet absorber, ultraviolet light cannot be effectively used for power generation.
  • the present invention has been made in view of the above problems, and provides a photovoltaic module that has a high degree of freedom in selecting a material for a sealing layer and can obtain better power generation efficiency.
  • a photovoltaic module comprising photovoltaic elements
  • the photovoltaic element is A first conductivity type crystalline semiconductor substrate;
  • An intrinsic third amorphous semiconductor film, a second conductivity type fourth amorphous semiconductor film, a second translucent electrode film, and a second electrode are formed on the other surface side of the crystalline semiconductor substrate.
  • the first amorphous semiconductor film is a first conductivity type having an impurity concentration lower than that of the second amorphous semiconductor film, or is intrinsic.
  • the photovoltaic module further includes A plurality of first fine wires bonded and fixed to the first electrode on one surface of the photovoltaic element by a first adhesive layer;
  • the first resin having the plurality of first fine wirings sandwiched between the one surface of the photovoltaic element and bonded to the one surface of the photovoltaic element via the first adhesive layer With film, A translucent first protective layer;
  • a plurality of second fine wires bonded and fixed to the second electrode on the other surface of the photovoltaic element by a second adhesive layer;
  • the second resin having the plurality of second fine wirings sandwiched between the other surface of the photovoltaic element and bonded to the other surface of the photovoltaic element via the second adhesive layer With film, A second protective layer;
  • the first adhesive layer provides a photovoltaic module configured of a resin material including any of the following (A) and (B).
  • the present invention it is possible to provide a photovoltaic module that has a high degree of freedom in selecting a material for the sealing layer and can obtain better power generation efficiency.
  • the photovoltaic module 100 includes a photovoltaic element 10.
  • the photovoltaic device 10 includes a first conductive type crystalline semiconductor substrate 11, a first amorphous semiconductor film 12 and a first conductive type second semiconductor film on one surface side of the crystalline semiconductor substrate 11.
  • the amorphous semiconductor film 13, the first translucent electrode film 14, and the first electrode 15 are provided in this order.
  • the photovoltaic element 10 further includes an intrinsic third amorphous semiconductor film 16, a second conductivity type fourth amorphous semiconductor film 17, and a second conductive film on the other surface side of the crystalline semiconductor substrate 11.
  • the translucent electrode film 18 and the second electrode 19 are provided in this order.
  • the first amorphous semiconductor film 12 is a first conductivity type having an impurity concentration lower than that of the second amorphous semiconductor film 13 or is intrinsic.
  • the photovoltaic module 100 further includes a plurality of first fine wirings 21 bonded and fixed to the first electrode 15 on one surface of the photovoltaic element 10 by the first adhesive layer 22, and one surface of the photovoltaic element 10.
  • the photovoltaic module 100 further includes a plurality of second fine wirings 51 bonded and fixed to the second electrode 19 on the other surface of the photovoltaic element 10 by the second adhesive layer 52, and the other surface of the photovoltaic element 10.
  • a second resin film 53 bonded to the other surface of the photovoltaic device 10 via the second adhesive layer 52, a second protective layer 70, And a second sealing layer 60 filled between the second protective layer 70 and the second resin film 53.
  • the 1st contact bonding layer 22 is comprised by the resin material containing either of the following (A) and (B).
  • B A copolymer containing ethylene and glycidyl (meth) acrylate is described in detail below.
  • the photovoltaic device 10 is a heterojunction photovoltaic device.
  • the conductivity type of each component of the photovoltaic element 10 will be described.
  • the crystalline semiconductor substrate 11 is, for example, n-type.
  • the second amorphous semiconductor film 13 is n-type
  • the first amorphous semiconductor film 12 is intrinsic or n ⁇ -type (n-type having a lower impurity concentration than the second amorphous semiconductor film 13).
  • the fourth amorphous semiconductor film 17 is p-type.
  • the crystal semiconductor substrate 11 is not particularly limited as long as it is a crystal having n-type semiconductor characteristics, and a known substrate can be used.
  • the n-type crystal semiconductor composing the crystalline semiconductor substrate 11 include SiC, SiGe, SiN and the like in addition to silicon (Si). Silicon is preferable from the viewpoint of productivity.
  • the crystalline semiconductor substrate 11 may be a single crystal or a polycrystal. Both surfaces (one surface and the other surface) of the crystalline semiconductor substrate 11 are preferably subjected to uneven processing (not shown) in order to make light confinement due to irregular reflection of light more effective. For example, by immersing the substrate material in an etching solution containing about 1 to 5% by weight of sodium hydroxide or potassium hydroxide, a large number of pyramidal irregularities can be formed.
  • the first amorphous semiconductor film 12, the second amorphous semiconductor film 13, the third amorphous semiconductor film 16, and the fourth amorphous semiconductor film 17 are each made of a silicon thin film. it can.
  • the first amorphous semiconductor film 12 is stacked on one surface of the crystalline semiconductor substrate 11 (upper surface in FIG. 1).
  • the second amorphous semiconductor film 13 is stacked on one surface (the upper surface in FIG. 1) of the first amorphous semiconductor film 12.
  • the total thickness of the first amorphous semiconductor film 12 and the second amorphous semiconductor film 13 is not particularly limited, but is preferably 1 nm to 20 nm, for example, and more preferably 4 nm to 10 nm. By setting the film thickness within such a range, it is possible to reduce the short-circuit current and the occurrence of carrier recombination in a well-balanced manner.
  • the first translucent electrode film 14 is stacked on one surface (the upper surface in FIG. 1) of the second amorphous semiconductor film 13.
  • the transparent electrode material constituting the first translucent electrode film 14 include indium tin oxide (ITO), tungsten-doped indium oxide (InWO), and cerium-doped indium oxide (ITO).
  • ITO indium tin oxide
  • ITO cerium-doped indium oxide
  • Well-known materials such as Indium Cerium Oxide (ICO), IZO (Indium Zinc Oxide), AZO (aluminum doped ZnO), and GZO (gallium doped ZnO) can be exemplified.
  • the third amorphous semiconductor film 16 is stacked on the other surface (the lower surface in FIG. 1) of the crystalline semiconductor substrate 11. In other words, the third amorphous semiconductor film 16 is interposed between the crystalline semiconductor substrate 11 and the fourth amorphous semiconductor film 17.
  • the film thickness of the third amorphous semiconductor film 16 is not particularly limited, but may be, for example, 1 nm or more and 10 nm or less.
  • the fourth amorphous semiconductor film 17 is laminated on one surface (the lower surface in FIG. 1) of the third amorphous semiconductor film 16.
  • the film thickness of the 4th amorphous semiconductor film 17 is not specifically limited, For example, 1 nm or more and 20 nm or less are preferable, and 3 nm or more and 10 nm or less are more preferable.
  • the second translucent electrode film 18 is laminated on one surface (the lower surface in FIG. 1) of the fourth amorphous semiconductor film 17.
  • the material constituting the second translucent electrode film 18 is the same as that of the first translucent electrode film 14.
  • intrinsic means that impurities are not intentionally doped. Therefore, the intrinsic amorphous semiconductor film includes impurities that are originally included in the raw material and impurities that are unintentionally mixed in the manufacturing process. Moreover, an amorphous system means that not only an amorphous body but a microcrystal body is included.
  • An n-type amorphous semiconductor film refers to a film containing impurities of about 10 ⁇ 5 or more relative to silicon as a number density ratio of elements contained in a thin film.
  • the first electrode 15 is, for example, a finger electrode, or a metal film formed on the entire surface of one surface (the upper surface in FIG. 1) of the first light-transmissive electrode film 14.
  • the second electrode 19 is, for example, a finger electrode or a metal film formed on the entire surface of one surface (the lower surface in FIG. 1) of the second translucent electrode film 18.
  • a conductive adhesive such as a silver paste or a metal conductor such as a copper wire can be used.
  • the width of the finger electrode is, for example, about 20 ⁇ m or more and 80 ⁇ m or less.
  • silver, a silver alloy, an aluminum alloy, or the like can be used as a material of the metal film constituting the first electrode 15 and the second electrode 19.
  • the plurality of first fine wirings 21 are, for example, a plurality of wires or bus bars arranged in parallel to each other.
  • the first fine wiring 21 has a core 21a and a low melting point metal film 21b coated on the surface of the core 21a.
  • the metal material of the core 21a include copper.
  • the metal material of the low melting point metal film 21b include an alloy of indium and tin.
  • the diameter of the first fine wiring 21 is preferably 100 ⁇ m or more and 400 ⁇ m or less, and more preferably 200 ⁇ m or more and 300 ⁇ m or less.
  • the second fine wiring 51 is configured in the same manner as the first fine wiring 21.
  • the 1st electrode 15 is a finger electrode
  • the some 1st fine wiring 21 is orthogonally crossed with the 1st electrode 15 (refer FIG. 2).
  • the second electrode 19 is a finger electrode
  • the plurality of second fine wirings 51 are orthogonal to the second electrode 19.
  • the first adhesive layer 22 is translucent.
  • the 1st contact bonding layer 22 is comprised with the resin material containing either of the following (A) and (B).
  • Examples of the copolymer of ethylene and unsaturated carboxylic acid include an ionomer of a copolymer of ethylene and unsaturated carboxylic acid.
  • the ionomer of the copolymer of ethylene and unsaturated carboxylic acid may contain a metal species derived from an alkali metal such as lithium or sodium, or a polyvalent metal such as calcium, magnesium, cerium, zinc or aluminum. it can. Among these, sodium, magnesium, and zinc are preferably used.
  • ionomers are known to have excellent transparency and a high storage elastic modulus E ′ at high temperatures.
  • the ionomer neutralization degree of the copolymer of ethylene and unsaturated carboxylic acid according to this embodiment is preferably 80% or less, and more preferably 60% or less from the viewpoint of adhesiveness. Most preferably, it is 40% or less.
  • the unsaturated carboxylic acid component in the ionomer of a copolymer of ethylene and an unsaturated carboxylic acid or a copolymer of ethylene and an unsaturated carboxylic acid includes acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, maleic acid. Examples thereof include monomethyl acid and maleic anhydride. Among these, (meth) acrylic acid is preferable as the unsaturated carboxylic acid component. Therefore, the ethylene / unsaturated carboxylic acid copolymer is preferably an ethylene / (meth) acrylic acid copolymer.
  • the ethylene / unsaturated carboxylic acid copolymer according to the present embodiment is not limited to a binary copolymer of ethylene and unsaturated carboxylic acid, but an ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer. Also included are multicomponent copolymers containing ethylene and unsaturated carboxylic acids. Examples of the unsaturated carboxylic acid ester component in the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer include alkyl esters having 1 to 20 carbon atoms of various carboxylic acids used as the unsaturated carboxylic acid component described above. It is done.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 2-ethylhexyl group, and an isooctyl group.
  • the content of unsaturated carboxylic acid units such as (meth) acrylic acid units in the copolymer of ethylene and unsaturated carboxylic acid or its ionomer according to the present embodiment is preferable from the viewpoint of realizing excellent ultraviolet transparency. Is 2 wt% or more and 30 wt% or less, more preferably 9 wt% or more and 25 wt% or less, and most preferably 12 wt% or more and 20 wt% or less.
  • the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is preferably 1% by weight or more and 35% by weight or less, and preferably 3% by weight or more and 32% by weight or less. Is more preferable, and 5 to 30 weight% is further more preferable.
  • the content of the unsaturated carboxylic acid with respect to the total amount of the copolymer is preferably 1% by weight or more. % Or more, more preferably 3% by weight or more.
  • the content of the unsaturated carboxylic acid with respect to the total amount of the copolymer is preferably 20% by weight or less, and more preferably 15% by weight or less from the viewpoint of reducing hygroscopicity.
  • the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is 1% by weight or more from the viewpoint of improving the transparency and adhesiveness of the copolymer. Preferably, it is 3% by weight or more, more preferably 5% by weight or more.
  • the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is preferably 35% by weight or less, more preferably, from the viewpoint of reducing hygroscopicity. Is 32% by weight or less, more preferably 30% by weight or less.
  • the copolymer of ethylene and unsaturated carboxylic acid according to this embodiment can be obtained by performing a radical copolymerization reaction under high temperature and high pressure conditions. Further, an ionomer of a copolymer of ethylene and unsaturated carboxylic acid can be obtained by reacting a copolymer of ethylene and unsaturated carboxylic acid with a metal compound.
  • the glycidyl (meth) acrylate contained in the copolymer containing ethylene and glycidyl (meth) acrylate contained in the first adhesive layer 22 refers to at least one of glycidyl methacrylate or glycidyl acrylate.
  • the copolymer containing ethylene and glycidyl (meth) acrylate include ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid glycidyl / vinyl acetate copolymer, and ethylene / (meta ) One or more selected from glycidyl acrylate / (meth) acrylic acid ester copolymer and the like.
  • the content ratio of the structural unit derived from glycidyl (meth) acrylate in the copolymer containing ethylene and glycidyl (meth) acrylate is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25%. % By weight or less.
  • the content ratio of the structural unit derived from glycidyl (meth) acrylate is within the above range, the balance of the adhesiveness, flexibility, handleability, workability, etc. of the obtained first adhesive layer 22 is further improved. It can be.
  • the content ratio of the “ethylene-derived structural unit” in the copolymer containing ethylene and glycidyl (meth) acrylate is preferably 65% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more. is there.
  • the copolymer containing ethylene and glycidyl (meth) acrylate further contains other monomer units (for example, vinyl acetate, (meth) acrylate ester, etc.) other than ethylene and glycidyl (meth) acrylate. Can do.
  • a composition derived from vinyl acetate in addition to these two structural units, a composition derived from vinyl acetate.
  • examples thereof include a copolymer containing at least one of a unit and a structural unit derived from a (meth) acrylic acid ester.
  • the content ratio of the structural unit derived from vinyl acetate and the structural unit derived from (meth) acrylic acid ester is preferably 30% by weight or less, and more preferably 20% by weight or less.
  • the lower limit of the content ratio of the structural unit derived from vinyl acetate and the structural unit derived from (meth) acrylic acid ester is not particularly limited, but is preferably 0.1% by weight or more, more preferably 0.5% by weight. More preferably, 1% by weight or more is desirable. Further, the content ratio of the structural unit derived from vinyl acetate or the structural unit derived from (meth) acrylic acid ester is preferably in the range of 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, particularly 1 A range of ⁇ 20% by weight is preferred.
  • a copolymer containing ethylene and glycidyl (meth) acrylate is used alone or in combination of two or more of copolymers having different copolymerization ratios or two or more of copolymers having different monomer types. be able to.
  • At least a part of the copolymer containing ethylene and glycidyl (meth) acrylate may be modified with a silane coupling agent.
  • the content of the silane coupling agent is preferably 0.01 to 5% by weight in 100% by weight of the copolymer containing ethylene and glycidyl (meth) acrylate.
  • the first adhesive layer 22 only needs to contain one of the above (A) and (B), but the above-mentioned (A) and (B) are contained in 100% by weight of the resin component of the first adhesive layer 22.
  • ) In total is preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more.
  • the upper limit is not particularly limited, but when it contains (B), it is preferably 80% by weight or less, more preferably 60% by weight or less.
  • the resin material forming the first adhesive layer 22 may include other resins.
  • other resins include propylene-based resins and ethylene-based resins.
  • ethylene resins include ethylene / ⁇ -olefin copolymers and ethylene / polar monomer copolymers in which the content of structural units derived from ⁇ -olefins having 3 to 20 carbon atoms is 5 mol% or more and less than 50 mol%. Examples include coalescence.
  • ⁇ -olefin having 3 to 20 carbon atoms examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene.
  • Linear ⁇ -olefins such as 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicocene;
  • Examples include branched ⁇ -olefins such as 1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. These can be used in combination of two types.
  • the number of carbon atoms of the ⁇ -olefin is preferably 3 to 10, more preferably 3 to 8 in view of versatility (cost, mass productivity, or availability).
  • the ethylene / ⁇ -olefin copolymer is preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 4-methyl-1-pentene copolymer, or an ethylene / 1-hexene copolymer.
  • This is an ethylene / 1-octene copolymer, and any ethylene / ⁇ -olefin copolymer means that the content of the structural unit derived from ethylene is 50 mol% or more.
  • the ethylene / ⁇ -olefin copolymer can be produced by, for example, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, or a gas phase polymerization method using a metallocene catalyst.
  • the ethylene / polar monomer copolymer examples include an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer.
  • the polar monomer means a monomer having a functional group.
  • the ethylene / vinyl ester copolymer is selected from, for example, an ethylene / vinyl acetate copolymer, an ethylene / vinyl propionate copolymer, an ethylene / vinyl butyrate copolymer, an ethylene / vinyl stearate copolymer, and the like. One kind or two or more kinds can be used.
  • the ethylene / unsaturated carboxylic acid ester copolymer according to this embodiment is a polymer obtained by copolymerizing ethylene and at least one unsaturated carboxylic acid ester.
  • a copolymer composed of ethylene and an alkyl ester of an unsaturated carboxylic acid can be exemplified.
  • the unsaturated carboxylic acid in the unsaturated carboxylic acid ester include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
  • alkyl moiety in the alkyl ester of the unsaturated carboxylic acid examples include those having 1 to 12 carbon atoms, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl. And alkyl groups such as 2-ethylhexyl and isooctyl.
  • the alkyl moiety of the alkyl ester preferably has 1 to 8 carbon atoms.
  • unsaturated carboxylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid It is preferable to include one or more selected from (meth) acrylic acid esters such as n-butyl, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These unsaturated carboxylic acid esters may be used alone or in combination of two or more.
  • a preferable ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylic acid ester copolymer.
  • a copolymer composed of one kind of compound is preferable as the (meth) acrylic acid ester.
  • examples of such copolymers include ethylene / methyl (meth) acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) isopropyl acrylate copolymer, ethylene / (meth).
  • N-propyl acrylate copolymer ethylene / (meth) acrylate isobutyl copolymer, ethylene / (meth) acrylate n-butyl copolymer, ethylene / (meth) acrylate isooctyl copolymer, ethylene / ( And (meth) acrylic acid 2-ethylhexyl copolymer.
  • the ethylene / polar monomer copolymer includes ethylene / vinyl acetate copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) acrylate isopropyl copolymer.
  • the ethylene / polar monomer copolymer may be used alone or in combination of two or more. These other resins may be modified with a silane coupling agent.
  • the content of the silane coupling agent is preferably 0.01 to 5% by weight in 100% by weight of other resin components.
  • Examples of the resin material forming the first adhesive layer 22 include antioxidants such as hydroquinone monobenzyl ether and triphenyl phosphite, thermal stabilizers such as lead stearate and barium laurate, fine titanium oxide, Various additives such as fillers such as zinc oxide, pigments, dyes, lubricants, antiblocking agents, foaming agents, foaming aids, crosslinking agents, crosslinking aids, flame retardants, and the like may be blended.
  • the content of each component is preferably 0.005 to 2 parts by weight and more preferably 0.008 to 1 part by weight with respect to 100 parts by weight of the resin component in the first adhesive layer 22.
  • a metal fatty acid salt such as cadmium or barium may be arbitrarily blended as a discoloration preventing agent.
  • the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is 70% or more. By doing so, light energy derived from ultraviolet rays can be efficiently contributed to power generation.
  • light energy derived from ultraviolet rays refers to light energy derived from light in a wavelength region of less than 380 nm.
  • the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is preferably 75% or more, and more preferably 80% or more. By doing so, it becomes possible to more effectively contribute light energy derived from ultraviolet rays to power generation.
  • the layer thickness T (FIG. 3) of the first adhesive layer 22 can be, for example, 8 ⁇ m or more and 100 ⁇ m or less, and preferably 16 ⁇ m or more and 75 ⁇ m or less.
  • the layer thickness T of the first adhesive layer 22 is preferably set in a range of D / 6 ⁇ D / 12. That is, as an example, when the first fine wiring 21 is a wire having a diameter of 300 ⁇ m, the layer thickness T can be set to 25 ⁇ m or more and 75 ⁇ m or less.
  • the layer thickness T of the first adhesive layer 22 is a layer thickness in a range where the layer thickness of the first adhesive layer 22 is substantially constant in the interval between adjacent wires (see FIG. 3). ).
  • the 1st resin film 23 is formed with the material containing 1 or more selected from the group which consists of a fluororesin and an acrylic resin, for example.
  • the fluororesin include tetrafluoroethylene / ethylene copolymer (ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polychlorotriethylene.
  • EFE tetrafluoroethylene / ethylene copolymer
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer
  • PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
  • PCTFE fluoroethylene
  • PCTFEE chlorotrifluoroethylene / ethylene copolymer
  • PVDF polyvinylidene fluoride
  • the acrylic resin include acrylic acid ester polymers and methacrylic acid ester polymers.
  • a methacrylic resin that is a polymer mainly composed of methyl methacrylate units is preferable.
  • the methacrylic resin include polymethyl methacrylate (PMMA), a copolymer of methyl methacrylate and another monomer, and the like.
  • the thickness of the 1st resin film 23 can be 5 micrometers or more and 100 micrometers or less (preferably 10 micrometers or more and 80 micrometers or less), for example.
  • the first sealing layer 30 is translucent.
  • the material of the first sealing layer 30 may be the same as that of the first adhesive layer 22, TPO (olefin elastomer), or silicon resin.
