WO2018088322A1 - Solar cell rear surface sealant sheet set, solar cell module and method for producing solar cell module - Google Patents

Solar cell rear surface sealant sheet set, solar cell module and method for producing solar cell module Download PDF

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Publication number
WO2018088322A1
WO2018088322A1 PCT/JP2017/039714 JP2017039714W WO2018088322A1 WO 2018088322 A1 WO2018088322 A1 WO 2018088322A1 JP 2017039714 W JP2017039714 W JP 2017039714W WO 2018088322 A1 WO2018088322 A1 WO 2018088322A1
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WIPO (PCT)
Prior art keywords
solar cell
sealing sheet
surface side
back surface
ethylene
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PCT/JP2017/039714
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French (fr)
Japanese (ja)
Inventor
貴信 室伏
貢 大和
大枝　靖雄
徳弘　淳
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三井化学東セロ株式会社
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Priority to JP2018550175A priority Critical patent/JPWO2018088322A1/en
Publication of WO2018088322A1 publication Critical patent/WO2018088322A1/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
    • H01L31/048—Encapsulation of modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • 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 solar cell back side sealing sheet set, a solar cell module, and a method for manufacturing a solar cell module.
  • solar cells are attracting attention as a means of generating energy that is clean and free from depletion.
  • a solar cell When a solar cell is used outdoors such as a roof portion of a building, it is generally used in the form of a solar cell module.
  • a solar cell module is manufactured by the following procedures, for example. First, a protective sheet for a solar cell module (surface-side transparent protective member) / solar cell sealing material (hereinafter, a sheet-like solar cell sealing material is also referred to as a sealing sheet) / solar cell element / solar cell sealing material. / Laminate in order of solar cell module protective sheet (back side protective member). Then, a solar cell module is manufactured by utilizing the lamination method etc. which vacuum-suck these and heat-press them. The solar cell module manufactured in this way has weather resistance and is suitable for outdoor use such as a roof portion of a building.
  • an ethylene-based copolymer such as an ethylene / ⁇ -olefin copolymer or an ethylene / polar monomer copolymer is used (for example, Patent Documents 1 to 3).
  • the non-light-receiving surface side (hereinafter referred to as the back surface side) of the solar cell element
  • a colored sealing sheet containing a colorant is used.
  • the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene-based copolymer and the colorant is between after being molded and laminated. It became clear that the adhesiveness with respect to a solar cell element and a back surface side protection member will fall with time.
  • the present invention has been made in view of the above circumstances, and provides a solar cell back surface side sealing sheet excellent in temporal stability of adhesiveness to the solar cell element and the back surface side protection member.
  • the inventors of the present invention diligently studied to realize a solar cell back surface side sealing sheet excellent in the temporal stability of adhesiveness to the solar cell element and the back surface side protection member.
  • the present inventors separately prepared a transparent encapsulating sheet containing no colorant and a colored encapsulating sheet containing a colorant, and laminating these sheets at the stage of sealing the solar cell element.
  • the transparent encapsulating sheet is disposed on the solar cell element side
  • the colored encapsulating sheet is disposed on the back surface side protective member side to be used, whereby the solar cell back surface side sealing with respect to the solar cell element and the back surface side protective member It has been found that the stability over time of the adhesiveness of the sheet can be improved.
  • the following solar cell back side sealing sheet set, solar cell module, and solar cell module manufacturing method are provided.
  • the transparent encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / ⁇ -olefin copolymer and an ethylene / polar monomer copolymer, and is disposed on the solar cell element side.
  • the colored encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / ⁇ -olefin copolymer and an ethylene / polar monomer copolymer, and a colorant, and on the back side protective member side Is to be placed,
  • the solar cell back surface side sealing sheet set which laminates and uses the said transparent sealing sheet and the said colored sealing sheet when sealing the said solar cell element.
  • At least one of the transparent sealing sheet and the colored sealing sheet contains the ethylene / ⁇ -olefin copolymer as the ethylene copolymer, and the ethylene / ⁇ -olefin copolymer has the following requirements a1) and The solar cell back surface side sealing sheet set which satisfy
  • a1) The density measured according to ASTM D1505 is 0.865 to 0.895 g / cm 3 .
  • Shore A hardness measured according to ASTM D2240 is 60-95.
  • At least one of the transparent sealing sheet and the colored sealing sheet includes the ethylene / polar monomer copolymer as the ethylene copolymer, The solar cell back side sealing sheet set in which the ethylene / polar monomer copolymer contains an ethylene / vinyl acetate copolymer.
  • the solar cell back surface side sealing sheet set whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less.
  • the solar cell back surface side sealing sheet set whose said back surface side protection member is a glass plate.
  • each of the front surface side transparent protective member and the back surface side protective member is a glass plate, A solar cell module in which the solar cell module is a laminated glass solar cell module.
  • the solar cell element is heated in a state sandwiched between the solar cell light receiving surface side sealing sheet and the solar cell back surface side sealing sheet, and the solar cell element is heated to the solar cell light receiving surface side sealing sheet and the solar cell back surface side.
  • the solar cell back surface side sealing sheet includes the solar cell back surface side sealing sheet set according to any one of the above [1] to [14], In the above step of separately preparing the transparent sealing sheet and the colored sealing sheet and sealing the solar cell element, the solar cell module is manufactured by laminating the transparent sealing sheet and the colored sealing sheet.
  • the present invention it is possible to realize a solar cell back side sealing sheet excellent in the temporal stability of adhesiveness to the solar cell element and the back side protective member.
  • the solar cell back side sealing sheet set is arranged between the solar cell element and the back side protective member to seal the non-light-receiving surface side of the solar cell element. It is used to stop and includes a transparent sealing sheet and a colored sealing sheet.