  • the layer thickness of the 1st sealing layer 30 can be 300 micrometers or more and 500 micrometers or less, for example.
  • the thickness of the first sealing layer 30 is set to be thicker than the protruding length of the first fine wiring 21 from the adhesive layer 22 (the protruding length to the first protective layer 40 side).
  • the surface of the first protective layer 40 on the first sealing layer 30 side may be embossed. In that case, it is preferable to fill the unevenness of the embossment in the first protective layer 40 with the first sealing layer 30. For this reason, it is preferable that the thickness of the first sealing layer 30 has at least a thickness obtained by adding the height of the unevenness of the emboss to the protruding length of the first fine wiring 21 from the adhesive layer 22.
  • the first protective layer 40 is a translucent substrate.
  • Examples of the material of the first protective layer 40 include glass, acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
  • the second protective layer 70 may be a translucent substrate similar to the first protective layer 40, or may be a non-translucent (eg, light reflective) backsheet.
  • the back sheet for example, a single-layer or multi-layer sheet formed of a metal such as tin, aluminum, and stainless steel, an inorganic material such as glass, a polyester, an inorganic vapor-deposited polyester, a fluorine-containing resin, and a thermoplastic resin such as polyolefin. Is mentioned.
  • the photovoltaic module 100 can receive light on both sides (the first protective layer 40 side and the second protective layer 70 side).
  • the second adhesive layer 52 can be made of the same material as the first adhesive layer 22.
  • the second resin film 53 can be made of the same material as the first resin film 23.
  • the second sealing layer 60 can be made of the same material as the first sealing layer 30. However, when light reception on both sides is not necessary, the second sealing layer 60 may contain a pigment or the like as described later.
  • the light receiving surface of the photovoltaic module 100 is one side (the first protective layer 40 side).
  • the material of the second adhesive layer 52 can be the same resin material as that of the first adhesive layer 22.
  • the material of the second sealing layer 60 when the second protective layer 70 is a non-translucent backsheet may be the same as that of the first sealing layer 30, but in this case, the second sealing layer 60 Since the stop layer 60 is not required to be transparent, it is preferable to blend a pigment, a dye, and an inorganic filler from the viewpoint of improving the power generation efficiency.
  • the pigment examples include white pigments such as titanium oxide and calcium carbonate, blue pigments such as ultramarine, and black pigments such as carbon black.
  • blending an inorganic pigment such as titanium oxide is preferable from the viewpoint of preventing the insulation resistance of the photovoltaic module 100 from being lowered.
  • the blending amount of the inorganic pigment is preferably 0 parts by weight or more and 100 parts by weight or less, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the resin component contained in the second sealing layer 60. 50 parts by weight or less, and most preferably 4 parts by weight or more and 50 parts by weight or less.
  • the material of the second resin film 53 when the second protective layer 70 is a non-translucent back sheet may be the same as that of the first resin film 23 or may be other resin materials.
  • the second adhesive layer 52 can have the same thickness as the first adhesive layer 22. That is, when the second fine wiring 51 is a wire having a diameter D, the layer thickness T of the second adhesive layer 52 is preferably set in a range of D / 6 ⁇ D / 12. That is, as an example, when the second fine wiring 51 is a wire having a diameter of 300 ⁇ m, the layer thickness T can be set to 25 ⁇ m or more and 75 ⁇ m or less.
  • the second resin film 53 can have the same thickness as the first resin film 23.
  • the second protective layer 70 may be a hard substrate such as a glass substrate, or may be a flexible resin sheet.
  • the second adhesive layer 52 can have the same thickness as the first adhesive layer 22.
  • the second protective layer 70 is a flexible resin sheet, even if the second fine wiring 51 protrudes on the back surface side (the lower side in FIG. 1) of the second sealing layer 60, The second protective layer 70 can be deformed along the protruding portion of the second fine wiring 51 (the surface of the second protective layer 70 has a shape reflecting the protruding portion of the second fine wiring 51).
  • the second protective layer 70 can suitably protect the back surface of the photovoltaic module 100 while being in close contact with the second sealing layer 60 and the second fine wiring 51. For this reason, when the second protective layer 70 is a flexible resin sheet, the second sealing layer 60 can be made thinner than the first sealing layer 30. Even when the second protective layer 70 is a flexible resin sheet, it is needless to say that the thickness of the second sealing layer 60 may be equal to the thickness of the first sealing layer 30.
  • the photovoltaic module 100 is normally used by connecting a plurality in series. By using a plurality of photovoltaic modules 100 connected in series, the generated voltage can be increased.
  • the first amorphous semiconductor film 12, the second amorphous semiconductor film 13, and the first light-transmissive electrode film 14 are arranged in this order on one surface of the crystalline semiconductor substrate 11.
  • the third amorphous semiconductor film 16, the fourth amorphous semiconductor film 17, and the second translucent electrode film 18 are formed in this order on the other surface of the crystalline semiconductor substrate 11.
  • the first electrode 15 is formed on one surface (the upper surface in FIG. 1) of the first light-transmissive electrode film 14, and the first surface (the lower surface in FIG. 1) of the second light-transmissive electrode film 18. It is obtained by forming the second electrodes 19 respectively.
  • a first wiring sheet (see the wiring sheet 200 shown in FIGS. 4 and 5) in which the first resin film 23, the first adhesive layer 22, and the first fine wiring 21 are integrated, and the first protection.
  • a layer 40 and a sheet-like first sealing layer 30 are prepared.
  • the wiring sheet 200 includes a resin film (the first resin film 23 or the second resin film 53) and an adhesive layer (the first adhesive layer 22 or the second adhesive layer 52) laminated on each other, and the resin film side in the adhesive layer.
  • the fine wiring is preferably a plurality of wires arranged in parallel to each other, and in this way, the amount of the metal material used for forming the fine wiring is reduced. Can be reduced.
  • the resin film is formed of a material including one or more selected from the group consisting of a fluororesin and an acrylic resin.
  • the thickness of the resin film is preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 10 ⁇ m or more and 80 ⁇ m or less.
  • the first resin film 23 disposed on the light receiving surface side preferably has a light transmittance of 70% or more at a wavelength of 350 nm measured according to JIS-K7105. . By doing so, it is possible to realize a module capable of efficiently contributing to the power generation by light energy derived from ultraviolet rays.
  • the second resin film 53 preferably has a light transmittance at a wavelength of 350 nm measured in accordance with JIS-K7105 of 70% or more. By doing so, it is possible to realize a module capable of efficiently contributing to the power generation by light energy derived from ultraviolet rays.
  • the first wiring sheet is interposed between the first electrode 15 on one side of the photovoltaic element 10 and the first protective layer 40, and between the first wiring sheet and the first protective layer 40.
  • the first sealing layer 30 is interposed.
  • a second wiring sheet (see the wiring sheet 200 shown in FIGS. 4 and 5) in which the second resin film 53, the second adhesive layer 52, and the second fine wiring 51 are integrated, and the second protective layer 70.
  • a sheet-like second sealing layer 60 are prepared.
  • the second wiring sheet is interposed between the second electrode 19 on the other surface of the photovoltaic element 10 and the second protective layer 70, and the second wiring sheet is interposed between the second wiring sheet and the second protective layer 70.
  • Two sealing layers 60 are interposed.
  • the first fine wiring 21 is welded to the first electrode 15 via the first adhesive layer 22 and the first sealing layer 30 is interposed.
  • the first resin film 23 and the first protective layer 40 are welded, the second fine wiring 51 is welded to the second electrode 19 through the second adhesive layer 52, and the second sealing layer 60 is used.
  • the second resin film 53 and the second protective layer 70 are welded.
  • the core 21 a and the first electrode 15 are welded by melting the low melting point metal film 21 b on the surface layer of the first fine wiring 21.
  • the low melting point metal film (not shown) on the surface layer of the second fine wiring 51 is melted, so that the core (not shown) of the second fine wiring 51 and the second electrode 19 are welded.
  • the photovoltaic module 100 can be obtained.
  • the wiring sheet 200 having the structure shown in FIG. 4 is used as the first wiring sheet and the second wiring sheet has been described, but the structure shown in FIG. 6 is used as the first wiring sheet and the second wiring sheet.
  • the wiring sheet 200 may be used.
  • a resin film (first resin film 23, second resin film 53) is prepared separately from the wiring sheet 200 (first wiring sheet, second wiring sheet).
  • the first The layer thickness T (FIG. 3) of the one adhesive layer 22 is preferably set in a range of D / 6 ⁇ D / 12.
  • the layer thickness T is preferably in the range of 50 ⁇ m ⁇ 25 ⁇ m.
  • the first resin film 23 can be bonded to the first electrode 15 with sufficient adhesive strength by the first adhesive layer 22.
  • the layer thickness T of the first adhesive layer 22 is set to D / 6 ⁇ D / 12 or more, reliability is reduced due to the formation of voids (cavities) around the first fine wiring 21. Can be suppressed.
  • the layer thickness T of the second adhesive layer 52 is D / 6. It is preferable to be set within a range of ⁇ D / 12. By doing so, it is possible to suppress the floating of the second fine wiring 51 from the second electrode 19, and more reliably weld the second fine wiring 51 to the second electrode 19, and the second resin.
  • the film 53 can be adhered to the second electrode 19 with sufficient adhesive strength by the second adhesive layer 52.
  • the layer thickness T of the second adhesive layer 52 to be equal to or greater than D / 6-D / 12, it is possible to suppress a decrease in reliability due to the formation of voids around the second fine wiring 51. Can do.
  • the copolymer including the heterojunction photovoltaic element 10 and the first adhesive layer 22 includes (A) ethylene and an unsaturated carboxylic acid. Or an ionomer of the above copolymer and (B) a resin material containing either a copolymer containing ethylene and glycidyl (meth) acrylate.
  • said (A) and (B) have the characteristic that a moisture permeability is low. For this reason, even if a material having a relatively high moisture permeability is selected as the first protective layer 40, the second amorphous semiconductor film 13 and the first amorphous semiconductor are formed by the first adhesive layer 22.
  • the membrane 12 can be protected from moisture.
  • the sodium component contained in the first protective layer 40 can also be prevented from migrating to the second amorphous semiconductor film 13 and the first amorphous semiconductor film 12 side together with moisture. For this reason, the freedom degree of selection of the material of the 1st sealing layer 30 becomes high. Further, (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the above copolymer and (B) a copolymer containing ethylene and glycidyl (meth) acrylate have good resistance to ultraviolet rays. . Therefore, even when the first sealing layer 30 does not substantially contain the ultraviolet absorber, it is possible to ensure good resistance of the first adhesive layer 22. For this reason, since ultraviolet light can be used effectively for power generation, better power generation efficiency can be obtained.
  • the copolymer in the resin material (resin material containing a copolymer of ethylene and unsaturated carboxylic acid) constituting the first adhesive layer 22 is an ionomer, good transparency of the first adhesive layer 22; Since the ultraviolet resistance and the low transmittance of moisture can be realized, the above-described effects can be obtained more reliably.
  • the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is set to 70% or more, light energy derived from ultraviolet rays can be efficiently contributed to power generation. Therefore, good power generation efficiency of the photovoltaic module 100 can be obtained.
  • the light transmittance is more preferably 75% or more, and more preferably 80% or more.
  • the light transmittance at a wavelength of 350 nm of the first sealing layer 30 measured according to JIS-K7105 can be set to 70% or more. Good power generation efficiency can be obtained.
  • This light transmittance is also preferably 75% or more, and more preferably 80% or more.
  • the layer thickness T of the first adhesive layer 22 is D / 6 ⁇ D. / 12 can be set.
  • the first fine wiring 21 can be more securely welded to the first electrode 15 by suppressing the floating of the first fine wiring 21 from the first electrode 15.
  • the first resin film 23 can be bonded to the first electrode 15 with sufficient adhesive strength by the first adhesive layer 22.
  • the second adhesive layer 52 is made of (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or the above copolymer, as with the first adhesive layer 22. It can be constituted by a resin material containing either a polymer ionomer or a copolymer containing (B) ethylene and glycidyl (meth) acrylate. By doing so, the same effect as that of the first adhesive layer 22 is obtained by the second adhesive layer 52. That is, even if a material having a relatively high moisture permeability is selected as the second protective layer 70, the fourth amorphous semiconductor film 17 and the third amorphous semiconductor film are formed by the second adhesive layer 52.
  • the copolymer in the resin material (resin material containing a copolymer of ethylene and unsaturated carboxylic acid) constituting the second adhesive layer 52 is an ionomer, good transparency of the second adhesive layer 52, Since the ultraviolet light resistance and the low moisture transmittance can be realized, the above-described effects can be obtained more reliably.
  • the light transmittance at a wavelength of 350 nm of the second adhesive layer 52 measured in accordance with JIS-K7105 for the second adhesive layer 52 is 70% or more, light energy derived from ultraviolet rays contributes to power generation efficiently. Therefore, good power generation efficiency of the photovoltaic module 100 can be obtained.
  • This light transmittance is also preferably 75% or more, and more preferably 80% or more.
  • the light transmittance at a wavelength of 350 nm of the second protective layer 70 measured according to JIS-K7105 can be set to 70% or more. Power generation efficiency can be obtained.
  • This light transmittance is also preferably 75% or more, and more preferably 80% or more.
  • each component of the photovoltaic device 10 may be reversed from the above example.
  • Example 1 The photovoltaic module according to Example 1 was manufactured by the following method. A light-transmitting substrate (first protective layer), a first sealing layer (using a resin sheet 1 described later), a first wiring sheet (using a wiring sheet 1 described later), and a photovoltaic element were stacked in this order. Furthermore, on the photovoltaic element, a second wiring sheet (using a wiring sheet 1 described later), a second sealing layer (using a resin sheet 3 described later), and a back sheet (second protective layer) in this order. These were stacked and laminated using a vacuum laminator to produce a photovoltaic module.
  • first protective layer A light-transmitting substrate (first protective layer), a first sealing layer (using a resin sheet 1 described later), a first wiring sheet (using a wiring sheet 1 described later), and a photovoltaic element were stacked in this order. Furthermore, on the photovoltaic element, a second wiring sheet (using a wiring sheet 1 described later), a second sealing layer (using a resin sheet 3 described
  • Comparative Example 1 The photovoltaic module according to Comparative Example 1 uses the resin sheet 4 described later as the first sealing layer and the second sealing layer, and uses the wiring sheet 2 described later as the first wiring sheet and the second wiring sheet, respectively. Except that, the photovoltaic power generation module according to Example 1 was produced.
  • Examples 2 to 5 Each was produced in the same manner as the photovoltaic module according to Example 1, except that wiring sheets 3 to 6 described later were used as the first wiring sheet and the second wiring sheet, respectively.
  • a base sheet (corresponding to a first resin film or a second resin film) formed of tetrafluoroethylene / ethylene copolymer (ETFE) having a thickness of 25 ⁇ m, and a thickness formed on one surface of the base sheet
  • EFE tetrafluoroethylene / ethylene copolymer
  • a metal micro-wiring with a diameter of 300 ⁇ m is arranged at equal intervals on the surface of the sheet having a thickness of 75 ⁇ m resin sheet 2 (which will be described later: corresponding to the first adhesive layer or the second adhesive layer) and thermocompression-bonded.
  • the wiring sheet 2 was produced by heat-pressing the metal fine wiring with a diameter of 300 micrometers on the surface of the resin sheet 4 (after-mentioned) with a thickness of 100 micrometers, arranging it at equal intervals. In the obtained wiring sheet 2, wires were embedded in the resin sheet 4.
  • ⁇ Wiring sheet 3> Instead of using the sheet obtained by bonding the resin sheet 5 having a thickness of 60 ⁇ m to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 ⁇ m instead of the resin sheet 2 Produced a wiring sheet 3 in the same manner as in Example 1. In the obtained wiring sheet 3, a wire was embedded in the resin sheet 5.
  • PMMA polymethyl methacrylate
  • ⁇ Wiring sheet 4> Instead of using the sheet obtained by bonding the resin sheet 6 having a thickness of 60 ⁇ m to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 ⁇ m instead of the resin sheet 2 In the same manner as in Example 1, a wiring sheet 4 was produced. In the obtained wiring sheet 4, the wire was embedded in the resin sheet 6.
  • PMMA polymethyl methacrylate
  • ⁇ Wiring sheet 5> In place of the resin sheet 2, except that a sheet obtained by bonding a resin sheet 7 having a thickness of 60 ⁇ m to one side of a sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 ⁇ m was used. In the same manner as in Example 1, a wiring sheet 5 was produced. In the obtained wiring sheet 5, the wire was embedded in the resin sheet 7.
  • PMMA polymethyl methacrylate
  • ⁇ Wiring sheet 6> Instead of using the sheet obtained by adhering the resin sheet 8 having a thickness of 60 ⁇ m to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 ⁇ m instead of the resin sheet 2 In the same manner as in Example 1, a wiring sheet 6 was produced. In the obtained wiring sheet 6, wires were embedded in the resin sheet 8.
  • PMMA polymethyl methacrylate
  • Each of the resin sheets 1 to 8 includes an A layer ((A) -1, (A) -2, (A) -3, (A) -4, (A) -5 or (A) -6) described later).
  • the resin sheet 1 is a three-layer sheet, and has a structure in which a surface layer (A) -1, an intermediate layer (B) -1, and a surface layer (A) -1 are laminated in this order. It has become.
  • the resin sheet 2 is a single-layer sheet and is configured by (A) -1.
  • the resin sheet 3 is a three-layer sheet having a structure in which the surface layer (A) -2, the intermediate layer (B) -2, and the surface layer (A) -2 are laminated in this order. It has become.
  • the resin sheet 5 is a single-layer sheet and is made of (A) -3.
  • the resin sheet 6 is a single-layer sheet and is configured by (A) -4.
  • the resin sheet 7 is a single layer sheet, and is constituted by (A) -5.
  • the resin sheet 8 is a single layer sheet and is constituted by (A) -6.
  • Additive- Antioxidant Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1010)
  • UV absorber 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenolLight stabilizer: bis (2,2,6,6, -tetramethyl-4-piperidyl )
  • Sebacate silane coupling agent N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane
  • the same resin as the resin for each layer, the antioxidant, the ultraviolet absorber, and the light stabilizer are resin / antioxidant / ultraviolet absorber.
  • / Light stabilizer 93.7 / 0.3 / 4/2
  • the weight ratio of the mixture was used and the mixture was extruded in advance with a biaxial extruder.
  • a weight ratio of 96/2/2 was used and the mixture was previously extruded by a twin screw extruder.
  • a white masterbatch PE-M 13N4700 manufactured by Dainichi Seika Kogyo Co., Ltd., an antioxidant, an ultraviolet absorber, and a light stabilizer are mixed in a predetermined weight ratio, and a twin-screw extruder is prepared in advance. What was produced in (1) was used.
  • the stabilizer masterbatch 3 used for the layer A includes an ethylene / ⁇ -olefin copolymer (Tafmer A-4090S manufactured by Mitsui Chemicals) as a base resin, an antioxidant, and a light stabilizer. Antioxidants / light stabilizers were mixed at a weight ratio of 96/2/2, and those prepared in advance by a twin screw extruder were used.
  • EVA1 Ethylene / glycidyl methacrylate / vinyl acetate copolymer (EGMAVA, manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B, ethylene content: 83 wt%, glycidyl methacrylate content: 12 wt%, vinyl acetate content: 5 wt% %, MFR (190 ° C., 2160 g load): 7 g / 10 min): 49.1 parts by weight, ethylene / vinyl acetate copolymer (vinyl acetate content: 10% by weight): 49.1 parts by weight, 3-methacrylic acid Roxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM503”): 1.5 parts by weight and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Arkema Yoshitomi
  • EMA1 ethylene / methyl methacrylate copolymer (ethylene content: 80% by weight, methyl methacrylate content: 20% by weight) was used instead of ethylene / vinyl acetate copolymer. EMA1 was obtained in the same manner as EVA1.
  • EOC1 was obtained in the same manner as EVA1, except that EOC1: ethylene / ⁇ -olefin copolymer (Tafmer A-4090S manufactured by Mitsui Chemicals) was used instead of ethylene / vinyl acetate copolymer in preparation of EVA1.
  • EOC2 was obtained in the same manner as EVA1, except that EOC2: ethylene / ⁇ -olefin copolymer (Tafmer H-5030S manufactured by Mitsui Chemicals) was used instead of ethylene / vinyl acetate copolymer in the preparation of EVA1.
  • Resin sheets 1 and 3 which are multilayer resin sheets, are each extruded into two types and three layers of multilayer cast molding machine (manufactured by Tanabe Plastics Machinery), feed block type (manufactured by EDI), 40 mm ⁇ single screw extruder, and die width 500 mm extrusion It was produced by forming into a sheet shape at a processing temperature of 140 ° C. using a machine. Further, the resin sheets 2 and 4 to 8 which are single layer resin sheets were respectively converted into the above using a single layer T-die molding machine (manufactured by Tanabe Plastics Machinery Co., Ltd.), 40 mm ⁇ single screw extruder, and die width 500 mm extruder.
  • the sheet was formed into a sheet shape at a processing temperature of 140 ° C.
  • the wiring sheet 1 having a laminated structure of the base sheet and the resin sheet 2 was manufactured by supplying the base sheet from the feeding portion of the molding machine and heat-pressing the resin sheet 2 with a nip roll at the time of molding.
  • the wiring sheets 3 to 6 were manufactured by supplying a base sheet from the feeding portion of the molding machine and heat-pressing the resin sheets 5 to 8 with a nip roll at the time of molding.
  • Wiring connection quality The wiring connection quality of the photovoltaic modules according to the examples and comparative examples was evaluated by an EL (electroluminescence) method. That is, an EL image was acquired in a state where a current was inputted to each photovoltaic module to emit light, and the quality was evaluated.
  • an EL image inspection device manufactured by ITES, PVX100
  • the measurement conditions for acquiring the EL image were as follows: shutter time 15 seconds, aperture 8, ISO sensitivity 800, input voltage 0.73V to the photovoltaic module, and input current 8A to the photovoltaic module.
  • the evaluation results were as follows: A: no shadow (good connection), C: shadow (part of wiring connection was difficult). The results were all A in Examples 1 to 5 and C in Comparative Example 1.
  • Maximum output (Pmax) About the photovoltaic module which concerns on an Example and a comparative example, the maximum output (Pmax) was measured. That is, the current was measured while changing the bias voltage input to each photovoltaic module, and the obtained data was plotted to obtain an IV curve (not shown).
  • Sumitomo Heavy Industries, Ltd. M130-DDYTB383 J-JA was used.
  • the bias voltage is changed in the range of ⁇ 0.1V to 0.8V. Within this range, the bias voltage is changed in increments of 0.02V from ⁇ 0.1V to 0.4V.
  • the bias voltage was changed in increments of 0.01V up to 0.8V.
  • AM1.5G and 1SUN were adopted as measurement conditions, and measurement was performed at 25 ° C.
  • the fill factor (FF) is the maximum output (Pmax) / (Voc ⁇ Isc), 0.789 in the first embodiment, 0.770 in the second embodiment, 0.755 in the third embodiment, and 0 in the fourth embodiment. 789, 0.789 in Example 5, and 0.743 in Comparative Example 1.
  • Light transmittance of resin sheet at a wavelength of 350 nm was measured according to JIS-K7105 under the condition of 25 ° C. The unit is%.
  • the light transmittance at a wavelength of 350 nm was 85%.
  • the light transmittance at a wavelength of 350 nm was 85%.
  • the light transmittance at a wavelength of 350 nm was 85%.
  • the light transmittance at a wavelength of 350 nm was 85%.
  • the light transmittance at a wavelength of 350 nm was 85%.
  • the wiring sheet 6 of Example 5 the light transmittance at a wavelength of 350 nm was 85%.
  • the light transmittance at a wavelength of 350 nm was 4.3%.
  • Total light transmittance Under the condition of 25 ° C., the total light transmittance of the resin sheet was measured according to JIS-K7105. The unit is%. In the wiring sheet 1 of Example 1, the total light transmittance was 89.6%. In the wiring sheet 3 of Example 2, the total light transmittance was 88.9%. In the wiring sheet 4 of Example 3, the total light transmittance was 88.8%. In the wiring sheet 5 of Example 4, the total light transmittance was 90.2%. In the wiring sheet 6 of Example 5, the total light transmittance was 90.2%. On the other hand, in the wiring sheet 2 of the comparative example, the total light transmittance was 92.2%.

Abstract

A photovoltaic module (100) is provided with the following: a heterojunction-type photovoltaic element (10); a plurality of first super-fine wires (21) that are joined and fixed, by a first adhesive layer (22), to a first electrode (15) of one surface of the photovoltaic element (10); and a first resin film (23) that sandwiches the plurality of first super-fine wires (21) between the film itself and the one surface of the photovoltaic element (10), and that is joined to the one surface of the photovoltaic element (10) via the first adhesive layer (22). The photovoltaic module (100) is further provided with a first protective layer (40) which is light transmissive, and a first sealing layer (30) which is filled in between the first protective layer (40) and the first resin film (23). The first adhesive layer (22) is formed from a resin material which includes any of (A) and (B) below. (A) A copolymer containing ethylene and unsaturated carboxylic acid, or an ionomer of the copolymer. (B) A copolymer containing ethylene and glycidyl (meth)acrylate.

Description

光発電モジュールPhotovoltaic module
　本発明は、光発電モジュールに関する。 The present invention relates to a photovoltaic module.
　光発電モジュールの一種として、ヘテロ接合型の光発電素子を有するタイプのものがある。 As a type of photovoltaic module, there is a type having a heterojunction photovoltaic element.
　ヘテロ接合型の光発電素子は、第１導電型（主としてｎ型）の結晶半導体基板の一方の面側に、第１非晶質系半導体膜と、第１導電型の第２非晶質系半導体膜と、第１透光性電極膜と、第１電極と、をこの順に備えている。ここで、第１非晶質系半導体膜は、真性の非晶質系半導体膜であるか、又は、第２非晶質系半導体膜よりも不純物濃度が低い第１導電型の非晶質系半導体膜である。
　更に、光発電素子は、結晶半導体基板の他方の面側に、真性非晶質系半導体膜と、第２導電型（主としてｐ型）の非晶質系半導体膜と、第２透光性電極膜と、第２電極と、をこの順に備えている。 The heterojunction type photovoltaic device includes a first amorphous semiconductor film and a first conductive type second amorphous system on one surface side of a first conductive type (mainly n-type) crystalline semiconductor substrate. A semiconductor film, a first translucent electrode film, and a first electrode are provided in this order. Here, the first amorphous semiconductor film is an intrinsic amorphous semiconductor film, or the first conductivity type amorphous system having an impurity concentration lower than that of the second amorphous semiconductor film. It is a semiconductor film.
Further, the photovoltaic element has an intrinsic amorphous semiconductor film, a second conductive type (mainly p-type) amorphous semiconductor film, and a second light-transmitting electrode on the other surface side of the crystalline semiconductor substrate. The membrane and the second electrode are provided in this order.
　光発電モジュールは、光発電素子の一方の面の第１電極に第１接着層により接合固定された複数の第１微細配線と、第１接着層を介して光発電素子の一方の面に接合されているとともに光発電素子の一方の面との間に複数の第１微細配線を挟んでいる第１樹脂フィルムと、透光性基板と、透光性基板と第１樹脂フィルムとの間に充填された第１封止層と、を備えている。
　更に、光発電モジュールは、光発電素子の他方の面の第２電極に第２接着層により接合固定された複数の第２微細配線と、第２接着層を介して光発電素子の前記他方の面に接合されているとともに光発電素子の他方の面との間に複数の第２微細配線を挟んでいる第２樹脂フィルムと、バックシート又は第２の透光性基板と、バックシート又は第２の透光性基板と第２樹脂フィルムとの間に充填された第２封止層と、を備えている。 The photovoltaic module is bonded to one surface of the photovoltaic element via the first adhesive layer and a plurality of first fine wirings bonded and fixed to the first electrode on one surface of the photovoltaic element by the first adhesive layer. And a first resin film sandwiching a plurality of first fine wirings between one surface of the photovoltaic device, a translucent substrate, and between the translucent substrate and the first resin film And a filled first sealing layer.
Further, the photovoltaic module includes a plurality of second fine wirings bonded and fixed to the second electrode on the other surface of the photovoltaic element by the second adhesive layer, and the other of the photovoltaic elements via the second adhesive layer. A second resin film bonded to the surface and sandwiching a plurality of second fine wirings between the other surface of the photovoltaic element, a back sheet or a second translucent substrate, and a back sheet or first And a second sealing layer filled between the translucent substrate 2 and the second resin film.
　特許文献１には、第１接着層の材料として、エポキシ接着剤、アクリル接着剤、ゴム接着剤、シリコン接着剤、ポリビニル・エーテル接着剤が記載されている。 Patent Document 1 describes an epoxy adhesive, an acrylic adhesive, a rubber adhesive, a silicon adhesive, and a polyvinyl ether adhesive as materials for the first adhesive layer.
特表２００５－５３６８９４号公報JP 2005-536894 A
　上述のように、ヘテロ接合型の光発電素子は、結晶半導体基板の両面に、非晶質系半導体膜を有する。
　ここで、非晶質系半導体膜は、水分やナトリウムに対して脆弱である。
　このため、封止層の材料として、水分やナトリウムに対するバリア性が十分でないものを用いた場合、非晶質系半導体膜が劣化してしまう。 As described above, the heterojunction photovoltaic device has an amorphous semiconductor film on both surfaces of a crystalline semiconductor substrate.
Here, the amorphous semiconductor film is vulnerable to moisture and sodium.
For this reason, when a material having an insufficient barrier property against moisture or sodium is used as the material of the sealing layer, the amorphous semiconductor film is deteriorated.
　また、特許文献１に記載された第１接着層の材料は、紫外線に対する耐性が非常に弱い。このため、このような材料を用いる場合、一般的に、第１封止層に紫外線吸収剤を含有させることにより、第１接着層を保護する。
　しかしながら、第１封止層が紫外線吸収剤を含有する場合、紫外光を発電に有効に利用することができない。 Moreover, the material of the 1st contact bonding layer described in patent document 1 has very weak tolerance with respect to an ultraviolet-ray. For this reason, when using such a material, generally, the first adhesive layer is protected by including an ultraviolet absorber in the first sealing layer.
However, when the first sealing layer contains an ultraviolet absorber, ultraviolet light cannot be effectively used for power generation.
　本発明は、上記の課題に鑑みなされたものであり、封止層の材料の選択の自由度が高く、且つ、より良好な発電効率を得ることが可能な光発電モジュールを提供する。 The present invention has been made in view of the above problems, and provides a photovoltaic module that has a high degree of freedom in selecting a material for a sealing layer and can obtain better power generation efficiency.
　本発明は、
　光発電素子を備える光発電モジュールであって、
　前記光発電素子は、
　第１導電型の結晶半導体基板を備えているとともに、
　前記結晶半導体基板の一方の面側に、第１非晶質系半導体膜と、第１導電型の第２非晶質系半導体膜と、第１透光性電極膜と、第１電極と、をこの順に備え、
　前記結晶半導体基板の他方の面側に、真性の第３非晶質系半導体膜と、第２導電型の第４非晶質系半導体膜と、第２透光性電極膜と、第２電極と、をこの順に備え、
　前記第１非晶質系半導体膜は、前記第２非晶質系半導体膜よりも不純物濃度が低い第１導電型であるか、又は、真性であり、
　当該光発電モジュールは、更に、
　前記光発電素子の一方の面の前記第１電極に第１接着層により接合固定された複数の第１微細配線と、
　前記光発電素子の前記一方の面との間に前記複数の第１微細配線を挟んでいるとともに、前記第１接着層を介して前記光発電素子の前記一方の面に接合された第１樹脂フィルムと、
　透光性の第１保護層と、
　前記第１保護層と前記第１樹脂フィルムとの間に充填された第１封止層と、
　前記光発電素子の他方の面の前記第２電極に第２接着層により接合固定された複数の第２微細配線と、
　前記光発電素子の前記他方の面との間に前記複数の第２微細配線を挟んでいるとともに、前記第２接着層を介して前記光発電素子の前記他方の面に接合された第２樹脂フィルムと、
　第２保護層と、
　前記第２保護層と前記第２樹脂フィルムとの間に充填された第２封止層と、
　を備え、
　前記第１接着層は、以下の（Ａ）および（Ｂ）のいずれかを含む樹脂材料により構成されている光発電モジュールを提供する。
（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または前記共重合体のアイオノマー
（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体 The present invention
A photovoltaic module comprising photovoltaic elements,
The photovoltaic element is
A first conductivity type crystalline semiconductor substrate;
A first amorphous semiconductor film, a first conductive type second amorphous semiconductor film, a first translucent electrode film, a first electrode, on one surface side of the crystalline semiconductor substrate; In this order,
An intrinsic third amorphous semiconductor film, a second conductivity type fourth amorphous semiconductor film, a second translucent electrode film, and a second electrode are formed on the other surface side of the crystalline semiconductor substrate. And in this order,
The first amorphous semiconductor film is a first conductivity type having an impurity concentration lower than that of the second amorphous semiconductor film, or is intrinsic.
The photovoltaic module further includes
A plurality of first fine wires bonded and fixed to the first electrode on one surface of the photovoltaic element by a first adhesive layer;
The first resin having the plurality of first fine wirings sandwiched between the one surface of the photovoltaic element and bonded to the one surface of the photovoltaic element via the first adhesive layer With film,
A translucent first protective layer;
A first sealing layer filled between the first protective layer and the first resin film;
A plurality of second fine wires bonded and fixed to the second electrode on the other surface of the photovoltaic element by a second adhesive layer;
The second resin having the plurality of second fine wirings sandwiched between the other surface of the photovoltaic element and bonded to the other surface of the photovoltaic element via the second adhesive layer With film,
A second protective layer;
A second sealing layer filled between the second protective layer and the second resin film;
With
The first adhesive layer provides a photovoltaic module configured of a resin material including any of the following (A) and (B).
(A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the copolymer (B) a copolymer containing ethylene and glycidyl (meth) acrylate
　本発明によれば、封止層の材料の選択の自由度が高く、且つ、より良好な発電効率を得ることが可能な光発電モジュールを提供することができる。 According to the present invention, it is possible to provide a photovoltaic module that has a high degree of freedom in selecting a material for the sealing layer and can obtain better power generation efficiency.
　上述した目的、およびその他の目的、特徴および利点は、以下に述べる好適な実施の形態、およびそれに付随する以下の図面によってさらに明らかになる。 The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.
実施形態に係る光発電モジュールの層構造を示す模式的な断面図である。It is typical sectional drawing which shows the layer structure of the photovoltaic module which concerns on embodiment. 実施形態に係る光発電モジュールの模式的な平面図である。It is a typical top view of the photovoltaic module concerning an embodiment. 実施形態に係る光発電モジュールの一部分を示す模式的な断面図である。It is typical sectional drawing which shows a part of photovoltaic module which concerns on embodiment. 実施形態に係る光発電モジュールの製造に用いられる配線シートの一例を示す模式的な断面図である。It is typical sectional drawing which shows an example of the wiring sheet used for manufacture of the photovoltaic module which concerns on embodiment. 実施形態に係る光発電モジュールの製造に用いられる配線シートの一例を示す模式的な平面図である。It is a typical top view which shows an example of the wiring sheet used for manufacture of the photovoltaic module which concerns on embodiment. 実施形態に係る光発電モジュールの製造に用いられる配線シートの他の一例を示す模式的な断面図である。It is typical sectional drawing which shows another example of the wiring sheet used for manufacture of the photovoltaic module which concerns on embodiment.
　以下、本発明の実施形態について、図面を用いて説明する。なお、すべての図面において、同様の構成要素には同一の符号を付し、適宜に説明を省略する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will be omitted as appropriate.
　図１に示すように、本実施形態に係る光発電モジュール１００は、光発電素子１０を備えている。
　光発電素子１０は、第１導電型の結晶半導体基板１１を備えているとともに、結晶半導体基板１１の一方の面側に、第１非晶質系半導体膜１２と、第１導電型の第２非晶質系半導体膜１３と、第１透光性電極膜１４と、第１電極１５と、をこの順に備えている。
　光発電素子１０は、更に、結晶半導体基板１１の他方の面側に、真性の第３非晶質系半導体膜１６と、第２導電型の第４非晶質系半導体膜１７と、第２透光性電極膜１８と、第２電極１９と、をこの順に備えている。
　第１非晶質系半導体膜１２は、第２非晶質系半導体膜１３よりも不純物濃度が低い第１導電型であるか、又は、真性である。
　光発電モジュール１００は、更に、光発電素子１０の一方の面の第１電極１５に第１接着層２２により接合固定された複数の第１微細配線２１と、光発電素子１０の一方の面との間に複数の第１微細配線２１を挟んでいるとともに第１接着層２２を介して光発電素子１０の一方の面に接合された第１樹脂フィルム２３と、透光性の第１保護層４０と、第１保護層４０と第１樹脂フィルム２３との間に充填された第１封止層３０と、を備えている。
　光発電モジュール１００は、更に、光発電素子１０の他方の面の第２電極１９に第２接着層５２により接合固定された複数の第２微細配線５１と、光発電素子１０の他方の面との間に複数の第２微細配線５１を挟んでいるとともに、第２接着層５２を介して光発電素子１０の他方の面に接合された第２樹脂フィルム５３と、第２保護層７０と、第２保護層７０と第２樹脂フィルム５３との間に充填された第２封止層６０と、を備えている。
　そして、第１接着層２２は、以下の（Ａ）および（Ｂ）のいずれかを含む樹脂材料により構成されている。
（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマー
（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体
　以下、詳細に説明する。 As shown in FIG. 1, the photovoltaic module 100 according to this embodiment includes a photovoltaic element 10.
The photovoltaic device 10 includes a first conductive type crystalline semiconductor substrate 11, a first amorphous semiconductor film 12 and a first conductive type second semiconductor film on one surface side of the crystalline semiconductor substrate 11. The amorphous semiconductor film 13, the first translucent electrode film 14, and the first electrode 15 are provided in this order.
The photovoltaic element 10 further includes an intrinsic third amorphous semiconductor film 16, a second conductivity type fourth amorphous semiconductor film 17, and a second conductive film on the other surface side of the crystalline semiconductor substrate 11. The translucent electrode film 18 and the second electrode 19 are provided in this order.
The first amorphous semiconductor film 12 is a first conductivity type having an impurity concentration lower than that of the second amorphous semiconductor film 13 or is intrinsic.
The photovoltaic module 100 further includes a plurality of first fine wirings 21 bonded and fixed to the first electrode 15 on one surface of the photovoltaic element 10 by the first adhesive layer 22, and one surface of the photovoltaic element 10. A first resin film 23 sandwiched between the plurality of first fine wirings 21 and bonded to one surface of the photovoltaic element 10 via the first adhesive layer 22, and a translucent first protective layer 40 and a first sealing layer 30 filled between the first protective layer 40 and the first resin film 23.
The photovoltaic module 100 further includes a plurality of second fine wirings 51 bonded and fixed to the second electrode 19 on the other surface of the photovoltaic element 10 by the second adhesive layer 52, and the other surface of the photovoltaic element 10. A second resin film 53 bonded to the other surface of the photovoltaic device 10 via the second adhesive layer 52, a second protective layer 70, And a second sealing layer 60 filled between the second protective layer 70 and the second resin film 53.
And the 1st contact bonding layer 22 is comprised by the resin material containing either of the following (A) and (B).
(A) A copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the above copolymer (B) A copolymer containing ethylene and glycidyl (meth) acrylate is described in detail below.
　光発電素子１０は、ヘテロ接合型の光発電素子である。 The photovoltaic device 10 is a heterojunction photovoltaic device.
　光発電素子１０の各構成要素の導電型について説明すると、結晶半導体基板１１は、例えばｎ型である。この場合、第２非晶質系半導体膜１３はｎ型、第１非晶質系半導体膜１２は真性又はｎ－型（第２非晶質系半導体膜１３よりも不純物濃度が低いｎ型）、第４非晶質系半導体膜１７はｐ型である。 The conductivity type of each component of the photovoltaic element 10 will be described. The crystalline semiconductor substrate 11 is, for example, n-type. In this case, the second amorphous semiconductor film 13 is n-type, and the first amorphous semiconductor film 12 is intrinsic or n − -type (n-type having a lower impurity concentration than the second amorphous semiconductor film 13). The fourth amorphous semiconductor film 17 is p-type.
　結晶半導体基板１１としては、ｎ型の半導体特性を有する結晶体であれば特に限定されず公知のものを用いることができる。結晶半導体基板１１を構成するｎ型の結晶半導体としては、シリコン（Ｓｉ）の他、ＳｉＣ、ＳｉＧｅ、ＳｉＮ等を挙げることができるが、生産性等の点からシリコンが好ましい。結晶半導体基板１１は、単結晶体であってもよいし、多結晶体であってもよい。結晶半導体基板１１の両面（一方の面及び他方の面）には、光の乱反射による光閉じ込めをより有効にするために、凹凸加工が施されているのが好ましい（不図示）。なお、例えば、約１～５重量％の水酸化ナトリウム、又は水酸化カリウムを含むエッチング液に基板材料を浸漬することによって、多数のピラミッド状の凹凸部を形成することができる。 The crystal semiconductor substrate 11 is not particularly limited as long as it is a crystal having n-type semiconductor characteristics, and a known substrate can be used. Examples of the n-type crystal semiconductor composing the crystalline semiconductor substrate 11 include SiC, SiGe, SiN and the like in addition to silicon (Si). Silicon is preferable from the viewpoint of productivity. The crystalline semiconductor substrate 11 may be a single crystal or a polycrystal. Both surfaces (one surface and the other surface) of the crystalline semiconductor substrate 11 are preferably subjected to uneven processing (not shown) in order to make light confinement due to irregular reflection of light more effective. For example, by immersing the substrate material in an etching solution containing about 1 to 5% by weight of sodium hydroxide or potassium hydroxide, a large number of pyramidal irregularities can be formed.
　また、第１非晶質系半導体膜１２、第２非晶質系半導体膜１３、第３非晶質系半導体膜１６及び第４非晶質系半導体膜１７は、それぞれシリコン薄膜とすることができる。 The first amorphous semiconductor film 12, the second amorphous semiconductor film 13, the third amorphous semiconductor film 16, and the fourth amorphous semiconductor film 17 are each made of a silicon thin film. it can.