  • the transparent encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / ⁇ -olefin copolymer and an ethylene / polar monomer copolymer, and is disposed on the solar cell element side. is there.
  • the colored encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / ⁇ -olefin copolymer and an ethylene / polar monomer copolymer, and a colorant, and the back side protective member It is arranged on the side.
  • the solar cell back surface side sealing sheet set which concerns on this embodiment uses the said transparent sealing sheet and the said colored sealing sheet by laminating
  • the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene copolymer and the colorant is laminated after being molded. It became clear that the adhesiveness with respect to a solar cell element and a back surface side protection member fell with time in the meantime. Then, the present inventors diligently studied in order to realize a solar cell back surface side sealing sheet excellent in temporal stability of adhesion to the solar cell element and the back surface side protection member. As a result, the present inventors separately prepared a transparent encapsulating sheet containing no colorant and a colored encapsulating sheet containing a colorant, and laminating these sheets at the stage of sealing the solar cell element.
  • the transparent encapsulating sheet is disposed on the solar cell element side, and the colored encapsulating sheet is disposed on the back surface side protective member side to be used, whereby the solar cell back surface side sealing with respect to the solar cell element and the back surface side protective member is performed.
  • the stability over time of the adhesiveness of the sheet can be improved. That is, according to the solar cell back surface side sealing sheet set which concerns on this embodiment, by laminating
  • the temporal stability of the adhesiveness of the solar cell back surface side sealing sheet to the solar cell element and the back surface side protection member can be improved.
  • the conversion efficiency of a solar cell module is improved by light reflectivity by providing a colored sealing sheet, or the designability and heat of a sealing sheet Conductivity and the like can be improved.
  • the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene copolymer and the colorant is colored when the solar cell module is produced. It has been clarified that the sealing sheet may wrap around the surface of the solar cell element or the wiring. When the colored encapsulating sheet wraps around the surface side of the solar cell element or wiring, the yield of the solar cell module is deteriorated or the light incident on the solar cell element is blocked, resulting in a decrease in the power generation performance of the solar cell element. There is a concern that it may.
  • the present inventors diligently studied in order to realize a colored sealing layer in which wraparound to the surface of a solar cell element, wiring, or the like is suppressed.
  • the present inventors arrange the transparent sealing sheet on the solar cell element side, and arrange the colored sealing sheet on the back surface side protective member side, so that the wraparound to the surface of the solar cell element or wiring is prevented.
  • a suppressed back side sealing layer is obtained. That is, according to the solar cell back side sealing sheet set according to the present embodiment, the transparent sealing sheet is disposed on the solar cell element side, and the colored sealing sheet is disposed and used on the back surface side protection member side. It is possible to further suppress the back surface side sealing layer from wrapping around the surface of the solar cell element or the wiring.
  • the transparent sealing sheet is disposed so as to be in contact with the solar cell element, and the colored sealing sheet is disposed so as to be in contact with the back surface side protection member. preferable.
  • the total thickness of the transparent sealing sheet and the colored sealing sheet according to this embodiment is not particularly limited, but is preferably 200 ⁇ m or more and 2000 ⁇ m or less, and more preferably 300 ⁇ m or more and 1200 ⁇ m or less. When the thickness is within this range, damage to the back surface side protective member, the solar cell element, the thin film electrode, etc. in the laminating step can be suppressed. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
  • the thickness of the transparent sealing sheet according to the present embodiment is preferably 100 ⁇ m or more, more preferably 130 ⁇ m or more, from the viewpoint that the colored sealing sheet can better suppress the wrapping around the surface of the solar cell element or the wiring. 180 ⁇ m or more is more preferable, 220 ⁇ m or more is even more preferable, and 280 ⁇ m or more is particularly preferable.
  • the thickness of the colored sealing sheet according to the present embodiment is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, from the viewpoint that the colored sealing sheet can more effectively prevent the colored sealing sheet from wrapping around the surface of the solar cell element or the wiring. 120 ⁇ m or less is particularly preferable.
  • the thickness of the transparent encapsulating sheet equal to or more than the above lower limit value, it is possible to better suppress the colored encapsulating sheet from wrapping around the surface of the solar cell element or the wiring when the solar cell module is manufactured. Can do. Furthermore, by making the thickness of the colored encapsulating sheet equal to or less than the above upper limit value, the colored encapsulating sheet can be further suppressed from wrapping around the surface of the solar cell element, the wiring or the like when the solar cell module is manufactured. be able to.
  • the transparent sealing sheet and the colored sealing sheet according to this embodiment contain at least one ethylene-based copolymer selected from an ethylene / ⁇ -olefin copolymer and an ethylene / polar monomer copolymer as essential components.
  • the content of the ethylene copolymer is 100% by mass of the entire resin component contained in the transparent sealing sheet and the colored sealing sheet, respectively. Respectively, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.
  • flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
  • the content of the resin component is preferably 70% by mass or more, more preferably 80% by mass or more, further when the entire transparent encapsulating sheet is 100% by mass. Preferably it is 90 mass% or more, Most preferably, it is 95 mass% or more.
  • the transparent sealing sheet excellent in balance of various characteristics, such as transparency, adhesiveness, heat resistance, a softness
  • the content of the resin component is preferably 40% by mass or more, more preferably 50% by mass or more when the entire colored sealing sheet is 100% by mass.