　第１非晶質系半導体膜１２は、結晶半導体基板１１の一方の面（図１における上面）に積層されている。
　第２非晶質系半導体膜１３は、第１非晶質系半導体膜１２の一方の面（図１における上面）に積層されている。
　第１非晶質系半導体膜１２と第２非晶質系半導体膜１３との合計の膜厚は、特に限定されないが、例えば１ｎｍ以上２０ｎｍ以下が好ましく、４ｎｍ以上１０ｎｍ以下がより好ましい。このような範囲の膜厚とすることにより、短絡電流とキャリアの再結合の発生とをバランス良く低減することができる。 The first amorphous semiconductor film 12 is stacked on one surface of the crystalline semiconductor substrate 11 (upper surface in FIG. 1).
The second amorphous semiconductor film 13 is stacked on one surface (the upper surface in FIG. 1) of the first amorphous semiconductor film 12.
The total thickness of the first amorphous semiconductor film 12 and the second amorphous semiconductor film 13 is not particularly limited, but is preferably 1 nm to 20 nm, for example, and more preferably 4 nm to 10 nm. By setting the film thickness within such a range, it is possible to reduce the short-circuit current and the occurrence of carrier recombination in a well-balanced manner.
　第１透光性電極膜１４は、第２非晶質系半導体膜１３の一方の面（図１における上面）に積層されている。
　第１透光性電極膜１４を構成する透明電極材料としては、例えば、インジウム錫酸化物（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ：ＩＴＯ）、タングステンドープインジウム酸化物（Ｉｎｄｉｕｍ　Ｔｕｎｇｓｔｅｎ　Ｏｘｉｄｅ：ＩＷＯ）、セリウムドープインジウム酸化物（Ｉｎｄｉｕｍ　Ｃｅｒｉｕｍ　Ｏｘｉｄｅ：ＩＣＯ）、ＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）、ＡＺＯ（アルミニウムドープＺｎＯ）、ＧＺＯ（ガリウムドープＺｎＯ）等の公知の材料を挙げることができる。 The first translucent electrode film 14 is stacked on one surface (the upper surface in FIG. 1) of the second amorphous semiconductor film 13.
Examples of the transparent electrode material constituting the first translucent electrode film 14 include indium tin oxide (ITO), tungsten-doped indium oxide (InWO), and cerium-doped indium oxide (ITO). Well-known materials such as Indium Cerium Oxide (ICO), IZO (Indium Zinc Oxide), AZO (aluminum doped ZnO), and GZO (gallium doped ZnO) can be exemplified.
　第３非晶質系半導体膜１６は、結晶半導体基板１１の他方の面（図１における下面）に積層されている。換言すれば、第３非晶質系半導体膜１６は、結晶半導体基板１１と第４非晶質系半導体膜１７との間に介在している。第３非晶質系半導体膜１６の膜厚は特に限定されないが、例えば１ｎｍ以上１０ｎｍ以下とすることができる。 The third amorphous semiconductor film 16 is stacked on the other surface (the lower surface in FIG. 1) of the crystalline semiconductor substrate 11. In other words, the third amorphous semiconductor film 16 is interposed between the crystalline semiconductor substrate 11 and the fourth amorphous semiconductor film 17. The film thickness of the third amorphous semiconductor film 16 is not particularly limited, but may be, for example, 1 nm or more and 10 nm or less.
　第４非晶質系半導体膜１７は、第３非晶質系半導体膜１６の一方の面（図１における下面）に積層されている。第４非晶質系半導体膜１７の膜厚は、特に限定されないが、例えば１ｎｍ以上２０ｎｍ以下が好ましく、３ｎｍ以上１０ｎｍ以下がより好ましい。 The fourth amorphous semiconductor film 17 is laminated on one surface (the lower surface in FIG. 1) of the third amorphous semiconductor film 16. Although the film thickness of the 4th amorphous semiconductor film 17 is not specifically limited, For example, 1 nm or more and 20 nm or less are preferable, and 3 nm or more and 10 nm or less are more preferable.
　第２透光性電極膜１８は、第４非晶質系半導体膜１７の一方の面（図１における下面）に積層されている。第２透光性電極膜１８を構成する材料は、第１透光性電極膜１４と同様である。 The second translucent electrode film 18 is laminated on one surface (the lower surface in FIG. 1) of the fourth amorphous semiconductor film 17. The material constituting the second translucent electrode film 18 is the same as that of the first translucent electrode film 14.
　ここで、真性とは、不純物が意図的にドープされていないことをいう。したがって、真性の非晶質系半導体膜には、原料に本来含まれる不純物や製造過程において非意図的に混入した不純物が存在するものも含まれる。
　また、非晶質系とは、非晶質体のみならず、微結晶体を含むことを意味する。
　ｎ型の非晶質半導体膜とは、薄膜中に含有される元素の数密度比として、シリコンに対して１０－５程度以上の不純物が含有されているものをいう。 Here, intrinsic means that impurities are not intentionally doped. Therefore, the intrinsic amorphous semiconductor film includes impurities that are originally included in the raw material and impurities that are unintentionally mixed in the manufacturing process.
Moreover, an amorphous system means that not only an amorphous body but a microcrystal body is included.
An n-type amorphous semiconductor film refers to a film containing impurities of about 10 −5 or more relative to silicon as a number density ratio of elements contained in a thin film.
　第１電極１５は、例えば、フィンガー電極であるか、又は、第１透光性電極膜１４の一方の面（図１における上面）の全面に成膜された金属膜である。
　同様に、第２電極１９は、例えば、フィンガー電極であるか、又は、第２透光性電極膜１８の一方の面（図１における下面）の全面に成膜された金属膜である。
　第１電極１５及び第２電極１９を構成するフィンガー電極の材料としては、銀ペースト等の導電性接着剤や、銅線等の金属導線を用いることができる。フィンガー電極の幅は、例えば、２０μｍ以上８０μｍ以下程度である。
　また、第１電極１５及び第２電極１９を構成する金属膜の材料としては、銀、銀合金又はアルミニウム合金等を用いることができる。 The first electrode 15 is, for example, a finger electrode, or a metal film formed on the entire surface of one surface (the upper surface in FIG. 1) of the first light-transmissive electrode film 14.
Similarly, the second electrode 19 is, for example, a finger electrode or a metal film formed on the entire surface of one surface (the lower surface in FIG. 1) of the second translucent electrode film 18.
As a material of the finger electrode constituting the first electrode 15 and the second electrode 19, a conductive adhesive such as a silver paste or a metal conductor such as a copper wire can be used. The width of the finger electrode is, for example, about 20 μm or more and 80 μm or less.
In addition, as a material of the metal film constituting the first electrode 15 and the second electrode 19, silver, a silver alloy, an aluminum alloy, or the like can be used.
　複数の第１微細配線２１は、例えば、互いに平行に配置された複数のワイヤ又はバスバーである。
　以下、第１微細配線２１がワイヤである場合の構成を説明する。
　この場合、第１微細配線２１は、コア２１ａと、コア２１ａの表面にコーティングされている低融点金属膜２１ｂと、を有している。コア２１ａの金属材料としては、銅等が挙げられる。低融点金属膜２１ｂの金属材料としては、インジウムとスズとの合金等が挙げられる。
　第１微細配線２１の直径は、１００μｍ以上４００μｍ以下が好ましく、２００μｍ以上３００μｍ以下がより好ましい。
　第２微細配線５１は、第１微細配線２１と同様に構成されている。 The plurality of first fine wirings 21 are, for example, a plurality of wires or bus bars arranged in parallel to each other.
Hereinafter, a configuration in the case where the first fine wiring 21 is a wire will be described.
In this case, the first fine wiring 21 has a core 21a and a low melting point metal film 21b coated on the surface of the core 21a. Examples of the metal material of the core 21a include copper. Examples of the metal material of the low melting point metal film 21b include an alloy of indium and tin.
The diameter of the first fine wiring 21 is preferably 100 μm or more and 400 μm or less, and more preferably 200 μm or more and 300 μm or less.
The second fine wiring 51 is configured in the same manner as the first fine wiring 21.
　なお、第１電極１５がフィンガー電極である場合、複数の第１微細配線２１は、第１電極１５と直交している（図２参照）。
　同様に、第２電極１９がフィンガー電極である場合、複数の第２微細配線５１は、第２電極１９と直交している。 In addition, when the 1st electrode 15 is a finger electrode, the some 1st fine wiring 21 is orthogonally crossed with the 1st electrode 15 (refer FIG. 2).
Similarly, when the second electrode 19 is a finger electrode, the plurality of second fine wirings 51 are orthogonal to the second electrode 19.
　第１接着層２２は、透光性である。
　第１接着層２２は、以下の（Ａ）および（Ｂ）のいずれかを含む樹脂材料により構成されている。
（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマー
（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体 The first adhesive layer 22 is translucent.
The 1st contact bonding layer 22 is comprised with the resin material containing either of the following (A) and (B).
(A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the above copolymer (B) a copolymer containing ethylene and glycidyl (meth) acrylate
　エチレンと不飽和カルボン酸との共重合体としては、たとえば、エチレンと不飽和カルボン酸との共重合体のアイオノマーが挙げられる。このエチレンと不飽和カルボン酸との共重合体のアイオノマーには、リチウム、ナトリウム等のアルカリ金属、カルシウム、マグネシウム、セリウム、亜鉛、アルミニウム等の多価金属等に由来する金属種を含有させることができる。これらの中でも、ナトリウム、マグネシウム、亜鉛が好ましく用いられる。一般に、アイオノマーは、透明性に優れ、かつ高温における貯蔵弾性率Ｅ´が高いことが知られている。また、本実施形態に係るエチレンと不飽和カルボン酸との共重合体のアイオノマーの中和度は、好ましくは、８０％以下であり、さらに好ましくは、接着性の観点から６０％以下であり、最も好ましくは、４０％以下である。 Examples of the copolymer of ethylene and unsaturated carboxylic acid include an ionomer of a copolymer of ethylene and unsaturated carboxylic acid. The ionomer of the copolymer of ethylene and unsaturated carboxylic acid may contain a metal species derived from an alkali metal such as lithium or sodium, or a polyvalent metal such as calcium, magnesium, cerium, zinc or aluminum. it can. Among these, sodium, magnesium, and zinc are preferably used. Generally, ionomers are known to have excellent transparency and a high storage elastic modulus E ′ at high temperatures. Further, the ionomer neutralization degree of the copolymer of ethylene and unsaturated carboxylic acid according to this embodiment is preferably 80% or less, and more preferably 60% or less from the viewpoint of adhesiveness. Most preferably, it is 40% or less.
　エチレンと不飽和カルボン酸との共重合体またはエチレンと不飽和カルボン酸との共重合体のアイオノマーにおける不飽和カルボン酸成分としては、アクリル酸、メタクリル酸、エタクリル酸、フマル酸、マレイン酸、マレイン酸モノメチル、無水マレイン酸等が挙げられる。中でも、不飽和カルボン酸成分としては、（メタ）アクリル酸が好ましい。そのため、エチレンと不飽和カルボン酸との共重合体としては、エチレン・（メタ）アクリル酸共重合体が好ましい。なお、本実施形態に係るエチレン・不飽和カルボン酸共重合体は、エチレンと不飽和カルボン酸との２元共重合体に限らず、エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体等のエチレンと不飽和カルボン酸を含む多元共重合体も包含している。上記エチレン・不飽和カルボン酸・不飽和カルボン酸エステル共重合体における不飽和カルボン酸エステル成分としては、上述した不飽和カルボン酸成分として用いられる各種カルボン酸の炭素数１～２０のアルキルエステルが挙げられる。具体的に、アルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、２－エチルヘキシル基、イソオクチル基等が挙げられる。 The unsaturated carboxylic acid component in the ionomer of a copolymer of ethylene and an unsaturated carboxylic acid or a copolymer of ethylene and an unsaturated carboxylic acid includes acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, maleic acid. Examples thereof include monomethyl acid and maleic anhydride. Among these, (meth) acrylic acid is preferable as the unsaturated carboxylic acid component. Therefore, the ethylene / unsaturated carboxylic acid copolymer is preferably an ethylene / (meth) acrylic acid copolymer. The ethylene / unsaturated carboxylic acid copolymer according to the present embodiment is not limited to a binary copolymer of ethylene and unsaturated carboxylic acid, but an ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer. Also included are multicomponent copolymers containing ethylene and unsaturated carboxylic acids. Examples of the unsaturated carboxylic acid ester component in the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer include alkyl esters having 1 to 20 carbon atoms of various carboxylic acids used as the unsaturated carboxylic acid component described above. It is done. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 2-ethylhexyl group, and an isooctyl group.
　本実施形態に係るエチレンと不飽和カルボン酸との共重合体またはそのアイオノマーにおける（メタ）アクリル酸単位等の不飽和カルボン酸単位の含有量は、優れた紫外線透過性を実現する観点から、好ましくは、２重量％以上３０重量％以下であり、より好ましくは、９重量％以上２５重量％以下であり、最も好ましくは、１２重量％以上２０重量％以下である。
　また、共重合体が不飽和カルボン酸エステルを含有する場合、共重合体全量に対する不飽和カルボン酸エステルの含有量は、１重量％以上３５重量％以下が好ましく、３重量％以上３２重量％以下がより好ましく、５重量％以上３０重量％以下がさらに好ましい。 The content of unsaturated carboxylic acid units such as (meth) acrylic acid units in the copolymer of ethylene and unsaturated carboxylic acid or its ionomer according to the present embodiment is preferable from the viewpoint of realizing excellent ultraviolet transparency. Is 2 wt% or more and 30 wt% or less, more preferably 9 wt% or more and 25 wt% or less, and most preferably 12 wt% or more and 20 wt% or less.
In addition, when the copolymer contains an unsaturated carboxylic acid ester, the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is preferably 1% by weight or more and 35% by weight or less, and preferably 3% by weight or more and 32% by weight or less. Is more preferable, and 5 to 30 weight% is further more preferable.
　エチレンと不飽和カルボン酸との共重合体の透明性および接着性を良好にする観点から、共重合体全量に対する不飽和カルボン酸の含有量は、１重量％以上であることが好ましく、２重量％以上であることがより好ましく、３重量％以上であることがさらに好ましい。
　一方、共重合体全量に対する不飽和カルボン酸の含有量は、吸湿性を低減させる観点から、好ましくは、２０重量％以下であり、さらに好ましくは、１５重量％以下である。
　また、共重合体が不飽和カルボン酸エステルを含有する場合、共重合体の透明性および接着性を良好にする観点から、共重合体全量に対する不飽和カルボン酸エステルの含有量は１重量％以上であることが好ましく、３重量％以上であることがより好ましく、５重量％以上であることがさらに好ましい。一方、共重合体が不飽和カルボン酸エステルを含有する場合、吸湿性を低減させる観点から、共重合体全量に対する不飽和カルボン酸エステルの含有量は、好ましくは３５重量％以下であり、より好ましくは３２重量％以下であり、さらに好ましくは３０重量％以下である。 From the viewpoint of improving the transparency and adhesiveness of the copolymer of ethylene and unsaturated carboxylic acid, the content of the unsaturated carboxylic acid with respect to the total amount of the copolymer is preferably 1% by weight or more. % Or more, more preferably 3% by weight or more.
On the other hand, the content of the unsaturated carboxylic acid with respect to the total amount of the copolymer is preferably 20% by weight or less, and more preferably 15% by weight or less from the viewpoint of reducing hygroscopicity.
In addition, when the copolymer contains an unsaturated carboxylic acid ester, the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is 1% by weight or more from the viewpoint of improving the transparency and adhesiveness of the copolymer. Preferably, it is 3% by weight or more, more preferably 5% by weight or more. On the other hand, when the copolymer contains an unsaturated carboxylic acid ester, the content of the unsaturated carboxylic acid ester with respect to the total amount of the copolymer is preferably 35% by weight or less, more preferably, from the viewpoint of reducing hygroscopicity. Is 32% by weight or less, more preferably 30% by weight or less.
　本実施形態に係るエチレンと不飽和カルボン酸との共重合体は、高温、高圧条件下、ラジカル共重合反応を行うことにより得ることができる。また、エチレンと不飽和カルボン酸との共重合体のアイオノマーは、エチレンと不飽和カルボン酸との共重合体と金属化合物とを反応させることによって得ることができる。 The copolymer of ethylene and unsaturated carboxylic acid according to this embodiment can be obtained by performing a radical copolymerization reaction under high temperature and high pressure conditions. Further, an ionomer of a copolymer of ethylene and unsaturated carboxylic acid can be obtained by reacting a copolymer of ethylene and unsaturated carboxylic acid with a metal compound.
　第１接着層２２に含まれるエチレンと（メタ）アクリル酸グリシジルを含む共重合体に含まれる（メタ）アクリル酸グリシジルとは、メタクリル酸グリシジルまたはアクリル酸グリシジルの少なくとも一方を指す。
　エチレンと（メタ）アクリル酸グリシジルを含む共重合体としては、例えば、エチレン・（メタ）アクリル酸グリシジル共重合体、エチレン・（メタ）アクリル酸グリシジル・酢酸ビニル共重合体、およびエチレン・（メタ）アクリル酸グリシジル・（メタ）アクリル酸エステル共重合体等から選択される一種または二種以上が挙げられる。 The glycidyl (meth) acrylate contained in the copolymer containing ethylene and glycidyl (meth) acrylate contained in the first adhesive layer 22 refers to at least one of glycidyl methacrylate or glycidyl acrylate.
Examples of the copolymer containing ethylene and glycidyl (meth) acrylate include ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid glycidyl / vinyl acetate copolymer, and ethylene / (meta ) One or more selected from glycidyl acrylate / (meth) acrylic acid ester copolymer and the like.
　エチレンと（メタ）アクリル酸グリシジルを含む共重合体中の（メタ）アクリル酸グリシジルに由来の構成単位の含有割合は、好ましくは２重量％以上３０重量％以下、より好ましくは３重量％以上２５重量％以下である。
　（メタ）アクリル酸グリシジルに由来の構成単位の含有割合が上記範囲内であると、得られる第１接着層２２の接着性や柔軟性、取扱い性、加工性等のバランスをより一層良好なものとすることができる。 The content ratio of the structural unit derived from glycidyl (meth) acrylate in the copolymer containing ethylene and glycidyl (meth) acrylate is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25%. % By weight or less.
When the content ratio of the structural unit derived from glycidyl (meth) acrylate is within the above range, the balance of the adhesiveness, flexibility, handleability, workability, etc. of the obtained first adhesive layer 22 is further improved. It can be.
　エチレンと（メタ）アクリル酸グリシジルを含む共重合体中の「エチレン由来の構成単位」の含有割合は、好ましくは６５重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上である。このとき、エチレンと（メタ）アクリル酸グリシジルを含む共重合体は、エチレン、（メタ）アクリル酸グリシジル以外の他のモノマー単位（例えば、酢酸ビニル、（メタ）アクリル酸エステル等）をさらに含むことができる。 The content ratio of the “ethylene-derived structural unit” in the copolymer containing ethylene and glycidyl (meth) acrylate is preferably 65% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more. is there. At this time, the copolymer containing ethylene and glycidyl (meth) acrylate further contains other monomer units (for example, vinyl acetate, (meth) acrylate ester, etc.) other than ethylene and glycidyl (meth) acrylate. Can do.
　具体的には、エチレンに由来の構成単位と、（メタ）アクリル酸グリシジルに由来の構成単位とを含有する共重合体のほか、この２つの構成単位のほかに、さらに酢酸ビニルに由来の構成単位および（メタ）アクリル酸エステルに由来の構成単位の少なくとも一方を含有する共重合体等が挙げられる。
　酢酸ビニルに由来の構成単位および（メタ）アクリル酸エステルに由来の構成単位の含有割合は３０重量％以下であることが好ましく、２０重量％以下であることがより好ましい。 Specifically, in addition to a copolymer containing a structural unit derived from ethylene and a structural unit derived from glycidyl (meth) acrylate, in addition to these two structural units, a composition derived from vinyl acetate. Examples thereof include a copolymer containing at least one of a unit and a structural unit derived from a (meth) acrylic acid ester.
The content ratio of the structural unit derived from vinyl acetate and the structural unit derived from (meth) acrylic acid ester is preferably 30% by weight or less, and more preferably 20% by weight or less.
　酢酸ビニルに由来の構成単位および（メタ）アクリル酸エステルに由来の構成単位の含有割合の下限値は、特に制限はないが、好ましくは０．１重量％以上、より好ましくは０．５重量％以上、さらに好ましくは１重量％以上が望ましい。さらには、酢酸ビニルに由来の構成単位または（メタ）アクリル酸エステルに由来の構成単位の含有割合は、０．１～３０重量％の範囲が好ましく、さらに０．５～２０重量％、特に１～２０重量％の範囲が好ましい。
　エチレンと（メタ）アクリル酸グリシジルを含む共重合体は、１種を単独でまたは共重合比等の異なる共重合体の２種以上またはモノマー種の異なる共重合体の２種以上を組み合わせて用いることができる。 The lower limit of the content ratio of the structural unit derived from vinyl acetate and the structural unit derived from (meth) acrylic acid ester is not particularly limited, but is preferably 0.1% by weight or more, more preferably 0.5% by weight. More preferably, 1% by weight or more is desirable. Further, the content ratio of the structural unit derived from vinyl acetate or the structural unit derived from (meth) acrylic acid ester is preferably in the range of 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, particularly 1 A range of ˜20% by weight is preferred.
A copolymer containing ethylene and glycidyl (meth) acrylate is used alone or in combination of two or more of copolymers having different copolymerization ratios or two or more of copolymers having different monomer types. be able to.
　エチレンと（メタ）アクリル酸グリシジルを含む共重合体の少なくとも一部はシランカップリング剤により変性されていてもよい。
　シランカップリング剤の含有量はエチレンと（メタ）アクリル酸グリシジルを含む共重合体１００重量％中０．０１～５重量％が好ましい。 At least a part of the copolymer containing ethylene and glycidyl (meth) acrylate may be modified with a silane coupling agent.
The content of the silane coupling agent is preferably 0.01 to 5% by weight in 100% by weight of the copolymer containing ethylene and glycidyl (meth) acrylate.
　第１接着層２２には、上記の（Ａ）および（Ｂ）のいずれか一方を含んでいればよいが、第１接着層２２の樹脂成分１００重量％中に上記の（Ａ）および（Ｂ）を合計で３０重量％以上含むことが好ましく、４０重量％以上含むことがより好ましく、５０重量％以上含むことがさらに好ましい。上限値は特に制限はないが上記の（Ｂ）を含む場合は８０重量％以下が好ましく、６０重量％以下がより好ましい。 The first adhesive layer 22 only needs to contain one of the above (A) and (B), but the above-mentioned (A) and (B) are contained in 100% by weight of the resin component of the first adhesive layer 22. ) In total is preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more. The upper limit is not particularly limited, but when it contains (B), it is preferably 80% by weight or less, more preferably 60% by weight or less.
　また、第１接着層２２を形成する樹脂材料は、その他の樹脂を含んでもよい。その他の樹脂としては、例えば、プロピレン系樹脂やエチレン系樹脂等が挙げられる。 Further, the resin material forming the first adhesive layer 22 may include other resins. Examples of other resins include propylene-based resins and ethylene-based resins.
　エチレン系樹脂としては、炭素数３～２０のα－オレフィンに由来する構成単位の含有割合が、５モル％以上５０モル％未満であるエチレン・α-オレフィン共重合体やエチレン・極性モノマー共重合体等が挙げられる。 Examples of ethylene resins include ethylene / α-olefin copolymers and ethylene / polar monomer copolymers in which the content of structural units derived from α-olefins having 3 to 20 carbon atoms is 5 mol% or more and less than 50 mol%. Examples include coalescence.
　上記炭素数３～２０のα－オレフィンの具体例としては、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－へプテン、１－オクテン、１－ノネン、１－デセン、１－ウンデセン、１－ドデセン、１－トリデセン、１－テトラデセン、１－ペンタデセン、１－ヘキサデセン、１－ヘプタデセン、１－オクタデセン、１－ナノデセン、１－エイコセン等の直鎖状のα－オレフィン；３－メチル－１－ブテン、３－メチル－１－ペンテン、４－メチル－１－ペンテン、２－エチル－１－ヘキセン、２，２，４－トリメチル－１－ペンテン等の分岐状のα－オレフィン等が挙げられ、これらは２種類を組み合わせて使用することもできる。
　中でも、上記α－オレフィンの炭素数は、汎用性（コストや量産性あるいは入手のしやすさ）の点で、３～１０が好ましく、さらには３～８が好ましい。 Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. Linear α-olefins such as 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicocene; Examples include branched α-olefins such as 1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. These can be used in combination of two types.
In particular, the number of carbon atoms of the α-olefin is preferably 3 to 10, more preferably 3 to 8 in view of versatility (cost, mass productivity, or availability).
　エチレン・α－オレフィン共重合体としては、好ましくは、エチレン・プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－オクテン共重合体であり、いずれのエチレン・α－オレフィン共重合体も、エチレン由来の構成単位の含有割合が５０モル％以上であることを意味する。
　エチレン・α－オレフィン共重合体は、例えば、メタロセン系触媒を用いた、スラリー重合法、溶液重合法、塊状重合法、気相重合法等で製造できる。 The ethylene / α-olefin copolymer is preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 4-methyl-1-pentene copolymer, or an ethylene / 1-hexene copolymer. This is an ethylene / 1-octene copolymer, and any ethylene / α-olefin copolymer means that the content of the structural unit derived from ethylene is 50 mol% or more.
The ethylene / α-olefin copolymer can be produced by, for example, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, or a gas phase polymerization method using a metallocene catalyst.
　エチレン・極性モノマー共重合体は、例えば、エチレン・ビニルエステル共重合体およびエチレン・不飽和カルボン酸エステル共重合体等が挙げられる。本実施形態において極性モノマーとは官能基を有するモノマーを意味する。
　エチレン・ビニルエステル共重合体としては、例えば、エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・酪酸ビニル共重合体、エチレン・ステアリン酸ビニル共重合体等から選択される一種または二種以上を用いることができる。 Examples of the ethylene / polar monomer copolymer include an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer. In the present embodiment, the polar monomer means a monomer having a functional group.
The ethylene / vinyl ester copolymer is selected from, for example, an ethylene / vinyl acetate copolymer, an ethylene / vinyl propionate copolymer, an ethylene / vinyl butyrate copolymer, an ethylene / vinyl stearate copolymer, and the like. One kind or two or more kinds can be used.
　本実施形態に係るエチレン・不飽和カルボン酸エステル共重合体は、エチレンと、不飽和カルボン酸エステルの少なくとも１種とを共重合した重合体である。
　具体的には、エチレンと、不飽和カルボン酸のアルキルエステルと、からなる共重合体を例示することができる。
　不飽和カルボン酸エステルにおける不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、エタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等が挙げられる。
　不飽和カルボン酸のアルキルエステルにおけるアルキル部位としては、炭素数１～１２のものを挙げることができ、より具体的には、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、セカンダリーブチル、２－エチルヘキシル、イソオクチル等のアルキル基を例示することができる。本実施形態では、アルキルエステルのアルキル部位の炭素数は、１～８が好ましい。 The ethylene / unsaturated carboxylic acid ester copolymer according to this embodiment is a polymer obtained by copolymerizing ethylene and at least one unsaturated carboxylic acid ester.
Specifically, a copolymer composed of ethylene and an alkyl ester of an unsaturated carboxylic acid can be exemplified.
Examples of the unsaturated carboxylic acid in the unsaturated carboxylic acid ester include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
Examples of the alkyl moiety in the alkyl ester of the unsaturated carboxylic acid include those having 1 to 12 carbon atoms, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl. And alkyl groups such as 2-ethylhexyl and isooctyl. In this embodiment, the alkyl moiety of the alkyl ester preferably has 1 to 8 carbon atoms.
　不飽和カルボン酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシル等の（メタ）アクリル酸エステル等から選択される一種または二種以上を含むことが好ましい。これらの不飽和カルボン酸エステルは１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。これら中でも、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソブチル、および（メタ）アクリル酸ｎ－ブチル等から選択される一種または二種以上を含むことがより好ましい。 Examples of unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid It is preferable to include one or more selected from (meth) acrylic acid esters such as n-butyl, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These unsaturated carboxylic acid esters may be used alone or in combination of two or more. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, etc. It is more preferable that 1 type or 2 types or more selected from are included.
　本実施形態において、好ましいエチレン・不飽和カルボン酸エステル共重合体は、エチレン・（メタ）アクリル酸エステル共重合体である。その中でも（メタ）アクリル酸エステルとして１種類の化合物からなる共重合体が好ましい。このような共重合体としては、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸イソプロピル共重合体、エチレン・（メタ）アクリル酸ｎ－プロピル共重合体、エチレン・（メタ）アクリル酸イソブチル共重合体、エチレン・（メタ）アクリル酸ｎ－ブチル共重合体、エチレン・（メタ）アクリル酸イソオクチル共重合体、エチレン・（メタ）アクリル酸２－エチルヘキシル共重合体等が挙げられる。 In this embodiment, a preferable ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylic acid ester copolymer. Among them, a copolymer composed of one kind of compound is preferable as the (meth) acrylic acid ester. Examples of such copolymers include ethylene / methyl (meth) acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) isopropyl acrylate copolymer, ethylene / (meth). N-propyl acrylate copolymer, ethylene / (meth) acrylate isobutyl copolymer, ethylene / (meth) acrylate n-butyl copolymer, ethylene / (meth) acrylate isooctyl copolymer, ethylene / ( And (meth) acrylic acid 2-ethylhexyl copolymer.
　エチレン・極性モノマー共重合体は、エチレン・酢酸ビニル共重合体、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸イソプロピル共重合体、エチレン・（メタ）アクリル酸ｎ－プロピル共重合体、エチレン・（メタ）アクリル酸イソブチル共重合体、エチレン・（メタ）アクリル酸ｎ－ブチル共重合体から選択される一種または二種以上を含むことが好ましく、エチレン・酢酸ビニル共重合体を含むことがより好ましい。
　なお、本実施形態においてはエチレン・極性モノマー共重合体は、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
　これらのその他の樹脂はシランカップリング剤で変性されていてもよい。
　シランカップリング剤の含有量はその他の樹脂成分１００重量％中０．０１～５重量％が好ましい。 The ethylene / polar monomer copolymer includes ethylene / vinyl acetate copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) acrylate isopropyl copolymer. One or two types selected from polymers, ethylene / (meth) acrylate n-propyl copolymer, ethylene / (meth) acrylate isobutyl copolymer, ethylene / (meth) acrylate n-butyl copolymer It is preferable to include the above, and it is more preferable to include an ethylene / vinyl acetate copolymer.
In the present embodiment, the ethylene / polar monomer copolymer may be used alone or in combination of two or more.
These other resins may be modified with a silane coupling agent.
The content of the silane coupling agent is preferably 0.01 to 5% by weight in 100% by weight of other resin components.
　また、第１接着層２２を形成する樹脂材料中には、たとえば、ヒドロキノンモノベンジルエーテル、トリフェニルホスファイト等の酸化防止剤、ステアリン酸鉛、ラウリン酸バリウム等の熱安定剤、微粒酸化チタン、酸化亜鉛等の充填剤、顔料、染料、滑剤、ブロッキング防止剤、発泡剤、発泡助剤、架橋剤、架橋助剤、難燃剤等の各種添加剤を配合してもよい。各成分の含有量は、第１接着層２２中の樹脂成分１００重量部に対して０．００５～２重量部が好ましく、０．００８～１重量部がより好ましい。 Examples of the resin material forming the first adhesive layer 22 include antioxidants such as hydroquinone monobenzyl ether and triphenyl phosphite, thermal stabilizers such as lead stearate and barium laurate, fine titanium oxide, Various additives such as fillers such as zinc oxide, pigments, dyes, lubricants, antiblocking agents, foaming agents, foaming aids, crosslinking agents, crosslinking aids, flame retardants, and the like may be blended. The content of each component is preferably 0.005 to 2 parts by weight and more preferably 0.008 to 1 part by weight with respect to 100 parts by weight of the resin component in the first adhesive layer 22.
　第１接着層２２を形成する樹脂材料中には、たとえば、変色防止剤として、カドミウム、バリウム等の金属の脂肪酸塩を任意に配合してもよい。 In the resin material forming the first adhesive layer 22, for example, a metal fatty acid salt such as cadmium or barium may be arbitrarily blended as a discoloration preventing agent.
　ＪＩＳ－Ｋ７１０５に準じて測定した第１接着層２２の３５０ｎｍの波長における光線透過率が、７０％以上であることが好ましい。こうすることで、紫外線由来の光エネルギーを効率よく発電に寄与させることが可能となる。本明細書において、紫外線由来の光エネルギーとは、３８０ｎｍ未満の波長領域の光に由来する光エネルギーを指す。
　第１接着層２２の材料として、上述した材料を用いることにより、このような光線透過率を実現することができる。
　第１接着層２２が紫外線吸収剤を実質的に含まない構成とすることによって、より確実に、このような光線透過率を実現することができる。
　なお、ＪＩＳ－Ｋ７１０５に準じて測定した第１接着層２２の３５０ｎｍの波長における光線透過率は、好ましくは、７５％以上であり、より好ましくは、８０％以上である。こうすることで、より一層効果的に紫外線に由来する光エネルギーを発電に寄与させることが可能となる。 It is preferable that the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is 70% or more. By doing so, light energy derived from ultraviolet rays can be efficiently contributed to power generation. In this specification, light energy derived from ultraviolet rays refers to light energy derived from light in a wavelength region of less than 380 nm.
By using the above-described material as the material of the first adhesive layer 22, such light transmittance can be realized.
Such a light transmittance can be realized more reliably by adopting a configuration in which the first adhesive layer 22 does not substantially contain an ultraviolet absorber.
Note that the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is preferably 75% or more, and more preferably 80% or more. By doing so, it becomes possible to more effectively contribute light energy derived from ultraviolet rays to power generation.
　第１接着層２２の層厚Ｔ（図３）は、例えば、８μｍ以上１００μｍ以下とすることができ、好ましくは、１６μｍ以上７５μｍ以下とすることができる。後述するように、第１微細配線２１が直径Ｄのワイヤである場合、第１接着層２２の層厚Ｔは、Ｄ／６±Ｄ／１２の範囲に設定されていることが好ましい。すなわち、一例として、第１微細配線２１が直径３００μｍのワイヤである場合、層厚Ｔは２５μｍ以上７５μｍ以下とすることができる。ここで、第１接着層２２の層厚Ｔは、隣り合うワイヤどうしの間隔において、第１接着層２２の層厚がほぼ一定となっている範囲における層厚であるものとする（図３参照）。 The layer thickness T (FIG. 3) of the first adhesive layer 22 can be, for example, 8 μm or more and 100 μm or less, and preferably 16 μm or more and 75 μm or less. As will be described later, when the first fine wiring 21 is a wire having a diameter D, the layer thickness T of the first adhesive layer 22 is preferably set in a range of D / 6 ± D / 12. That is, as an example, when the first fine wiring 21 is a wire having a diameter of 300 μm, the layer thickness T can be set to 25 μm or more and 75 μm or less. Here, the layer thickness T of the first adhesive layer 22 is a layer thickness in a range where the layer thickness of the first adhesive layer 22 is substantially constant in the interval between adjacent wires (see FIG. 3). ).
　第１樹脂フィルム２３は、例えば、フッ素樹脂およびアクリル樹脂からなる群より選択される１以上を含む材料により形成されている。
　上記フッ素樹脂としては、テトラフルオロエチレン・エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、クロロトリフルオロエチレン・エチレン共重合体（ＰＣＴＦＥＥ）、ポリフッ化ビニル（ＰＶＦ）及びポリフッ化ビニリデン（ＰＶＤＦ）等が挙げられる。中でも、テトラフルオロエチレン・エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）およびポリフッ化ビニル（ＰＶＦ）からなる群より選択される１種以上であることが好ましい。
　上記アクリル樹脂としては、アクリル酸エステルの重合体、メタクリル酸エステルの重合体等が挙げられる。中でも、メタクリル酸メチル単位を主成分とした重合体であるメタクリル樹脂が好ましい。このメタクリル樹脂としては、ポリメタクリル酸メチル（ＰＭＭＡ）、メタクリル酸メチルと他の単量体との共重合体等が挙げられる。
　第１樹脂フィルム２３の厚さは、例えば、５μｍ以上１００μｍ以下（好ましくは１０μｍ以上８０μｍ以下）とすることができる。 The 1st resin film 23 is formed with the material containing 1 or more selected from the group which consists of a fluororesin and an acrylic resin, for example.
Examples of the fluororesin include tetrafluoroethylene / ethylene copolymer (ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polychlorotriethylene. Examples include fluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (PCTFEE), polyvinyl fluoride (PVF), and polyvinylidene fluoride (PVDF). Among these, at least one selected from the group consisting of tetrafluoroethylene / ethylene copolymer (ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), and polyvinyl fluoride (PVF) is preferable.
Examples of the acrylic resin include acrylic acid ester polymers and methacrylic acid ester polymers. Among these, a methacrylic resin that is a polymer mainly composed of methyl methacrylate units is preferable. Examples of the methacrylic resin include polymethyl methacrylate (PMMA), a copolymer of methyl methacrylate and another monomer, and the like.
The thickness of the 1st resin film 23 can be 5 micrometers or more and 100 micrometers or less (preferably 10 micrometers or more and 80 micrometers or less), for example.
　第１封止層３０は、透光性である。
　第１封止層３０の材料は、第１接着層２２と同様であってもよいし、ＴＰＯ（オレフィン系エラストマー）であってもよいし、シリコン樹脂であってもよい。
　第１封止層３０の層厚は、例えば、３００μｍ以上５００μｍ以下とすることができる。
　ここで、第１封止層３０の厚みは、接着層２２からの第１微細配線２１の突出長（第１保護層４０側への突出長）よりも厚く設定されている。
　ここで、第１保護層４０における第１封止層３０側の面には、エンボス加工が施されている場合がある。その場合、第１封止層３０により第１保護層４０におけるエンボスの凹凸を埋めることが好ましい。このため、第１封止層３０の厚みは、接着層２２からの第１微細配線２１の突出長に、エンボスの凹凸の高さを加えた厚さを少なくとも有することが好ましい。 The first sealing layer 30 is translucent.
The material of the first sealing layer 30 may be the same as that of the first adhesive layer 22, TPO (olefin elastomer), or silicon resin.
The layer thickness of the 1st sealing layer 30 can be 300 micrometers or more and 500 micrometers or less, for example.
Here, the thickness of the first sealing layer 30 is set to be thicker than the protruding length of the first fine wiring 21 from the adhesive layer 22 (the protruding length to the first protective layer 40 side).
Here, the surface of the first protective layer 40 on the first sealing layer 30 side may be embossed. In that case, it is preferable to fill the unevenness of the embossment in the first protective layer 40 with the first sealing layer 30. For this reason, it is preferable that the thickness of the first sealing layer 30 has at least a thickness obtained by adding the height of the unevenness of the emboss to the protruding length of the first fine wiring 21 from the adhesive layer 22.
　第１保護層４０は、透光性の基板である。第１保護層４０の材料としては、例えば、ガラス、アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂等が挙げられる。 The first protective layer 40 is a translucent substrate. Examples of the material of the first protective layer 40 include glass, acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
　第２保護層７０は、第１保護層４０と同様の透光性の基板であってもよいし、非透光性（例えば光反射性）のバックシートであってもよい。バックシートとしては、たとえば、錫、アルミ、ステンレススチール等の金属や、ガラス等の無機材料、ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィン等の熱可塑性樹脂により形成された１層もしくは多層のシートが挙げられる。 The second protective layer 70 may be a translucent substrate similar to the first protective layer 40, or may be a non-translucent (eg, light reflective) backsheet. As the back sheet, for example, a single-layer or multi-layer sheet formed of a metal such as tin, aluminum, and stainless steel, an inorganic material such as glass, a polyester, an inorganic vapor-deposited polyester, a fluorine-containing resin, and a thermoplastic resin such as polyolefin. Is mentioned.
　第２保護層７０が透光性の基板である場合、光発電モジュール１００は、両面（第１保護層４０側及び第２保護層７０側）での受光が可能となる。この場合、第２接着層５２は、第１接着層２２と同様の材料のものとすることができる。また、第２樹脂フィルム５３は、第１樹脂フィルム２３と同様の材料のものとすることができる。
　また、第２封止層６０は、第１封止層３０と同様の材料のものとすることができる。ただし、両面での受光が不要の場合には、後述のように、第２封止層６０に顔料等を含有させる場合がある。 When the second protective layer 70 is a translucent substrate, the photovoltaic module 100 can receive light on both sides (the first protective layer 40 side and the second protective layer 70 side). In this case, the second adhesive layer 52 can be made of the same material as the first adhesive layer 22. The second resin film 53 can be made of the same material as the first resin film 23.
The second sealing layer 60 can be made of the same material as the first sealing layer 30. However, when light reception on both sides is not necessary, the second sealing layer 60 may contain a pigment or the like as described later.
　第２保護層７０が非透光性のバックシートである場合、光発電モジュール１００の受光面は片面（第１保護層４０側）となる。この場合、第２接着層５２の材料は、第１接着層２２と同様の樹脂材料とすることができる。
　また、第２保護層７０が非透光性のバックシートである場合の第２封止層６０の材料は、第１封止層３０と同様であってもよいが、この場合の第２封止層６０には透明性は要求されないため、発電効率を向上させる観点から、顔料、染料、無機充填剤を配合することが好ましい。上記顔料としては、酸化チタンや炭酸カルシウム等の白色顔料、ウルトラマリン等の青色顔料、カーボンブラックのような黒色顔料等が挙げられる。特に、酸化チタンのような無機顔料を配合することは、光発電モジュール１００の絶縁抵抗が低下することを防止する観点から好ましい。上記無機顔料の配合量は、第２封止層６０に含まれる樹脂成分１００重量部に対して、好ましくは、０重量部以上１００重量部以下であり、さらに好ましくは、０．５重量部以上５０重量部以下であり、最も好ましくは、４重量部以上５０重量部以下である。
　第２保護層７０が非透光性のバックシートである場合の第２樹脂フィルム５３の材料は、第１樹脂フィルム２３と同様であってもよいし、その他の樹脂材料であってもよい。 In the case where the second protective layer 70 is a non-translucent back sheet, the light receiving surface of the photovoltaic module 100 is one side (the first protective layer 40 side). In this case, the material of the second adhesive layer 52 can be the same resin material as that of the first adhesive layer 22.