  • the coloring sealing sheet excellent in the balance of various characteristics, such as adhesiveness, heat resistance, a softness
  • the melt flow rate (MFR) of the ethylene copolymer measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238 is, for example, 0.1 g / It is 10 minutes or more and 50 g / 10 minutes or less, preferably 1 g / 10 minutes or more and 40 g / 10 minutes or less, more preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less, and further preferably 5 g / 10 minutes or more. It is 10 g / 10 minutes or less.
  • the melt flow rate (MFR) of the ethylene-based copolymer measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238 is, for example, 0.8.
  • the amount is from 01 g / 10 min to 30 g / 10 min, more preferably from 0.05 g / 10 min to 10 g / 10 min, particularly preferably from 0.5 g / 10 min to less than 5.0 g / 10 min.
  • the processing of the colored encapsulating sheet is preferably 0.05 g / 10 min or more, more preferably 0.1 g / 10 min or more, further preferably 0.2 g / 10 min or more, particularly preferably 0.5 g / 10 min or more.
  • the upper limit value of the MFR of the ethylene copolymer measured under the conditions of 190 ° C. and 2.16 kg load is based on ASTM D1238.
  • it is preferably less than 5.0 g / 10 minutes, more preferably less than 4.0 g / 10 minutes, and even more preferably less than 3.0 g / 10 minutes. Particularly preferably, it is less than 2.0 g / 10 minutes.
  • the MFR of the ethylene copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, the molar ratio of the ethylene monomer concentration to the hydrogen concentration in the polymerization system, and the like.
  • the ethylene / ⁇ -olefin copolymer according to this embodiment can be obtained, for example, by copolymerizing ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • ⁇ -olefin ⁇ -olefins having 3 to 20 carbon atoms can be used singly or in combination of two or more.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms include linear or branched ⁇ -olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3, 3 -Dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned.
  • ⁇ -olefins having 10 or less carbon atoms are preferable, and ⁇ -olefins having 3 to 8 carbon atoms are particularly preferable.
  • Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred because of their availability.
  • the ethylene / ⁇ -olefin copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferred from the viewpoint of flexibility.
  • the ethylene / ⁇ -olefin copolymer may be a copolymer containing ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
  • the ⁇ -olefin is the same as described above, and examples of the non-conjugated polyene include 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and dicyclopentadiene (DCPD).
  • ENB 5-ethylidene-2-norbornene
  • VNB 5-vinyl-2-norbornene
  • DCPD dicyclopentadiene
  • ethylene / ⁇ -olefin copolymer examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinyl benzoic acid, methyl vinylbenzoate, and vinyl.
  • Aromatic vinyl compounds such as benzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, 4-phenylpropylene, ⁇ -methylstyrene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, etc. Cyclic olefins having 3 to 20 carbon atoms may be used in combination.
  • examples of the ethylene / ⁇ -olefin copolymer include Tafmer (registered trademark) manufactured by Mitsui Chemicals, ENGAGE (registered trademark) manufactured by DOW, EXACT (registered trademark) manufactured by ExxonMobil, and Nippon Polyethylene. Kernel (trademark registration) manufactured by the company, etc. may be mentioned.
  • the ethylene / ⁇ -olefin copolymer preferably satisfies at least one of the following requirements a1) and a2).
  • the density of the ethylene / ⁇ -olefin copolymer measured according to ASTM D1505 is preferably 0.865 to 0.895 g / cm 3 , more preferably 0.866 to 0.890 g / cm 3 , It is preferably 0.866 to 0.884 g / cm 3 , particularly preferably 0.867 to 0.880 g / cm 3 .
  • the density of the ethylene / ⁇ -olefin copolymer can be adjusted by a balance between the content ratio of ethylene units and the content ratio of ⁇ -olefin units.
  • the density of the ethylene / ⁇ -olefin copolymer is not more than the above upper limit, the crystallinity becomes more appropriate, and the transparency of the resulting sealing sheet can be further increased. Furthermore, the crosslinkability can be made better. Moreover, it is excellent in a softness
  • the density of the ethylene / ⁇ -olefin copolymer is not less than the above lower limit, the crystallization speed of the ethylene / ⁇ -olefin copolymer can be increased, so that the sheet extruded from the extruder is not sticky, and cooling Peeling with a roll becomes easy and a sealing sheet can be obtained easily. Further, since stickiness is less likely to occur in the sheet, the occurrence of blocking can be suppressed, and the sheet feedability can be improved. Moreover, since it is made to fully bridge
  • the Shore A hardness of the ethylene / ⁇ -olefin copolymer is preferably 60 to 95, more preferably 62 to 90, still more preferably 62 to 85, and particularly preferably 65 to 95. 80.
  • the Shore A hardness of the ethylene / ⁇ -olefin copolymer can be adjusted by controlling the content and density of the ethylene units in the ethylene / ⁇ -olefin copolymer within the above-mentioned numerical range. That is, an ethylene / ⁇ -olefin copolymer having a high ethylene unit content and a high density has a high Shore A hardness. On the other hand, an ethylene / ⁇ -olefin copolymer having a low content of ethylene units and a low density has a low Shore A hardness.
  • the Shore A hardness is not less than the above lower limit, a sheet that is easily formed into a sheet and has good blocking resistance can be obtained, and heat resistance can also be improved.
  • the Shore A hardness is not more than the above upper limit, the transparency and flexibility can be improved and sheet molding can be facilitated.
  • Examples of the ethylene / polar monomer copolymer according to the present embodiment include an ethylene / (meth) ethyl acrylate copolymer, an ethylene / (meth) methyl acrylate copolymer, and an ethylene / (meth) acrylate propyl copolymer.
  • the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
  • the ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
  • the content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass.
  • the vinyl acetate content can be measured according to JIS K6730.
  • the ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate.
  • ethylene and vinyl acetate for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate.
  • vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof may be included as a copolymerization component. .
  • the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
  • the method for producing the ethylene / polar monomer copolymer is not particularly limited, and can be produced by a known method.
  • a radical generator copolymerization of ethylene, polar monomers, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
  • the transparent sealing sheet according to this embodiment preferably further contains a silane coupling agent.
  • the colored sealing sheet which concerns on this embodiment may further contain a silane coupling agent.
  • silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl.
  • 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane and vinyltriethoxysilane are more preferable because the adhesion is improved.
  • the content of the silane coupling agent in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 0. 100 parts by mass with respect to 100 parts by mass of the ethylene copolymer in the sheet containing the silane coupling agent. It is preferably 01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 2 parts by mass or less, further preferably 0.1 parts by mass or more and 1 part by mass or less. The amount is particularly preferably 1 part by mass or more and 0.6 part by mass or less.
  • the adhesive strength between the sealing sheet and the other member can be further improved.
  • the content of the silane coupling agent is not more than the above upper limit value, the balance between cost and performance is good, and deterioration of moisture permeability can be prevented. Moreover, adhesiveness with a solar cell element, an electrode, and a back surface side protection member becomes favorable, and adhesiveness also improves. Moreover, it can suppress that a silane coupling agent itself raise
  • the colored sealing sheet according to the present embodiment contains a colorant as an essential component.
  • the conversion efficiency of the solar cell module can be improved by the light reflectivity, and the designability and thermal conductivity of the colored sealing sheet can be improved.
  • the colorant examples include natural mica (mica), synthetic mica, titanium oxide, aluminum oxide, calcium carbonate, talc, clay, magnesium carbonate, kaolinite, diatomaceous earth, carbon black, infrared reflective pigment, and the like. These may be used alone or in combination of two or more. Among these, titanium oxide, aluminum oxide, calcium carbonate, talc, clay, magnesium carbonate, carbon black, and infrared reflecting pigment are preferable, and titanium oxide, aluminum oxide, calcium carbonate, carbon black, and infrared reflecting pigment are more preferable, and titanium oxide. Carbon black and infrared reflecting pigment are more preferable, and titanium oxide is particularly preferable.
  • natural mica mica
  • synthetic mica titanium oxide, aluminum oxide, calcium carbonate, talc, clay, magnesium carbonate, kaolinite, diatomaceous earth, carbon black, infrared reflective pigment, and the like. These may be used alone or in combination of two or more.
  • examples of the infrared reflecting pigment include copper / chromium / manganese composite oxide, iron / chromium composite oxide, manganese / bismuth composite oxide, calcium / titanium / manganese composite oxide, and the like. .
  • the content of the colorant in the colored sealing sheet according to the present embodiment is preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the colored sealing sheet.
  • Part to 50 parts by weight is more preferable, 1 part to 30 parts by weight is more preferable, and 1 part to 20 parts by weight is particularly preferable.
  • the transparent sealing sheet which concerns on this embodiment further contains a crosslinking agent (organic peroxide).
  • the colored sealing sheet which concerns on this embodiment may further contain a crosslinking agent.
  • the organic peroxide preferably has a half-life of 10 hours or less and a decomposition temperature of 105 ° C. or less. From the viewpoint of safety, it is preferable that the maximum storage temperature is 10 ° C. or higher.
  • the organic peroxide has a one-minute half-life temperature of 100 ° C. due to the balance between productivity in sheet molding such as extrusion molding and calender molding and the crosslinking rate at the time of laminate molding of the solar cell module. A temperature of 170 ° C. or lower is preferable.
  • the one-minute half-life temperature of the organic peroxide is 100 ° C. or more, sheet molding can be facilitated and the appearance of the sealing sheet can be improved.
  • the fall of the dielectric breakdown voltage of the sealing sheet obtained can be prevented, the fall of moisture permeability can also be prevented, and adhesiveness also improves.
  • the one-minute half-life temperature of the organic peroxide is 170 ° C. or lower, it is possible to suppress a decrease in the crosslinking rate when the solar cell module is laminated, and thus it is possible to prevent a decrease in the productivity of the solar cell module.
  • the heat resistance of a sealing sheet and the fall of adhesiveness can also be prevented.
  • organic peroxide examples include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, and di-t-butyl.
  • the said organic peroxide may be used individually by 1 type, and may mix and use 2 or more types. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylper Oxy-2-ethylhexyl carbonate, t-butyl peroxybenzoate.
  • Content of the said organic peroxide in the transparent sealing sheet and colored sealing sheet which concerns on this embodiment is respectively with respect to 100 mass parts of said ethylene-type copolymers in the sheet
  • the content of the organic peroxide is not less than the above lower limit value, the cross-linking property of the sealing sheet becomes better, and the heat resistance of the sealing sheet is further improved.
  • the graft reaction of the silane coupling agent to the main chain of the ethylene-based copolymer is further improved, and the heat resistance and adhesiveness are further improved.
  • the content of the organic peroxide is not more than the above upper limit value, the above cross-linking characteristics, heat resistance, and adhesiveness are better, and further gelation during sheet molding can be further suppressed, and the appearance is more A good sealing sheet can be obtained. Furthermore, the generation amount of the decomposition product of the organic peroxide is further reduced, and the generation of bubbles in the sealing sheet can be further suppressed.
  • the transparent sealing sheet and the colored sealing sheet according to the present embodiment may contain a crosslinking aid from the viewpoint of improving the crosslinkability.
  • a crosslinking aid from the viewpoint of improving the crosslinkability.
  • the 1 type (s) or 2 or more types selected from the group which consists of a divinyl aromatic compound, a cyanurate compound, a diallyl compound, an acrylate compound, a triallyl compound, an oxime compound, and a maleimide compound can be used, for example.