Further, the material of the second sealing layer 60 when the second protective layer 70 is a non-translucent backsheet may be the same as that of the first sealing layer 30, but in this case, the second sealing layer 60 Since the stop layer 60 is not required to be transparent, it is preferable to blend a pigment, a dye, and an inorganic filler from the viewpoint of improving the power generation efficiency. Examples of the pigment include white pigments such as titanium oxide and calcium carbonate, blue pigments such as ultramarine, and black pigments such as carbon black. In particular, blending an inorganic pigment such as titanium oxide is preferable from the viewpoint of preventing the insulation resistance of the photovoltaic module 100 from being lowered. The blending amount of the inorganic pigment is preferably 0 parts by weight or more and 100 parts by weight or less, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the resin component contained in the second sealing layer 60. 50 parts by weight or less, and most preferably 4 parts by weight or more and 50 parts by weight or less.
The material of the second resin film 53 when the second protective layer 70 is a non-translucent back sheet may be the same as that of the first resin film 23 or may be other resin materials.
　なお、第２接着層５２は、第１接着層２２と同様の厚さにすることができる。
　すなわち、第２微細配線５１が直径Ｄのワイヤである場合、第２接着層５２の層厚Ｔは、Ｄ／６±Ｄ／１２の範囲に設定されていることが好ましい。すなわち、一例として、第２微細配線５１が直径３００μｍのワイヤである場合、層厚Ｔは２５μｍ以上７５μｍ以下とすることができる。
　また、第２樹脂フィルム５３は、第１樹脂フィルム２３と同様の厚さにすることができる。 The second adhesive layer 52 can have the same thickness as the first adhesive layer 22.
That is, when the second fine wiring 51 is a wire having a diameter D, the layer thickness T of the second adhesive layer 52 is preferably set in a range of D / 6 ± D / 12. That is, as an example, when the second fine wiring 51 is a wire having a diameter of 300 μm, the layer thickness T can be set to 25 μm or more and 75 μm or less.
The second resin film 53 can have the same thickness as the first resin film 23.
　なお、第２保護層７０は、ガラス基板等の硬質の基板であってもよいし、可撓性の樹脂シートであってもよい。
　第２保護層７０がガラス基板等の硬質の基板である場合、第２接着層５２は、第１接着層２２と同様の厚さにすることができる。
　一方、第２保護層７０が可撓性の樹脂シートである場合は、仮に第２封止層６０の裏面側（図１における下側）に第２微細配線５１が突出していたとしても、第２微細配線５１の突出部分に沿って第２保護層７０が変形できる（第２保護層７０の表面が、第２微細配線５１の突出部分を反映した形状となる）。よって、第２保護層７０は、第２封止層６０及び第２微細配線５１に対して密着した状態で、光発電モジュール１００の裏面を好適に保護することができる。このため、第２保護層７０が可撓性の樹脂シートである場合は、第２封止層６０は第１封止層３０よりも薄くすることができる。なお、第２保護層７０が可撓性の樹脂シートである場合においても、第２封止層６０の厚さを第１封止層３０の厚さと同等としてもよいのは勿論である。 The second protective layer 70 may be a hard substrate such as a glass substrate, or may be a flexible resin sheet.
When the second protective layer 70 is a hard substrate such as a glass substrate, the second adhesive layer 52 can have the same thickness as the first adhesive layer 22.
On the other hand, when the second protective layer 70 is a flexible resin sheet, even if the second fine wiring 51 protrudes on the back surface side (the lower side in FIG. 1) of the second sealing layer 60, The second protective layer 70 can be deformed along the protruding portion of the second fine wiring 51 (the surface of the second protective layer 70 has a shape reflecting the protruding portion of the second fine wiring 51). Therefore, the second protective layer 70 can suitably protect the back surface of the photovoltaic module 100 while being in close contact with the second sealing layer 60 and the second fine wiring 51. For this reason, when the second protective layer 70 is a flexible resin sheet, the second sealing layer 60 can be made thinner than the first sealing layer 30. Even when the second protective layer 70 is a flexible resin sheet, it is needless to say that the thickness of the second sealing layer 60 may be equal to the thickness of the first sealing layer 30.
　なお、光発電モジュール１００は、通常、複数を直列に接続して用いられる。複数の光発電モジュール１００を直列接続して使用することにより、発電電圧を高めることができる。 In addition, the photovoltaic module 100 is normally used by connecting a plurality in series. By using a plurality of photovoltaic modules 100 connected in series, the generated voltage can be increased.
　次に、光発電モジュール１００を製造する方法の一例を説明する。 Next, an example of a method for manufacturing the photovoltaic module 100 will be described.
　先ず、光発電素子１０は、結晶半導体基板１１の一方の面上に、第１非晶質系半導体膜１２、第２非晶質系半導体膜１３及び第１透光性電極膜１４をこの順に成膜する一方で、結晶半導体基板１１の他方の面上に、第３非晶質系半導体膜１６、第４非晶質系半導体膜１７及び第２透光性電極膜１８をこの順に成膜し、更に、第１透光性電極膜１４の一方の面（図１における上面）上に第１電極１５を、第２透光性電極膜１８の一方の面（図１における下面）上に第２電極１９を、それぞれ形成することにより得られる。 First, in the photovoltaic device 10, the first amorphous semiconductor film 12, the second amorphous semiconductor film 13, and the first light-transmissive electrode film 14 are arranged in this order on one surface of the crystalline semiconductor substrate 11. On the other hand, the third amorphous semiconductor film 16, the fourth amorphous semiconductor film 17, and the second translucent electrode film 18 are formed in this order on the other surface of the crystalline semiconductor substrate 11. Further, the first electrode 15 is formed on one surface (the upper surface in FIG. 1) of the first light-transmissive electrode film 14, and the first surface (the lower surface in FIG. 1) of the second light-transmissive electrode film 18. It is obtained by forming the second electrodes 19 respectively.
　次に、例えば、第１樹脂フィルム２３、第１接着層２２及び第１微細配線２１が一体化した第１配線シート（図４、図５に示される配線シート２００を参照）と、第１保護層４０と、シート状の第１封止層３０を準備する。 Next, for example, a first wiring sheet (see the wiring sheet 200 shown in FIGS. 4 and 5) in which the first resin film 23, the first adhesive layer 22, and the first fine wiring 21 are integrated, and the first protection. A layer 40 and a sheet-like first sealing layer 30 are prepared.
　ここで、配線シート２００について説明する。
　配線シート２００は、相互に積層された樹脂フィルム（第１樹脂フィルム２３又は第２樹脂フィルム５３）及び接着層（第１接着層２２又は第２接着層５２）と、接着層における樹脂フィルム側とは反対側の面に設けられた微細配線（第１微細配線２１又は第２微細配線５１）と、を有する。
　図４に示すように、各微細配線の一部分は、接着層に埋設されていることが好ましく、このようにすることにより、接着層と微細配線との一体性を良好なものとすることができる。
　また、図５に示すように、微細配線は、互いに平行に配置されている複数のワイヤであることが好ましく、このようにすることにより、微細配線を形成するために使用する金属材料の量を低減させることができる。
　樹脂フィルムは、フッ素樹脂およびアクリル樹脂からなる群より選択される１以上を含む材料により形成されている。樹脂フィルムの厚みは、５μｍ以上１００μｍ以下であることが好ましく、１０μｍ以上８０μｍ以下であるとさらに好ましい。光発電モジュール１００の受光面が片面である場合、受光面側に配置する第１樹脂フィルム２３は、ＪＩＳ－Ｋ７１０５に準じて測定した３５０ｎｍの波長における光線透過率が７０％以上であることが好ましい。こうすることで、紫外線由来の光エネルギーも効率よく発電に寄与させることのできるモジュールを実現することができる。また、光発電モジュール１００の受光面が両面である場合、第２樹脂フィルム５３は、ＪＩＳ－Ｋ７１０５に準じて測定した３５０ｎｍの波長における光線透過率が７０％以上であることが好ましい。こうすることで、紫外線由来の光エネルギーも効率よく発電に寄与させることのできるモジュールを実現することができる。 Here, the wiring sheet 200 will be described.
The wiring sheet 200 includes a resin film (the first resin film 23 or the second resin film 53) and an adhesive layer (the first adhesive layer 22 or the second adhesive layer 52) laminated on each other, and the resin film side in the adhesive layer. Has fine wiring (first fine wiring 21 or second fine wiring 51) provided on the opposite surface.
As shown in FIG. 4, it is preferable that a part of each fine wiring is embedded in the adhesive layer, and by doing so, the integrity of the adhesive layer and the fine wiring can be improved. .
In addition, as shown in FIG. 5, the fine wiring is preferably a plurality of wires arranged in parallel to each other, and in this way, the amount of the metal material used for forming the fine wiring is reduced. Can be reduced.
The resin film is formed of a material including one or more selected from the group consisting of a fluororesin and an acrylic resin. The thickness of the resin film is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 80 μm or less. When the light receiving surface of the photovoltaic module 100 is a single side, the first resin film 23 disposed on the light receiving surface side preferably has a light transmittance of 70% or more at a wavelength of 350 nm measured according to JIS-K7105. . By doing so, it is possible to realize a module capable of efficiently contributing to the power generation by light energy derived from ultraviolet rays. When the light receiving surface of the photovoltaic module 100 is double-sided, the second resin film 53 preferably has a light transmittance at a wavelength of 350 nm measured in accordance with JIS-K7105 of 70% or more. By doing so, it is possible to realize a module capable of efficiently contributing to the power generation by light energy derived from ultraviolet rays.
　次に、第１配線シートを光発電素子１０の一方の面の第１電極１５と第１保護層４０との間に介在させ、且つ、第１配線シートと第１保護層４０との間に第１封止層３０を介在させる。
　同様に、第２樹脂フィルム５３、第２接着層５２及び第２微細配線５１が一体化した第２配線シート（図４、図５に示される配線シート２００を参照）と、第２保護層７０と、シート状の第２封止層６０とを準備する。
　そして、第２配線シートを光発電素子１０の他方の面の第２電極１９と第２保護層７０との間に介在させ、且つ、第２配線シートと第２保護層７０との間に第２封止層６０を介在させる。
　そして、これらを一括して加熱及び両面から加圧することにより、第１接着層２２を介して第１微細配線２１を第１電極１５に対して溶着するとともに、第１封止層３０を介して第１樹脂フィルム２３と第１保護層４０とを溶着し、第２接着層５２を介して第２微細配線５１を第２電極１９に対して溶着するとともに、第２封止層６０を介して第２樹脂フィルム５３と第２保護層７０とを溶着する。
　このとき、第１微細配線２１の表層の低融点金属膜２１ｂが溶融することにより、コア２１ａと第１電極１５とが溶着する。
　同様に、第２微細配線５１の表層の低融点金属膜（不図示）が溶融することにより、第２微細配線５１のコア（不図示）と第２電極１９とが溶着する。
　こうして、光発電モジュール１００を得ることができる。 Next, the first wiring sheet is interposed between the first electrode 15 on one side of the photovoltaic element 10 and the first protective layer 40, and between the first wiring sheet and the first protective layer 40. The first sealing layer 30 is interposed.
Similarly, a second wiring sheet (see the wiring sheet 200 shown in FIGS. 4 and 5) in which the second resin film 53, the second adhesive layer 52, and the second fine wiring 51 are integrated, and the second protective layer 70. And a sheet-like second sealing layer 60 are prepared.
Then, the second wiring sheet is interposed between the second electrode 19 on the other surface of the photovoltaic element 10 and the second protective layer 70, and the second wiring sheet is interposed between the second wiring sheet and the second protective layer 70. Two sealing layers 60 are interposed.
Then, these are collectively heated and pressurized from both sides, whereby the first fine wiring 21 is welded to the first electrode 15 via the first adhesive layer 22 and the first sealing layer 30 is interposed. The first resin film 23 and the first protective layer 40 are welded, the second fine wiring 51 is welded to the second electrode 19 through the second adhesive layer 52, and the second sealing layer 60 is used. The second resin film 53 and the second protective layer 70 are welded.
At this time, the core 21 a and the first electrode 15 are welded by melting the low melting point metal film 21 b on the surface layer of the first fine wiring 21.
Similarly, the low melting point metal film (not shown) on the surface layer of the second fine wiring 51 is melted, so that the core (not shown) of the second fine wiring 51 and the second electrode 19 are welded.
Thus, the photovoltaic module 100 can be obtained.
　ここでは、第１配線シート及び第２配線シートとして、図４に示される構造の配線シート２００を用いる例を説明したが、第１配線シート及び第２配線シートとしては、図６に示される構造の配線シート２００を用いてもよい。この場合、配線シート２００（第１配線シート、第２配線シート）とは別に、樹脂フィルム（第１樹脂フィルム２３、第２樹脂フィルム５３）を準備する。 Here, the example in which the wiring sheet 200 having the structure shown in FIG. 4 is used as the first wiring sheet and the second wiring sheet has been described, but the structure shown in FIG. 6 is used as the first wiring sheet and the second wiring sheet. The wiring sheet 200 may be used. In this case, a resin film (first resin film 23, second resin film 53) is prepared separately from the wiring sheet 200 (first wiring sheet, second wiring sheet).
　ここで、本発明者の検討によれば、複数の第１微細配線２１が、互いに平行に配置された複数のワイヤである場合に、このワイヤの外径をＤ（図３）とすると、第１接着層２２の層厚Ｔ（図３）は、Ｄ／６±Ｄ／１２の範囲に設定されていることが好ましい。例えば、ワイヤの外径Ｄが３００μｍの場合、層厚Ｔは５０μｍ±２５μｍの範囲が好ましい。
　このようにすることにより、図３に示すように、第１電極１５からの第１微細配線２１の浮き上がりを抑制し、より確実に第１電極１５に対して第１微細配線２１を溶着させることができるとともに、第１接着層２２により第１樹脂フィルム２３を第１電極１５に対して十分な接着強度で接着することができる。また、第１接着層２２の層厚Ｔを、Ｄ／６－Ｄ／１２以上に設定することにより、第１微細配線２１の周辺にボイド（空洞）が形成されることによる信頼性の低下を抑制することができる。 Here, according to the study of the present inventor, when the plurality of first fine wirings 21 are a plurality of wires arranged in parallel to each other, when the outer diameter of the wires is D (FIG. 3), the first The layer thickness T (FIG. 3) of the one adhesive layer 22 is preferably set in a range of D / 6 ± D / 12. For example, when the outer diameter D of the wire is 300 μm, the layer thickness T is preferably in the range of 50 μm ± 25 μm.
By doing so, as shown in FIG. 3, the first fine wiring 21 can be more securely welded to the first electrode 15 by suppressing the floating of the first fine wiring 21 from the first electrode 15. In addition, the first resin film 23 can be bonded to the first electrode 15 with sufficient adhesive strength by the first adhesive layer 22. In addition, by setting the layer thickness T of the first adhesive layer 22 to D / 6−D / 12 or more, reliability is reduced due to the formation of voids (cavities) around the first fine wiring 21. Can be suppressed.
　同様に、複数の第２微細配線５１が、互いに平行に配置された複数のワイヤである場合に、このワイヤの外径をＤとすると、第２接着層５２の層厚Ｔは、Ｄ／６±Ｄ／１２の範囲に設定されていることが好ましい。
　このようにすることにより、第２電極１９からの第２微細配線５１の浮き上がりを抑制し、より確実に第２電極１９に対して第２微細配線５１を溶着させることができるとともに、第２樹脂フィルム５３を第２接着層５２により十分な接着強度で第２電極１９に対して接着することができる。また、第２接着層５２の層厚Ｔを、Ｄ／６－Ｄ／１２以上に設定することにより、第２微細配線５１の周辺にボイドが形成されることによる信頼性の低下を抑制することができる。 Similarly, when the plurality of second fine wirings 51 are a plurality of wires arranged in parallel to each other and the outer diameter of the wires is D, the layer thickness T of the second adhesive layer 52 is D / 6. It is preferable to be set within a range of ± D / 12.
By doing so, it is possible to suppress the floating of the second fine wiring 51 from the second electrode 19, and more reliably weld the second fine wiring 51 to the second electrode 19, and the second resin. The film 53 can be adhered to the second electrode 19 with sufficient adhesive strength by the second adhesive layer 52. Further, by setting the layer thickness T of the second adhesive layer 52 to be equal to or greater than D / 6-D / 12, it is possible to suppress a decrease in reliability due to the formation of voids around the second fine wiring 51. Can do.
　以上のような実施形態に係る光発電モジュール１００によれば、ヘテロ接合型の光発電素子１０を備え、且つ、第１接着層２２が、（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマーおよび（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体のいずれかを含む樹脂材料により構成されている。ここで、上記の（Ａ）および（Ｂ）は、水分透過率が低いという特性を有している。このため、第１保護層４０として、水分透過率が比較的高い材料を選択した場合であっても、第１接着層２２によって第２非晶質系半導体膜１３及び第１非晶質系半導体膜１２を水分から保護することができる。よって、例えば、第１保護層４０に含まれるナトリウム成分が水分とともに第２非晶質系半導体膜１３及び第１非晶質系半導体膜１２側に泳動することも抑制することができる。
　このため、第１封止層３０の材料の選択の自由度が高くなる。
　また、（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマーおよび（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体は、紫外線に対する耐性も良好である。よって、第１封止層３０が紫外線吸収剤を実質的に含んでいなくても、第１接着層２２の良好な耐性を確保できる。このため、紫外光を発電に有効に利用することができるので、より良好な発電効率を得ることができる。 According to the photovoltaic module 100 according to the embodiment as described above, the copolymer including the heterojunction photovoltaic element 10 and the first adhesive layer 22 includes (A) ethylene and an unsaturated carboxylic acid. Or an ionomer of the above copolymer and (B) a resin material containing either a copolymer containing ethylene and glycidyl (meth) acrylate. Here, said (A) and (B) have the characteristic that a moisture permeability is low. For this reason, even if a material having a relatively high moisture permeability is selected as the first protective layer 40, the second amorphous semiconductor film 13 and the first amorphous semiconductor are formed by the first adhesive layer 22. The membrane 12 can be protected from moisture. Therefore, for example, the sodium component contained in the first protective layer 40 can also be prevented from migrating to the second amorphous semiconductor film 13 and the first amorphous semiconductor film 12 side together with moisture.
For this reason, the freedom degree of selection of the material of the 1st sealing layer 30 becomes high.
Further, (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the above copolymer and (B) a copolymer containing ethylene and glycidyl (meth) acrylate have good resistance to ultraviolet rays. . Therefore, even when the first sealing layer 30 does not substantially contain the ultraviolet absorber, it is possible to ensure good resistance of the first adhesive layer 22. For this reason, since ultraviolet light can be used effectively for power generation, better power generation efficiency can be obtained.
　特に、第１接着層２２を構成する樹脂材料（エチレンと不飽和カルボン酸との共重合体を含む樹脂材料）における共重合体がアイオノマーである場合、第１接着層２２の良好な透明性、紫外線耐性及び水分の低い透過率を実現できるため、上述した効果をより確実に得ることができる。 In particular, when the copolymer in the resin material (resin material containing a copolymer of ethylene and unsaturated carboxylic acid) constituting the first adhesive layer 22 is an ionomer, good transparency of the first adhesive layer 22; Since the ultraviolet resistance and the low transmittance of moisture can be realized, the above-described effects can be obtained more reliably.
　また、ＪＩＳ－Ｋ７１０５に準じて測定した第１接着層２２の３５０ｎｍの波長における光線透過率を、７０％以上とすることにより、紫外線由来の光エネルギーを効率よく発電に寄与させることが可能となるので、光発電モジュール１００の良好な発電効率を得ることができる。この光線透過率は、７５％以上であることがより好ましく、８０％以上であることがより好ましい。
　第１封止層３０の光線透過率についても、ＪＩＳ－Ｋ７１０５に準じて測定した第１封止層３０の３５０ｎｍの波長における光線透過率を、７０％以上とすることができ、その場合、特に良好な発電効率を得ることができる。この光線透過率も、７５％以上であることがより好ましく、８０％以上であることがより好ましい。 In addition, when the light transmittance at a wavelength of 350 nm of the first adhesive layer 22 measured according to JIS-K7105 is set to 70% or more, light energy derived from ultraviolet rays can be efficiently contributed to power generation. Therefore, good power generation efficiency of the photovoltaic module 100 can be obtained. The light transmittance is more preferably 75% or more, and more preferably 80% or more.
Regarding the light transmittance of the first sealing layer 30, the light transmittance at a wavelength of 350 nm of the first sealing layer 30 measured according to JIS-K7105 can be set to 70% or more. Good power generation efficiency can be obtained. This light transmittance is also preferably 75% or more, and more preferably 80% or more.
　また、複数の第１微細配線２１が、互いに平行に配置された複数のワイヤである場合において、ワイヤの外径をＤとすると、第１接着層２２の層厚Ｔは、Ｄ／６±Ｄ／１２の範囲に設定することができる。このようにすることにより、図３に示すように、第１電極１５からの第１微細配線２１の浮き上がりを抑制し、より確実に第１電極１５に対して第１微細配線２１を溶着させることができるとともに、第１接着層２２により第１樹脂フィルム２３を第１電極１５に対して十分な接着強度で接着することができる。 Further, when the plurality of first fine wirings 21 are a plurality of wires arranged in parallel to each other, and the outer diameter of the wires is D, the layer thickness T of the first adhesive layer 22 is D / 6 ± D. / 12 can be set. By doing so, as shown in FIG. 3, the first fine wiring 21 can be more securely welded to the first electrode 15 by suppressing the floating of the first fine wiring 21 from the first electrode 15. In addition, the first resin film 23 can be bonded to the first electrode 15 with sufficient adhesive strength by the first adhesive layer 22.