  • the content of the crosslinking aid in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 3.0 masses per 100 parts by mass of the ethylene copolymer in the sheet containing the crosslinking aid. It is preferably no greater than 2.0 parts, more preferably no greater than 2.0 parts by mass, and particularly preferably no greater than 1.5 parts by mass.
  • the content of the crosslinking aid in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 0. 100 parts by mass with respect to 100 parts by mass of the ethylene copolymer in the sheet containing the crosslinking aid.
  • the amount is preferably 1 part by mass or more, more preferably 0.3 part by mass or more, and particularly preferably 0.5 part by mass or more. Thereby, it can be set as a moderate crosslinked structure and can improve the heat resistance of a sealing sheet, a mechanical physical property, and adhesiveness.
  • Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
  • Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
  • Examples of diallyl compounds include diallyl phthalate.
  • Examples of the triallyl compound include pentaerythritol triallyl ether.
  • Examples of the acrylate compound include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and tetramethylolmethane.
  • Examples include tetra (meth) acrylate and tetramethylolmethane tetra (meth) acrylate.
  • Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
  • Examples of the maleimide compound include m-phenylene dimaleimide.
  • crosslinking aid a compound having at least three functional crosslinkable unsaturated bonds such as a vinyl group is preferable.
  • a compound having at least three functional crosslinkable unsaturated bonds such as a vinyl group is preferable.
  • Propane tetra (meth) acrylate is preferred because it has good crosslinkability.
  • the transparent sealing sheet and the colored sealing sheet according to this embodiment may further contain at least one additive selected from an ultraviolet absorber, a light stabilizer, and a heat resistance stabilizer.
  • the total amount of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the sheet containing these additives. It is more preferable to contain at least two types of additives selected from the above three types, and it is particularly preferable that all the three types are included.
  • the blending amount of the additive is within the above range, it is possible to sufficiently ensure the effect of improving weather resistance stability and heat stability, and to prevent a decrease in adhesion to the solar cell element and the back surface side protection member. It is preferable because it is possible.
  • Examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2- Benzophenone ultraviolet absorbers such as carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate Select from UV absorbers, etc. It is the one or may be used two or more.
  • Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3. , 5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ]
  • the like selected from hindered amine compounds, hindered piperidine compounds and the like can be used.
  • heat stabilizers examples include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phosphite-based antioxidants such as phites; Lactone-based antioxidants such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′ , 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-
  • the manufacturing method of the transparent sealing sheet and the colored sealing sheet according to this embodiment is not particularly limited, but various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) Can be adopted. In particular, extrusion molding and calendar molding are preferable.
  • the manufacturing method of the transparent sealing sheet and colored sealing sheet which concern on this embodiment is not specifically limited, For example, the following methods are mentioned.
  • ethylene copolymer, silane coupling agent, colorant, cross-linking agent, cross-linking aid, UV absorber, light stabilizer, heat stabilizer, and other additives as required
  • the agent is blended manually in a bag such as a plastic bag or by using a stirring mixer such as a Henschel mixer, a tumbler, or a super mixer.
  • the obtained resin composition is put into, for example, a hopper of an extrusion sheet molding machine, and the resin composition is extruded into a sheet form from a T-die of the extrusion sheet molding machine while performing melt kneading to obtain a sealing sheet.
  • a part of additive can also be added in the middle of melt-kneading after throwing into an extrusion sheet molding machine.
  • calendar forming may be employed. The molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
  • the solar cell back surface side sealing sheet set which concerns on this embodiment is used in order to seal the non-light-receiving surface side of a solar cell element in a solar cell module.
  • a structure of a solar cell module the structure which laminated
  • seat back surface side protective member
  • the solar cell module 10 includes a front surface side transparent protective member 14, a back surface side protective member (back sheet) 15, a solar cell element 13, and the solar cell element 13 formed of a front surface side transparent protective member 14 and a back surface side protective member 15. And a sealing layer 1 for sealing between them.
  • the sealing layer 1 includes a light receiving surface side sealing layer 11 arranged on the light receiving surface side and a back surface side sealing layer 12 arranged on the non-light receiving surface side, and the back surface side sealing layer 12 is related to the present embodiment. It is formed by a solar cell back side sealing sheet set.
  • the back side transparent sealing layer 12A comprised by the transparent sealing sheet which concerns on this embodiment is arrange
  • the sealing layer 12B is disposed on the back surface side protection member 15 side.
  • the back side transparent sealing layer 12 ⁇ / b> A is formed from the viewpoint of improving the adhesion of the back side sealing layer 12 to the solar cell element 13 and the back side protection member 15. It is preferably in contact with the battery element 13 and the back side colored sealing layer 12B is in contact with the back side protection member 15.
  • solar cell element 13 examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductors such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium.
  • Various solar cell elements such as a system can be used.
  • the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
  • Examples of the surface-side transparent protective member 14 include a glass plate; a resin plate formed of acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
  • back surface side protection member (back sheet) 15 examples include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
  • the back surface side protection member 15 may be a single layer or a multilayer.
  • the laminated glass type solar cell module using a glass plate for the front surface side transparent protective member 14 and the back surface side protective member 15 is excellent in moisture resistance, a general sun using a resin sheet or the like for the back surface side protective member 15. Long-term reliability is superior to battery modules.
  • a glass plate is excellent in light transmittance but inferior in light reflectivity, a laminated glass type solar cell module generally has a problem that it is inferior in power generation efficiency.
  • the conversion efficiency of the solar cell module can be improved by the light reflectivity of the colored encapsulating sheet by using the solar cell back surface side sealing sheet set according to the present embodiment, the laminated glass solar cell module has a power generation efficiency. It is possible to solve the above problems.
  • the laminated glass type solar cell module which concerns on this embodiment excellent in the balance of long-term reliability and electric power generation efficiency is realizable. That is, the solar cell back surface side sealing sheet set can be suitably used for a laminated glass solar cell module using glass plates for the front surface side transparent protective member 14 and the back surface side protective member 15. Moreover, as a glass plate used for the surface side transparent protection member 14 and the back surface side protection member 15, the glass plate generally used for the laminated glass type solar cell module or laminated glass can be used.
  • the manufacturing method of the solar cell module 10 which concerns on this embodiment is not specifically limited, For example, the following method is mentioned.
  • a plurality of solar cell elements 13 electrically connected using the interconnector 16 are sandwiched between a solar cell light-receiving surface side sealing sheet and a solar cell back surface side sealing sheet, and further, these solar cell light-receiving surface side sealing sheets
  • a solar cell back surface side sealing sheet is sandwiched between the front surface side transparent protective member 14 and the back surface side protective member 15 to produce a laminate.
  • the solar cell element 13 is heated while being sandwiched between the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet, and the solar cell element 13 is heated to the solar cell light-receiving surface side sealing sheet and the solar cell back surface side. It seals between sealing sheets. That is, the obtained laminate is heated to cross-link the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet, respectively, to form the light-receiving surface side sealing layer 11 and the back surface side sealing layer 12, respectively. Thus, the solar cell element 13 is sealed between the light receiving surface side sealing layer 11 and the back surface side sealing layer 12.
  • the light receiving surface side sealing layer 11 and the back surface side sealing layer 12, the light receiving surface side sealing layer 11 and the front surface side transparent protective member 14, and the back surface side sealing layer 12 and the back surface side protective member 15 are bonded.
  • the solar cell back surface side sealing sheet set which concerns on this embodiment is used for a solar cell back surface side sealing sheet, and forms the back surface side sealing layer 12.
  • FIG. More specifically, the solar cell is heated to a temperature at which the crosslinking agent contained in the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet does not substantially decompose and the ethylene copolymer melts.
  • the battery light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet are heated, the light receiving surface side sealing layer 11 and the back surface side sealing layer 12, the light receiving surface side sealing layer 11 and the surface side transparent protective member 14, and the back surface.
  • the side sealing layer 12 and the back surface side protection member 15 are temporarily bonded to each other.
  • the temperature is raised, sufficient adhesion is performed, and the ethylene copolymer in the sealing layer is further crosslinked.
  • the bonding and crosslinking temperature may be any temperature at which a satisfactory crosslinking rate can be obtained and swelling does not occur, and can be in the temperature range of about 100 to 180 ° C., for example.
  • the transparent sealing sheet and colored sealing sheet which concern on this embodiment are prepared separately, and the solar cell element 13 is sealed between the light-receiving surface side sealing layer 11 and the back surface side sealing layer 12.
  • Ethylene / ⁇ -olefin copolymer As the ethylene / ⁇ -olefin copolymer, Tafmer (registered trademark) A-4070S, A-4085S, and A-1085S manufactured by Mitsui Chemicals, Inc. were used. Table 1 shows the physical properties of the ethylene / ⁇ -olefin copolymer used.
  • each resin composition was obtained by blending with the formulation shown in Table 2.
  • the obtained resin composition was respectively extruded into a sealing sheet with a T-die extruder.
  • the unit of the mixture ratio of each component in Table 2 is a mass part.
  • the details of each component other than the ethylene / ⁇ -olefin copolymer in Table 2 are as follows.
  • -Ethylene / vinyl acetate copolymer 1 content ratio of structural units derived from vinyl acetate: 28% by mass, MFR: 15 g / 10 min, density: 0.950 g / cm 3
  • Silane coupling agent 1 3-methacryloxypropyl trimethoxysilane
  • Colorant 1 Titanium oxide
  • Crosslinking agent 1 t-butylperoxy-2-ethylhexyl carbonate
  • Crosslinking aid 1 Triallyl isocyanurate
  • the sealing sheet shown in Table 3 was laminated on the solar cell element, placed on a hot plate adjusted to 150 ° C. in a vacuum laminator, vacuumed for 3 minutes, and then heated for 10 minutes. Thereby, the laminated body of the solar cell element / sealing sheet was produced.
  • each sealing sheet was laminated
  • the sealing sheet on this laminated body was cut into a width of 10 mm, and the peel strength by 180 degree peeling with respect to the solar cell element as the adherend was measured. The peel strength by 180 degree peel was measured at 23 ° C.
  • the transparent sealing sheet was made into the solar cell element side.
  • the sealing sheet shown in Table 3 was laminated on the back-side protective member (glass), placed on a hot plate adjusted to 150 ° C. in a vacuum laminator, vacuum-reduced for 3 minutes, and then heated for 10 minutes. Thereby, the laminated body of the back surface side protection member / sealing sheet was produced.
  • each sealing sheet was laminated
  • the sealing sheet on this laminated body was cut into a width of 10 mm, and the peel strength by 180 degree peeling with respect to the back surface side protective member as the adherend was measured. The peel strength by 180 degree peel was measured at 23 ° C.
  • the solar cell back surface side sealing sheet set of the example including the transparent sealing sheet and the colored sealing sheet is excellent in the temporal stability of the adhesiveness to the solar cell element and the back surface side protection member. It was.
  • the solar cell back side sealing sheet set of Comparative Example 1 using only the colored sealing sheet, and the multilayer sealing sheet of Comparative Example 2 prepared by previously laminating a transparent sealing sheet and a colored sealing sheet are: It was inferior to the temporal stability of the adhesiveness to the solar cell element and the back surface side protective member.