　また、第２保護層７０が透光性である場合において、第２接着層５２を、第１接着層２２と同様に、（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマーおよび（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体のいずれかを含む樹脂材料により構成することができる。このようにすることにより、第２接着層５２によって第１接着層２２と同様の効果が得られる。
　すなわち、第２保護層７０として、水分透過率が比較的高い材料を選択した場合であっても、第２接着層５２によって第４非晶質系半導体膜１７及び第３非晶質系半導体膜１６を水分から保護することができる。よって、例えば、第２保護層７０に含まれるナトリウム成分が水分とともに第４非晶質系半導体膜１７、及び第３非晶質系半導体膜１６側に泳動することも抑制することができる。
　このため、第２保護層７０の材料の選択の自由度が高くなる。
　また、（Ａ）エチレンと不飽和カルボン酸を含む共重合体、または上記共重合体のアイオノマーおよび（Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体は、紫外線に対する耐性も良好である。よって、第２保護層７０が紫外線吸収剤を実質的に含んでいなくても、第２接着層５２の良好な耐性を確保できる。このため、紫外光を発電に有効に利用することができるので、より良好な発電効率を得ることができる。
　特に、第２接着層５２を構成する樹脂材料（エチレンと不飽和カルボン酸との共重合体を含む樹脂材料）における共重合体がアイオノマーである場合、第２接着層５２の良好な透明性、紫外線耐性、水分の低い透過率を実現できるため、上述した効果をより確実に得ることができる。 In the case where the second protective layer 70 is translucent, the second adhesive layer 52 is made of (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or the above copolymer, as with the first adhesive layer 22. It can be constituted by a resin material containing either a polymer ionomer or a copolymer containing (B) ethylene and glycidyl (meth) acrylate. By doing so, the same effect as that of the first adhesive layer 22 is obtained by the second adhesive layer 52.
That is, even if a material having a relatively high moisture permeability is selected as the second protective layer 70, the fourth amorphous semiconductor film 17 and the third amorphous semiconductor film are formed by the second adhesive layer 52. 16 can be protected from moisture. Therefore, for example, migration of the sodium component contained in the second protective layer 70 to the fourth amorphous semiconductor film 17 and the third amorphous semiconductor film 16 side together with moisture can be suppressed.
For this reason, the freedom degree of selection of the material of the 2nd protective layer 70 becomes high.
Further, (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the above copolymer and (B) a copolymer containing ethylene and glycidyl (meth) acrylate have good resistance to ultraviolet rays. . Therefore, even if the second protective layer 70 does not substantially contain the ultraviolet absorber, it is possible to ensure good resistance of the second adhesive layer 52. For this reason, since ultraviolet light can be used effectively for power generation, better power generation efficiency can be obtained.
In particular, when the copolymer in the resin material (resin material containing a copolymer of ethylene and unsaturated carboxylic acid) constituting the second adhesive layer 52 is an ionomer, good transparency of the second adhesive layer 52, Since the ultraviolet light resistance and the low moisture transmittance can be realized, the above-described effects can be obtained more reliably.
　また、第２接着層５２についてＪＩＳ－Ｋ７１０５に準じて測定した第２接着層５２の３５０ｎｍの波長における光線透過率を、７０％以上とすることにより、紫外線由来の光エネルギーを効率よく発電に寄与させることが可能となるので、光発電モジュール１００の良好な発電効率を得ることができる。この光線透過率も、７５％以上であることがより好ましく、８０％以上であることがより好ましい。
　第２保護層７０の光線透過率についても、ＪＩＳ－Ｋ７１０５に準じて測定した第２保護層７０の３５０ｎｍの波長における光線透過率を、７０％以上とすることができ、その場合、特に良好な発電効率を得ることができる。この光線透過率も、７５％以上であることがより好ましく、８０％以上であることがより好ましい。 Further, by making the light transmittance at a wavelength of 350 nm of the second adhesive layer 52 measured in accordance with JIS-K7105 for the second adhesive layer 52 to be 70% or more, light energy derived from ultraviolet rays contributes to power generation efficiently. Therefore, good power generation efficiency of the photovoltaic module 100 can be obtained. This light transmittance is also preferably 75% or more, and more preferably 80% or more.
Regarding the light transmittance of the second protective layer 70, the light transmittance at a wavelength of 350 nm of the second protective layer 70 measured according to JIS-K7105 can be set to 70% or more. Power generation efficiency can be obtained. This light transmittance is also preferably 75% or more, and more preferably 80% or more.
　なお、光発電素子１０の各構成要素の導電型は、上述の例とは反転していてもよい。 In addition, the conductivity type of each component of the photovoltaic device 10 may be reversed from the above example.
　以下、本発明を実施例および比較例により説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.
（実施例１）
　実施例１に係る光発電モジュールを、以下の方法で作製した。
　透光性基板（第１保護層）、第１封止層（後述する樹脂シート１を使用）、第１配線シート（後述する配線シート１を使用）、光発電素子の順に重ねた。更に、光発電素子の上に、第２配線シート（後述する配線シート１を使用）、第２封止層（後述する樹脂シート３を使用）、バックシート（第２保護層）をこの順で重ね、これらを真空ラミネータを用いてラミネートし、光発電モジュールを作製した。 (Example 1)
The photovoltaic module according to Example 1 was manufactured by the following method.
A light-transmitting substrate (first protective layer), a first sealing layer (using a resin sheet 1 described later), a first wiring sheet (using a wiring sheet 1 described later), and a photovoltaic element were stacked in this order. Furthermore, on the photovoltaic element, a second wiring sheet (using a wiring sheet 1 described later), a second sealing layer (using a resin sheet 3 described later), and a back sheet (second protective layer) in this order. These were stacked and laminated using a vacuum laminator to produce a photovoltaic module.
（比較例１）
　比較例１に係る光発電モジュールは、第１封止層および第２封止層としてそれぞれ後述する樹脂シート４を使用し、第１配線シート及び第２配線シートとしてそれぞれ後述する配線シート２を使用した以外は、実施例１に係る光発電モジュールと同様に作製した。 (Comparative Example 1)
The photovoltaic module according to Comparative Example 1 uses the resin sheet 4 described later as the first sealing layer and the second sealing layer, and uses the wiring sheet 2 described later as the first wiring sheet and the second wiring sheet, respectively. Except that, the photovoltaic power generation module according to Example 1 was produced.
（実施例２～５）
　第１配線シート及び第２配線シートとしてそれぞれ後述する配線シート３～６を使用した以外は、実施例１に係る光発電モジュールと同様にそれぞれ作製した。 (Examples 2 to 5)
Each was produced in the same manner as the photovoltaic module according to Example 1, except that wiring sheets 3 to 6 described later were used as the first wiring sheet and the second wiring sheet, respectively.
　＜配線シート１＞
　厚さ２５μｍのテトラフルオロエチレン・エチレン共重合体（ＥＴＦＥ）により形成された基材シート（第１樹脂フィルム又は第２樹脂フィルムに相当）と、当該基材シートの一方の面に形成された厚さ７５μｍの樹脂シート２（後述：第１接着層又は第２接着層に相当）と、を有するシートにおける樹脂シート２側の表面に対して、直径３００μｍの金属微細配線を等間隔に並べて加熱圧着することにより、配線シート１を作製した。得られた配線シート１は、樹脂シート２にワイヤが埋設されていた。 <Wiring sheet 1>
A base sheet (corresponding to a first resin film or a second resin film) formed of tetrafluoroethylene / ethylene copolymer (ETFE) having a thickness of 25 μm, and a thickness formed on one surface of the base sheet A metal micro-wiring with a diameter of 300 μm is arranged at equal intervals on the surface of the sheet having a thickness of 75 μm resin sheet 2 (which will be described later: corresponding to the first adhesive layer or the second adhesive layer) and thermocompression-bonded. By doing this, the wiring sheet 1 was produced. In the obtained wiring sheet 1, wires were embedded in the resin sheet 2.
　＜配線シート２＞
　厚さ１００μｍの樹脂シート４（後述）の表面に対して、直径３００μｍの金属微細配線を等間隔に並べて加熱圧着することにより、配線シート２を作製した。得られた配線シート２は、樹脂シート４にワイヤが埋設されていた。 <Wiring sheet 2>
The wiring sheet 2 was produced by heat-pressing the metal fine wiring with a diameter of 300 micrometers on the surface of the resin sheet 4 (after-mentioned) with a thickness of 100 micrometers, arranging it at equal intervals. In the obtained wiring sheet 2, wires were embedded in the resin sheet 4.
　＜配線シート３＞
　樹脂シート２に代えて、厚さ５０μｍのポリメタクリル酸メチル（ＰＭＭＡ）により形成されたシートの片面に対して、厚さ６０μｍの樹脂シート５を接着して得られたシートを使用したという点以外は、実施例１と同様の方法で、配線シート３を作製した。得られた配線シート３は、樹脂シート５にワイヤが埋設されていた。 <Wiring sheet 3>
Instead of using the sheet obtained by bonding the resin sheet 5 having a thickness of 60 μm to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 μm instead of the resin sheet 2 Produced a wiring sheet 3 in the same manner as in Example 1. In the obtained wiring sheet 3, a wire was embedded in the resin sheet 5.
＜配線シート４＞
　樹脂シート２に代えて、厚さ５０μｍのポリメタクリル酸メチル（ＰＭＭＡ）により形成されたシートの片面に対して、厚さ６０μｍの樹脂シート６を接着して得られたシートを使用したという点以外は、実施例１と同様の方法で、配線シート４を作製した。得られた配線シート４は、樹脂シート６にワイヤが埋設されていた。 <Wiring sheet 4>
Instead of using the sheet obtained by bonding the resin sheet 6 having a thickness of 60 μm to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 μm instead of the resin sheet 2 In the same manner as in Example 1, a wiring sheet 4 was produced. In the obtained wiring sheet 4, the wire was embedded in the resin sheet 6.
＜配線シート５＞
　樹脂シート２に代えて、厚さ５０μｍのポリメタクリル酸メチル（ＰＭＭＡ）により形成されたシートの片面に対して、厚さ６０μｍの樹脂シート７を接着して得られたシートを使用したという点以外は、実施例１と同様の方法で、配線シート５を作製した。得られた配線シート５は、樹脂シート７にワイヤが埋設されていた。 <Wiring sheet 5>
In place of the resin sheet 2, except that a sheet obtained by bonding a resin sheet 7 having a thickness of 60 μm to one side of a sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 μm was used. In the same manner as in Example 1, a wiring sheet 5 was produced. In the obtained wiring sheet 5, the wire was embedded in the resin sheet 7.
＜配線シート６＞
　樹脂シート２に代えて、厚さ５０μｍのポリメタクリル酸メチル（ＰＭＭＡ）により形成されたシートの片面に対して、厚さ６０μｍの樹脂シート８を接着して得られたシートを使用したという点以外は、実施例１と同様の方法で、配線シート６を作製した。得られた配線シート６は、樹脂シート８にワイヤが埋設されていた。 <Wiring sheet 6>
Instead of using the sheet obtained by adhering the resin sheet 8 having a thickness of 60 μm to one side of the sheet formed of polymethyl methacrylate (PMMA) having a thickness of 50 μm instead of the resin sheet 2 In the same manner as in Example 1, a wiring sheet 6 was produced. In the obtained wiring sheet 6, wires were embedded in the resin sheet 8.
　各樹脂シート１～８は、後述するＡ層（（Ａ）－１、（Ａ）－２、（Ａ）－３、（Ａ）－４、（Ａ）－５又は（Ａ）－６）と、後述するＢ層（（Ｂ）－１又は（Ｂ）－２）と、のうちの少なくとも何れか１層を有する単層又は多層の樹脂シートである。 Each of the resin sheets 1 to 8 includes an A layer ((A) -1, (A) -2, (A) -3, (A) -4, (A) -5 or (A) -6) described later). A single-layer or multilayer resin sheet having at least one of a B layer ((B) -1 or (B) -2) described later.
　＜樹脂シート１＞
　樹脂シート１は、３層シートであり、表層である（Ａ）－１と、中間層である（Ｂ）－１と、表層である（Ａ）－１と、がこの順に積層された構造となっている。 <Resin sheet 1>
The resin sheet 1 is a three-layer sheet, and has a structure in which a surface layer (A) -1, an intermediate layer (B) -1, and a surface layer (A) -1 are laminated in this order. It has become.
　＜樹脂シート２＞
　樹脂シート２は、単層シートであり、（Ａ）－１により構成されている。 <Resin sheet 2>
The resin sheet 2 is a single-layer sheet and is configured by (A) -1.
　＜樹脂シート３＞
　樹脂シート３は、３層シートであり、表層である（Ａ）－２と、中間層である（Ｂ）－２と、表層である（Ａ）－２と、がこの順に積層された構造となっている。 <Resin sheet 3>
The resin sheet 3 is a three-layer sheet having a structure in which the surface layer (A) -2, the intermediate layer (B) -2, and the surface layer (A) -2 are laminated in this order. It has become.
　＜樹脂シート４＞
　樹脂シート４は、単層シートであり、エチレン－酢酸ビニル共重合体（酢酸ビニル単位含有量＝２８重量％）により構成されている。 <Resin sheet 4>
The resin sheet 4 is a single-layer sheet, and is composed of an ethylene-vinyl acetate copolymer (vinyl acetate unit content = 28 wt%).
　＜樹脂シート５＞
　樹脂シート５は、単層シートであり、（Ａ）－３により構成されている。 <Resin sheet 5>
The resin sheet 5 is a single-layer sheet and is made of (A) -3.
　＜樹脂シート６＞
　樹脂シート６は、単層シートであり、（Ａ）－４により構成されている。 <Resin sheet 6>
The resin sheet 6 is a single-layer sheet and is configured by (A) -4.
　＜樹脂シート７＞
　樹脂シート７は、単層シートであり、（Ａ）－５により構成されている。 <Resin sheet 7>
The resin sheet 7 is a single layer sheet, and is constituted by (A) -5.
　＜樹脂シート８＞
　樹脂シート８は、単層シートであり、（Ａ）－６により構成されている。 <Resin sheet 8>
The resin sheet 8 is a single layer sheet and is constituted by (A) -6.
　以下、各層の原料と配合を説明する。 Hereinafter, the raw materials and the composition of each layer will be described.
＜原料＞
－１．樹脂－
　（Ａ層）用の樹脂
・アイオノマー１：エチレン・メタクリル酸・アクリル酸ブチル三元共重合体（メタクリル酸単位含有量＝５重量％、アクリル酸ブチル７重量％）の亜鉛アイオノマー（中和度１０％、ＭＦＲ１１ｇ／１０分）
・アイオノマー２：エチレン・メタクリル酸共重合体（メタクリル酸単位含有量＝８．５重量％）の亜鉛アイオノマー（中和度１８％、ＭＦＲ６ｇ／１０分） <Raw material>
-1. resin-
Resin and ionomer for (A layer) 1: Zinc ionomer (degree of neutralization 10) of ethylene / methacrylic acid / butyl acrylate terpolymer (methacrylic acid unit content = 5 wt%, butyl acrylate 7 wt%) %, MFR11g / 10min)
Ionomer 2: Zinc ionomer of ethylene / methacrylic acid copolymer (methacrylic acid unit content = 8.5% by weight) (degree of neutralization 18%, MFR 6 g / 10 min)
　（Ｂ層）用の樹脂
・アイオノマー３：エチレン・メタクリル酸・アクリル酸ブチル三元共重合体（メタクリル酸単位含有量＝５重量％、アクリル酸ブチル７重量％）の亜鉛アイオノマー（中和度１０％、ＭＦＲ１１ｇ／１０分）
・アイオノマー４：エチレン・メタクリル酸共重合体（メタクリル酸単位含有量＝１２重量％）の亜鉛アイオノマー（中和度３６％、ＭＦＲ１．５g／１０分） Resin and ionomer 3 for (B layer): Zinc ionomer (degree of neutralization 10) of ethylene / methacrylic acid / butyl acrylate terpolymer (methacrylic acid unit content = 5 wt%, butyl acrylate 7 wt%) %, MFR11g / 10min)
-Ionomer 4: Zinc ionomer of ethylene / methacrylic acid copolymer (methacrylic acid unit content = 12 wt%) (degree of neutralization 36%, MFR 1.5 g / 10 min)
－２．添加剤－
・酸化防止剤：ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］（ＢＡＳＦ社製、Ｉｒｇａｎｏｘ１０１０）
・紫外線吸収剤：２－（２Ｈ－ベンゾトリアゾール－２－イル）－４,６－ジ－ｔｅｒｔ－ペンチルフェノール
・光安定剤：ビス（２，２，６，６，－テトラメチル－４－ピペリジル）セバケート
・シランカップリング剤：Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン -2. Additive-
Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1010)
UV absorber: 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenolLight stabilizer: bis (2,2,6,6, -tetramethyl-4-piperidyl ) Sebacate silane coupling agent: N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane
　なお、Ａ層およびＢ層に用いられる安定剤マスターバッチ１としては、各層用の樹脂と同じ樹脂と、酸化防止剤、紫外線吸収剤および光安定剤とを、樹脂／酸化防止剤／紫外線吸収剤／光安定剤＝９３．７／０．３／４／２の重量比で混合し、あらかじめ２軸押し出し機にて押し出したものを用いた。
　また、Ａ層およびＢ層に用いられる安定剤マスターバッチ２としては、各層用の樹脂と同じ樹脂と、酸化防止剤、紫外線吸収剤および光安定剤とを、樹脂／酸化防止剤／光安定剤＝９６／２／２の重量比で混合し、あらかじめ２軸押出機にて押し出したものを用いた。
　白色マスターバッチとしては、大日精化工業株式会社製白色マスターバッチＰＥ－Ｍ　１３Ｎ４７００と、酸化防止剤と、紫外線吸収剤と、光安定剤と、を所定重量比で混合し、あらかじめ２軸押出機にて作製したものを用いた。
　また、Ａ層に用いられる安定剤マスターバッチ３としては、ベース樹脂としてエチレン・α－オレフィン共重合体（三井化学製タフマーＡ－４０９０Ｓ）と、酸化防止剤、光安定剤とを、ベース樹脂／酸化防止剤／光安定剤＝９６／２／２の重量比で混合し、あらかじめ２軸押出機にて作製したものを用いた。 In addition, as the stabilizer masterbatch 1 used for the A layer and the B layer, the same resin as the resin for each layer, the antioxidant, the ultraviolet absorber, and the light stabilizer are resin / antioxidant / ultraviolet absorber. / Light stabilizer = 93.7 / 0.3 / 4/2 The weight ratio of the mixture was used and the mixture was extruded in advance with a biaxial extruder.
Further, as the stabilizer masterbatch 2 used for the A layer and the B layer, the same resin as the resin for each layer, an antioxidant, an ultraviolet absorber, and a light stabilizer are used as a resin / antioxidant / light stabilizer. = 96/2/2 A weight ratio of 96/2/2 was used and the mixture was previously extruded by a twin screw extruder.
As a white masterbatch, a white masterbatch PE-M 13N4700 manufactured by Dainichi Seika Kogyo Co., Ltd., an antioxidant, an ultraviolet absorber, and a light stabilizer are mixed in a predetermined weight ratio, and a twin-screw extruder is prepared in advance. What was produced in (1) was used.
The stabilizer masterbatch 3 used for the layer A includes an ethylene / α-olefin copolymer (Tafmer A-4090S manufactured by Mitsui Chemicals) as a base resin, an antioxidant, and a light stabilizer. Antioxidants / light stabilizers were mixed at a weight ratio of 96/2/2, and those prepared in advance by a twin screw extruder were used.