Abstract

This solar cell rear surface sealant sheet set is positioned between a solar cell element and a rear-side protective member, is used to seal the non-light-receiving side of the solar cell element, and is equipped with a transparent sealant sheet and a colored sealant sheet. The transparent sealant sheet contains at least one type of ethylene copolymer selected from an ethylene alpha-olefin copolymer and an ethylene polar monomer copolymer, and is positioned on the solar cell element side. The colored sealant sheet contains a coloring agent and at least one type of ethylene copolymer selected from an ethylene alpha-olefin copolymer and an ethylene polar monomer copolymer, and is positioned on the rear-side protective member side. When sealing the solar cell element, the transparent sealant sheet and the colored sealant sheet are used by being laminated to one another.

Description

太陽電池裏面側封止シートセット、太陽電池モジュールおよび太陽電池モジュールの製造方法Solar cell back side sealing sheet set, solar cell module, and method for manufacturing solar cell module
　本発明は、太陽電池裏面側封止シートセット、太陽電池モジュールおよび太陽電池モジュールの製造方法に関する。 The present invention relates to a solar cell back side sealing sheet set, a solar cell module, and a method for manufacturing a solar cell module.
　地球環境問題やエネルギーの問題等が深刻さを増す中、クリーンかつ枯渇の恐れの無いエネルギー生成手段として太陽電池が注目されている。太陽電池を建物の屋根部分等の屋外で使用する場合、太陽電池モジュールの形で使用することが一般的である。 As solar environment problems and energy problems become more serious, solar cells are attracting attention as a means of generating energy that is clean and free from depletion. When a solar cell is used outdoors such as a roof portion of a building, it is generally used in the form of a solar cell module.
　太陽電池モジュールは、例えば、以下の手順によって製造される。
　まず、太陽電池モジュール用保護シート（表面側透明保護部材）／太陽電池封止材（以下、シート状の太陽電池封止材を封止シートとも呼ぶ。）／太陽電池素子／太陽電池封止材／太陽電池モジュール用保護シート（裏面側保護部材）の順に積層する。
　その後、これらを真空吸引して加熱圧着するラミネーション法等を利用することにより、太陽電池モジュールが製造される。このようにして製造される太陽電池モジュールは、耐候性を有し、建物の屋根部分等の屋外での使用にも適したものとなっている。 A solar cell module is manufactured by the following procedures, for example.
First, a protective sheet for a solar cell module (surface-side transparent protective member) / solar cell sealing material (hereinafter, a sheet-like solar cell sealing material is also referred to as a sealing sheet) / solar cell element / solar cell sealing material. / Laminate in order of solar cell module protective sheet (back side protective member).
Then, a solar cell module is manufactured by utilizing the lamination method etc. which vacuum-suck these and heat-press them. The solar cell module manufactured in this way has weather resistance and is suitable for outdoor use such as a roof portion of a building.
　太陽電池素子を封止するために使用される封止シートには、例えば、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のエチレン系共重合体が用いられている（例えば、特許文献１～３参照）。 For the sealing sheet used for sealing the solar cell element, for example, an ethylene-based copolymer such as an ethylene / α-olefin copolymer or an ethylene / polar monomer copolymer is used (for example, Patent Documents 1 to 3).
特開２０１０－５３２９８号公報JP 2010-53298 A 特開２００６－２１０９０６号公報JP 2006-210906 A 国際公開第２０１１／１６２３２４号International Publication No. 2011/162324
　ここで、光反射能により太陽電池モジュールの変換効率を向上させたり、封止シートの意匠性や熱伝導性等を向上させたりする観点から、太陽電池素子の非受光面側（以下、裏面側とも呼ぶ。）には着色剤を含む着色封止シートが用いられることがある。
　しかし、本発明者らの検討によれば、太陽電池素子の非受光面側に用いられ、エチレン系共重合体および着色剤を含む着色封止シートは、成形後からラミネートされるまでの間に太陽電池素子や裏面側保護部材に対する接着性が経時的に低下してしまうことが明らかになった。 Here, from the viewpoint of improving the conversion efficiency of the solar cell module by the light reflectivity or improving the designability or thermal conductivity of the sealing sheet, the non-light-receiving surface side (hereinafter referred to as the back surface side) of the solar cell element In some cases, a colored sealing sheet containing a colorant is used.
However, according to the study by the present inventors, the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene-based copolymer and the colorant is between after being molded and laminated. It became clear that the adhesiveness with respect to a solar cell element and a back surface side protection member will fall with time.
　本発明は、上記事情に鑑みてなされたものであり、太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に優れた太陽電池裏面側封止シートを提供するものである。 The present invention has been made in view of the above circumstances, and provides a solar cell back surface side sealing sheet excellent in temporal stability of adhesiveness to the solar cell element and the back surface side protection member.
　本発明者らは、太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に優れた太陽電池裏面側封止シートを実現するために鋭意検討した。その結果、本発明者らは、着色剤を含まない透明封止シートと、着色剤を含む着色封止シートと、を別々に準備し、太陽電池素子を封止する段階でこれらのシートを積層し、さらに透明封止シートを太陽電池素子側に配置し、着色封止シートを裏面側保護部材側に配置して使用することにより、太陽電池素子および裏面側保護部材に対する太陽電池裏面側封止シートの接着性の経時的安定性を向上できることを見出した。 The inventors of the present invention diligently studied to realize a solar cell back surface side sealing sheet excellent in the temporal stability of adhesiveness to the solar cell element and the back surface side protection member. As a result, the present inventors separately prepared a transparent encapsulating sheet containing no colorant and a colored encapsulating sheet containing a colorant, and laminating these sheets at the stage of sealing the solar cell element. Furthermore, the transparent encapsulating sheet is disposed on the solar cell element side, and the colored encapsulating sheet is disposed on the back surface side protective member side to be used, whereby the solar cell back surface side sealing with respect to the solar cell element and the back surface side protective member It has been found that the stability over time of the adhesiveness of the sheet can be improved.