－３．配合－
＜Ａ層＞
・（Ａ）－１：アイオノマー１／安定剤マスターバッチ２／シランカップリング剤＝９０／１０／０．２
・（Ａ）－２：アイオノマー２／安定剤マスターバッチ１／白色マスターバッチ／シランカップリング剤＝８５／１０／５／０．２
・（Ａ）－３：ＥＶＡ１／安定剤マスターバッチ３＝９０／１０
・（Ａ）－４：ＥＭＡ１／安定剤マスターバッチ３＝９０／１０
・（Ａ）－５：ＥＯＣ１／安定剤マスターバッチ３＝９０／１０
・（Ａ）－６：ＥＯＣ２／安定剤マスターバッチ３＝９０／１０ -3. Formulation-
<A layer>
(A) -1: ionomer 1 / stabilizer masterbatch 2 / silane coupling agent = 90/10 / 0.2
(A) -2: ionomer 2 / stabilizer masterbatch 1 / white masterbatch / silane coupling agent = 85/10/5 / 0.2
(A) -3: EVA1 / stabilizer masterbatch 3 = 90/10
(A) -4: EMA1 / stabilizer masterbatch 3 = 90/10
(A) -5: EOC1 / stabilizer masterbatch 3 = 90/10
(A) -6: EOC2 / stabilizer masterbatch 3 = 90/10
（ＥＶＡ１の調製）
　エチレン・メタクリル酸グリシジル・酢酸ビニル共重合体（ＥＧＭＡＶＡ、住友化学（株）製、ボンドファースト７Ｂ、エチレン含有量：８３重量％、メタクリル酸グリシジル含有量：１２重量％、酢酸ビニル含有量：５重量％、ＭＦＲ（１９０℃、２１６０ｇ荷重）：７ｇ／１０分）：４９．１重量部、エチレン・酢酸ビニル共重合体（酢酸ビニル含有量：１０重量％）：４９．１重量部、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業(株)製、商品名「ＫＢＭ５０３」）：１．５重量部および２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン（アルケマ吉富（株）製、商品名「ルペロックス１０１」）：０．３重量部を予め混合し、溶融温度２２０℃にて４０ｍｍφ単軸押出機で、ＥＧＭＡＶＡおよびエチレン・酢酸ビニル共重合体にシランカップリング剤である３－メタクリロキシプロピルトリメトキシシランをグラフト変性させることにより、シランカップリグ剤により変性されたエチレンと（メタ）アクリル酸グリシジルを含むＥＶＡ１を得た。 (Preparation of EVA1)
Ethylene / glycidyl methacrylate / vinyl acetate copolymer (EGMAVA, manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B, ethylene content: 83 wt%, glycidyl methacrylate content: 12 wt%, vinyl acetate content: 5 wt% %, MFR (190 ° C., 2160 g load): 7 g / 10 min): 49.1 parts by weight, ethylene / vinyl acetate copolymer (vinyl acetate content: 10% by weight): 49.1 parts by weight, 3-methacrylic acid Roxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM503”): 1.5 parts by weight and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Arkema Yoshitomi ( Co., Ltd., trade name “Lupelox 101”): 0.3 parts by weight were mixed in advance and EGMAVA and D were mixed with a 40 mmφ single screw extruder at a melting temperature of 220 ° C. By graft-modifying 3-methacryloxypropyltrimethoxysilane, which is a silane coupling agent, to a ethylene / vinyl acetate copolymer, EVA1 containing ethylene modified with a silane coupling agent and glycidyl (meth) acrylate is obtained. It was.
（ＥＭＡ１の調製）
　ＥＶＡ１の調製において、エチレン・酢酸ビニル共重合体の代わりに、ＥＭＡ：エチレン・メタクリル酸メチル共重合体（エチレン含有量：８０重量％、メタクリル酸メチル含有量：２０重量％）を使用した以外はＥＶＡ１と同様にしてＥＭＡ１を得た。 (Preparation of EMA1)
In the preparation of EVA1, EMA: ethylene / methyl methacrylate copolymer (ethylene content: 80% by weight, methyl methacrylate content: 20% by weight) was used instead of ethylene / vinyl acetate copolymer. EMA1 was obtained in the same manner as EVA1.
（ＥＯＣ１の調製）
　ＥＶＡ１の調製において、エチレン・酢酸ビニル共重合体の代わりに、ＥＯＣ１：エチレン・α－オレフィン共重合体（三井化学製　タフマーＡ－４０９０Ｓ）を使用した以外はＥＶＡ１と同様にしてＥＯＣ１を得た。 (Preparation of EOC1)
EOC1 was obtained in the same manner as EVA1, except that EOC1: ethylene / α-olefin copolymer (Tafmer A-4090S manufactured by Mitsui Chemicals) was used instead of ethylene / vinyl acetate copolymer in preparation of EVA1.
（ＥＯＣ２の調製）
　ＥＶＡ１の調製において、エチレン・酢酸ビニル共重合体の代わりに、ＥＯＣ２：エチレン・α－オレフィン共重合体（三井化学製　タフマーＨ－５０３０Ｓ）を使用した以外はＥＶＡ１と同様にしてＥＯＣ２を得た。 (Preparation of EOC2)
EOC2 was obtained in the same manner as EVA1, except that EOC2: ethylene / α-olefin copolymer (Tafmer H-5030S manufactured by Mitsui Chemicals) was used instead of ethylene / vinyl acetate copolymer in the preparation of EVA1.
＜Ｂ層＞
・（Ｂ）－１：アイオノマー３／安定剤マスターバッチ２＝９０／１０
・（Ｂ）－２：アイオノマー４／安定剤マスターバッチ１／白色マスターバッチ＝８５／１０／５ <B layer>
(B) -1: ionomer 3 / stabilizer masterbatch 2 = 90/10
(B) -2: ionomer 4 / stabilizer masterbatch 1 / white masterbatch = 85/10/5
＜樹脂シートの作製＞
　多層樹脂シートである樹脂シート１および３を、それぞれ２種３層多層キャスト成形機（田辺プラスチックス機械社製）、フィードブロック式（ＥＤＩ社製）、４０ｍｍφ単軸押出機、およびダイ幅５００ｍｍ押出機を用いて加工温度１４０℃にてシート状に成形することにより作製した。
　また、単層樹脂シートである樹脂シート２、４～８を、それぞれ単層Ｔ－ダイ成形機（田辺プラスチックス機械社製）、４０ｍｍφ単軸押出機、ダイ幅５００ｍｍ押出機を用いて、上記樹脂シート１、３と同様に、加工温度１４０℃にてシート状に成形し、作製した。
　なお、基材シートと樹脂シート２との積層構造を有する配線シート１は、上記成形機の繰出し部分より基材シートを供給し、樹脂シート２を成形時にニップロールにて加熱圧着することで製造した。同様に、配線シート３～６も上記成形機の繰出し部分より基材シートを供給し、樹脂シート５～８を成形時にニップロールにて加熱圧着することで製造した。 <Production of resin sheet>
Resin sheets 1 and 3, which are multilayer resin sheets, are each extruded into two types and three layers of multilayer cast molding machine (manufactured by Tanabe Plastics Machinery), feed block type (manufactured by EDI), 40 mmφ single screw extruder, and die width 500 mm extrusion It was produced by forming into a sheet shape at a processing temperature of 140 ° C. using a machine.
Further, the resin sheets 2 and 4 to 8 which are single layer resin sheets were respectively converted into the above using a single layer T-die molding machine (manufactured by Tanabe Plastics Machinery Co., Ltd.), 40 mmφ single screw extruder, and die width 500 mm extruder. Similarly to the resin sheets 1 and 3, the sheet was formed into a sheet shape at a processing temperature of 140 ° C.
In addition, the wiring sheet 1 having a laminated structure of the base sheet and the resin sheet 2 was manufactured by supplying the base sheet from the feeding portion of the molding machine and heat-pressing the resin sheet 2 with a nip roll at the time of molding. . Similarly, the wiring sheets 3 to 6 were manufactured by supplying a base sheet from the feeding portion of the molding machine and heat-pressing the resin sheets 5 to 8 with a nip roll at the time of molding.
　実施例および比較例の光発電モジュールを用いて行った測定および評価について、以下に説明する。 Measures and evaluations performed using the photovoltaic modules of Examples and Comparative Examples are described below.
　配線接続良否（ＥＬ画像）： 
　実施例及び比較例に係る光発電モジュールの配線接続良否について、ＥＬ（エレクトロルミネッセンス）法により評価した。すなわち、各光発電モジュールに電流を入力して発光させた状態で、ＥＬ画像を取得し、良否の評価を行った。
　各光発電モジュールのＥＬ画像の取得には、ＥＬ画像検査装置（アイテス社製、ＰＶＸ１００）を用いた。また、ＥＬ画像を取得するための測定条件は、シャッター時間１５秒、絞り８、ＩＳＯ感度８００、光発電モジュールへの入力電圧０．７３Ｖ、光発電モジュールへの入力電流８Ａという条件を採用した。
　そして、得られたＥＬ画像を目視にて確認し、配線接続良否の評価を行った。
　評価結果は、Ａ：影なし（接続良好）、Ｃ：影あり（配線接続の一部に難あり）、とした。
　結果は、実施例１～５ではすべてＡ、比較例１ではＣとなった。 Wiring connection quality (EL image):
The wiring connection quality of the photovoltaic modules according to the examples and comparative examples was evaluated by an EL (electroluminescence) method. That is, an EL image was acquired in a state where a current was inputted to each photovoltaic module to emit light, and the quality was evaluated.
For obtaining the EL image of each photovoltaic module, an EL image inspection device (manufactured by ITES, PVX100) was used. The measurement conditions for acquiring the EL image were as follows: shutter time 15 seconds, aperture 8, ISO sensitivity 800, input voltage 0.73V to the photovoltaic module, and input current 8A to the photovoltaic module.
And the obtained EL image was confirmed visually and the quality of wiring connection was evaluated.
The evaluation results were as follows: A: no shadow (good connection), C: shadow (part of wiring connection was difficult).
The results were all A in Examples 1 to 5 and C in Comparative Example 1.
　最大出力（Ｐｍａｘ）：
　実施例及び比較例に係る光発電モジュールについて、最大出力（Ｐｍａｘ）を測定した。
　すなわち、各光発電モジュールに入力するバイアス電圧を変化させながら、電流を測定し、得られたデータをプロットすることにより、Ｉ－Ｖ曲線（図示略）を得た。
　ここで、電流の測定には、住友重機械工業株式会社　太陽電池ＩＶ測定装置Ｎｏ．Ｍ１３０－ＤＤＹＴＢ３８３　Ｊ－ＪＡを用いた。
　また、バイアス電圧は、－０．１Ｖから０．８Ｖの範囲で変化させ、この範囲のうち、－０．１Ｖから０．４Ｖまではバイアス電圧を０．０２Ｖ刻みで変化させ、０．４Ｖから０．８Ｖまではバイアス電圧を０．０１Ｖ刻みで変化させた。
　また、測定条件として、ＡＭ１．５Ｇ、１ＳＵＮを採用し、２５℃で測定を行った。
　そして、得られたＩ－Ｖ曲線に関し、電圧と電流の積が最大になる点、すなわち「最大出力（Ｐｍａｘ）」を求めた。
　その結果、最大出力（Ｐｍａｘ）は、実施例１では５．１３、実施例２では５．０６、実施例３では５．０４、実施例４では５．１３、実施例５では５．１３、比較例１では４．８２となった。 Maximum output (Pmax):
About the photovoltaic module which concerns on an Example and a comparative example, the maximum output (Pmax) was measured.
That is, the current was measured while changing the bias voltage input to each photovoltaic module, and the obtained data was plotted to obtain an IV curve (not shown).
Here, in the measurement of current, Sumitomo Heavy Industries, Ltd. M130-DDYTB383 J-JA was used.
The bias voltage is changed in the range of −0.1V to 0.8V. Within this range, the bias voltage is changed in increments of 0.02V from −0.1V to 0.4V. The bias voltage was changed in increments of 0.01V up to 0.8V.
Further, AM1.5G and 1SUN were adopted as measurement conditions, and measurement was performed at 25 ° C.
Then, with respect to the obtained IV curve, the point at which the product of voltage and current becomes maximum, that is, “maximum output (Pmax)” was obtained.
As a result, the maximum output (Pmax) is 5.13 in Example 1, 5.06 in Example 2, 5.04 in Example 3, 5.13 in Example 4, 5.13 in Example 5, In Comparative Example 1, it was 4.82.
　フィルファクタ（ＦＦ）：
　更に、上記の最大出力（Ｐｍａｘ）の測定結果を用いて、実施例及び比較例に係る光発電モジュールのフィルファクタ（ＦＦ）を求めた。
　ここで、電圧が０Ｖ時の電流は短絡電流（ｓｈｏｒｔ－ｃｉｒｃｕｉｔ　ｃｕｒｒｅｎｔ＝Ｉｓｃ）といい、光発電モジュールに電流が流れていない時の電圧を開放電圧（ｏｐｅｎ－ｃｉｒｃｕｉｔ　ｖｏｌｔａｇｅ＝Ｖｏｃ）という。
　フィルファクタ（ＦＦ）は、最大出力（Ｐｍａｘ）／（Ｖｏｃ×Ｉｓｃ）であり、実施例１では０．７８９、実施例２では０．７７０、実施例３では０．７５５、実施例４では０．７８９、実施例５では０．７８９、比較例１では０．７４３となった。 Fill factor (FF):
Furthermore, the fill factor (FF) of the photovoltaic module which concerns on an Example and a comparative example was calculated | required using the measurement result of said maximum output (Pmax).
Here, the current when the voltage is 0 V is called a short-circuit current (short-circuit current = Isc), and the voltage when no current flows through the photovoltaic module is called an open-circuit voltage (Voc).
The fill factor (FF) is the maximum output (Pmax) / (Voc × Isc), 0.789 in the first embodiment, 0.770 in the second embodiment, 0.755 in the third embodiment, and 0 in the fourth embodiment. 789, 0.789 in Example 5, and 0.743 in Comparative Example 1.
　また、上記の配線シート１～６を用いて行った測定および評価について、以下に説明する。 Further, the measurement and evaluation performed using the above wiring sheets 1 to 6 will be described below.
　・３５０ｎｍの波長における樹脂シートの光線透過率：２５℃という条件下、ＪＩＳ－Ｋ７１０５に準じて樹脂シートの３５０ｎｍの波長における光線透過率を測定した。なお、単位は、％とした。
　実施例１の配線シート１では、３５０ｎｍの波長における光線透過率は、８５％であった。
　実施例２の配線シート３では、３５０ｎｍの波長における光線透過率は、８５％であった。
　実施例３の配線シート４では、３５０ｎｍの波長における光線透過率は、８５％であった。
　実施例４の配線シート５では、３５０ｎｍの波長における光線透過率は、８５％であった。
　実施例５の配線シート６では、３５０ｎｍの波長における光線透過率は、８５％であった。
　一方、比較例１の配線シート２では、３５０ｎｍの波長における光線透過率は、４．３％であった。 Light transmittance of resin sheet at a wavelength of 350 nm: The light transmittance at a wavelength of 350 nm of the resin sheet was measured according to JIS-K7105 under the condition of 25 ° C. The unit is%.
In the wiring sheet 1 of Example 1, the light transmittance at a wavelength of 350 nm was 85%.
In the wiring sheet 3 of Example 2, the light transmittance at a wavelength of 350 nm was 85%.
In the wiring sheet 4 of Example 3, the light transmittance at a wavelength of 350 nm was 85%.
In the wiring sheet 5 of Example 4, the light transmittance at a wavelength of 350 nm was 85%.
In the wiring sheet 6 of Example 5, the light transmittance at a wavelength of 350 nm was 85%.
On the other hand, in the wiring sheet 2 of Comparative Example 1, the light transmittance at a wavelength of 350 nm was 4.3%.
　・全光線透過率：２５℃という条件下、ＪＩＳ－Ｋ７１０５に準じて樹脂シートの全光線透過率を測定した。なお、単位は、％とした。
　実施例１の配線シート１では、全光線透過率は、８９．６％であった。
　実施例２の配線シート３では、全光線透過率は、８８．９％であった。
　実施例３の配線シート４では、全光線透過率は、８８．８％であった。
　実施例４の配線シート５では、全光線透過率は、９０．２％であった。
　実施例５の配線シート６では、全光線透過率は、９０．２％であった。
　一方、比較例の配線シート２では、全光線透過率は、９２．２％であった。 Total light transmittance: Under the condition of 25 ° C., the total light transmittance of the resin sheet was measured according to JIS-K7105. The unit is%.
In the wiring sheet 1 of Example 1, the total light transmittance was 89.6%.
In the wiring sheet 3 of Example 2, the total light transmittance was 88.9%.
In the wiring sheet 4 of Example 3, the total light transmittance was 88.8%.
In the wiring sheet 5 of Example 4, the total light transmittance was 90.2%.
In the wiring sheet 6 of Example 5, the total light transmittance was 90.2%.
On the other hand, in the wiring sheet 2 of the comparative example, the total light transmittance was 92.2%.
　この出願は、２０１５年２月６日に出願された日本出願特願２０１５－０２２０７４号を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2015-022074 filed on February 6, 2015, the entire disclosure of which is incorporated herein.

Claims (5)

  1. 　光発電素子を備える光発電モジュールであって、
    　前記光発電素子は、
    　第１導電型の結晶半導体基板を備えているとともに、
    　前記結晶半導体基板の一方の面側に、第１非晶質系半導体膜と、第１導電型の第２非晶質系半導体膜と、第１透光性電極膜と、第１電極と、をこの順に備え、
    　前記結晶半導体基板の他方の面側に、真性の第３非晶質系半導体膜と、第２導電型の第４非晶質系半導体膜と、第２透光性電極膜と、第２電極と、をこの順に備え、
    　前記第１非晶質系半導体膜は、前記第２非晶質系半導体膜よりも不純物濃度が低い第１導電型であるか、又は、真性であり、
    　当該光発電モジュールは、更に、
    　前記光発電素子の一方の面の前記第１電極に第１接着層により接合固定された複数の第１微細配線と、
    　前記光発電素子の前記一方の面との間に前記複数の第１微細配線を挟んでいるとともに、前記第１接着層を介して前記光発電素子の前記一方の面に接合された第１樹脂フィルムと、
    　透光性の第１保護層と、
    　前記第１保護層と前記第１樹脂フィルムとの間に充填された第１封止層と、
    　前記光発電素子の他方の面の前記第２電極に第２接着層により接合固定された複数の第２微細配線と、
    　前記光発電素子の前記他方の面との間に前記複数の第２微細配線を挟んでいるとともに、前記第２接着層を介して前記光発電素子の前記他方の面に接合された第２樹脂フィルムと、
    　第２保護層と、
    　前記第２保護層と前記第２樹脂フィルムとの間に充填された第２封止層と、
    　を備え、
    　前記第１接着層は、以下の（Ａ）および（Ｂ）のいずれかを含む樹脂材料により構成されている光発電モジュール。
    （Ａ）エチレンと不飽和カルボン酸を含む共重合体、または前記共重合体のアイオノマー
    （Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体     A photovoltaic module comprising photovoltaic elements,
    The photovoltaic element is
    A first conductivity type crystalline semiconductor substrate;
    A first amorphous semiconductor film, a first conductive type second amorphous semiconductor film, a first translucent electrode film, a first electrode, on one surface side of the crystalline semiconductor substrate; In this order,
    An intrinsic third amorphous semiconductor film, a second conductivity type fourth amorphous semiconductor film, a second translucent electrode film, and a second electrode are formed on the other surface side of the crystalline semiconductor substrate. And in this order,
    The first amorphous semiconductor film is a first conductivity type having an impurity concentration lower than that of the second amorphous semiconductor film, or is intrinsic.
    The photovoltaic module further includes
    A plurality of first fine wires bonded and fixed to the first electrode on one surface of the photovoltaic element by a first adhesive layer;
    The first resin having the plurality of first fine wirings sandwiched between the one surface of the photovoltaic element and bonded to the one surface of the photovoltaic element via the first adhesive layer With film,
    A translucent first protective layer;
    A first sealing layer filled between the first protective layer and the first resin film;
    A plurality of second fine wires bonded and fixed to the second electrode on the other surface of the photovoltaic element by a second adhesive layer;
    The second resin having the plurality of second fine wirings sandwiched between the other surface of the photovoltaic element and bonded to the other surface of the photovoltaic element via the second adhesive layer With film,
    A second protective layer;
    A second sealing layer filled between the second protective layer and the second resin film;
    With
    The said 1st contact bonding layer is a photovoltaic module comprised by the resin material containing either of the following (A) and (B).
    (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the copolymer (B) a copolymer containing ethylene and glycidyl (meth) acrylate
  2. 　前記共重合体は、アイオノマーである請求項１に記載の光発電モジュール。 The photovoltaic module according to claim 1, wherein the copolymer is an ionomer.
  3. 　ＪＩＳ－Ｋ７１０５に準じて測定した前記第１接着層の３５０ｎｍの波長における光線透過率が、７０％以上である請求項１又は２に記載の光発電モジュール。 The photovoltaic module according to claim 1 or 2, wherein the light transmittance at a wavelength of 350 nm of the first adhesive layer measured in accordance with JIS-K7105 is 70% or more.
  4. 　前記複数の第１微細配線は、互いに平行に配置された複数のワイヤであり、
    　前記ワイヤの外径をＤとすると、
    　前記第１接着層の層厚Ｔは、Ｄ／６±Ｄ／１２の範囲に設定されている請求項１乃至３の何れか一項に記載の光発電モジュール。     The plurality of first fine wirings are a plurality of wires arranged in parallel to each other,
    If the outer diameter of the wire is D,
    4. The photovoltaic module according to claim 1, wherein a thickness T of the first adhesive layer is set in a range of D / 6 ± D / 12. 5.
  5. 　前記第２保護層は透光性であり、
    　前記第２接着層は、以下の（Ａ）および（Ｂ）のいずれかを含む樹脂材料により構成されている請求項１乃至４の何れか一項に記載の光発電モジュール。
    （Ａ）エチレンと不飽和カルボン酸を含む共重合体、または前記共重合体のアイオノマー
    （Ｂ）エチレンと（メタ）アクリル酸グリシジルを含む共重合体     The second protective layer is translucent;
    The photovoltaic module according to any one of claims 1 to 4, wherein the second adhesive layer is made of a resin material including any of the following (A) and (B).
    (A) a copolymer containing ethylene and an unsaturated carboxylic acid, or an ionomer of the copolymer (B) a copolymer containing ethylene and glycidyl (meth) acrylate
PCT/JP2016/053464 2015-02-06 2016-02-05 Photovoltaic module WO2016125882A1 (en)

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