　すなわち、本発明によれば、以下に示す太陽電池裏面側封止シートセット、太陽電池モジュールおよび太陽電池モジュールの製造方法が提供される。 That is, according to the present invention, the following solar cell back side sealing sheet set, solar cell module, and solar cell module manufacturing method are provided.
［１］
　太陽電池素子と裏面側保護部材との間に配置させて上記太陽電池素子の非受光面側を封止するために用いられ、透明封止シートと着色封止シートとを備える太陽電池裏面側封止シートセットであって、
　上記透明封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体を含み、かつ、上記太陽電池素子側に配置されるものであり、
　上記着色封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体と着色剤とを含み、かつ、上記裏面側保護部材側に配置されるものであり、
　上記太陽電池素子を封止する際に上記透明封止シートと上記着色封止シートとを積層させて使用する太陽電池裏面側封止シートセット。
［２］
　上記［１］に記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートの厚みが１００μｍ以上である太陽電池裏面側封止シートセット。
［３］
　上記［１］または［２］に記載の太陽電池裏面側封止シートセットにおいて、
　上記着色封止シートに含まれる上記着色剤が酸化チタン、カーボンブラックおよび赤外線反射顔料から選択される少なくとも一種を含む太陽電池裏面側封止シートセット。
［４］
　上記［３］に記載の太陽電池裏面側封止シートセットにおいて、
　上記着色封止シート中の上記着色剤の含有量が、上記着色封止シート中の上記エチレン系共重合体１００質量部に対して、０．５質量部以上５０質量部以下である太陽電池裏面側封止シートセット。
［５］
　上記［１］乃至［４］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートがシランカップリング剤を含む太陽電池裏面側封止シートセット。
［６］
　上記［５］に記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シート中の上記シランカップリング剤の含有量が、上記透明封止シート中の上記エチレン系共重合体１００質量部に対して、０．０１質量部以上５質量部以下である太陽電池裏面側封止シートセット。
［７］
　上記［１］乃至［６］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートおよび上記着色封止シートの少なくとも一方が上記エチレン系共重合体として上記エチレン・α－オレフィン共重合体を含み、上記エチレン・α－オレフィン共重合体が以下の要件ａ１）およびａ２）のうち少なくとも１つを満たす太陽電池裏面側封止シートセット。
　ａ１）ＡＳＴＭ　Ｄ１５０５に準拠して測定される密度が０．８６５～０．８９５ｇ／ｃｍ３である。
　ａ２）ＡＳＴＭ　Ｄ２２４０に準拠して測定されるショアＡ硬度が６０～９５である。
［８］
　上記［１］乃至［６］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートおよび上記着色封止シートの少なくとも一方が上記エチレン系共重合体として上記エチレン・極性モノマー共重合体を含み、
　上記エチレン・極性モノマー共重合体がエチレン・酢酸ビニル共重合体を含む太陽電池裏面側封止シートセット。
［９］
　上記［８］に記載の太陽電池裏面側封止シートセットにおいて、
　上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合が１０質量％以上４７質量％以下である太陽電池裏面側封止シートセット。
［１０］
　上記［１］乃至［９］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定される、上記着色封止シートに含まれる上記エチレン系共重合体のＭＦＲが０．０１ｇ／１０分以上３０ｇ／１０分以下である太陽電池裏面側封止シートセット。
［１１］
　上記［１］乃至［１０］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートおよび上記着色封止シートの少なくとも一方が有機過酸化物をさらに含む太陽電池裏面側封止シートセット。
［１２］
　上記［１１］に記載の太陽電池裏面側封止シートセットにおいて、
　上記有機過酸化物の含有量が、上記有機過酸化物を含むシート中の上記エチレン系共重合体１００質量部に対して、０．１質量部以上３質量部以下である太陽電池裏面側封止シートセット。
［１３］
　上記［１］乃至［１２］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記透明封止シートが上記太陽電池素子に接するように配置され、上記着色封止シートが上記裏面側保護部材に接するように配置される太陽電池裏面側封止シートセット。
［１４］
　上記［１］乃至［１３］のいずれか一つに記載の太陽電池裏面側封止シートセットにおいて、
　上記裏面側保護部材がガラス板である太陽電池裏面側封止シートセット。
［１５］
　表面側透明保護部材と、
　裏面側保護部材と、
　太陽電池素子と、
　上記太陽電池素子を上記表面側透明保護部材と上記裏面側保護部材との間に封止する封止層と、
を備え、
　上記封止層が受光面側に配置される受光面側封止層と非受光面側に配置される裏面側封止層とを含み、
　上記裏面側封止層が上記［１］乃至［１４］のいずれか一つに記載の太陽電池裏面側封止シートセットにより形成されており、
　上記透明封止シートにより構成された裏面側透明封止層が上記太陽電池素子側に配置されており、上記着色封止シートにより構成された裏面側着色封止層が上記裏面側保護部材側に配置されている太陽電池モジュール。
［１６］
　上記［１５］に記載の太陽電池モジュールにおいて、
　上記裏面側透明封止層が上記太陽電池素子に接しており、上記裏面側着色封止層が上記裏面側保護部材に接している太陽電池モジュール。
［１７］
　上記［１５］または［１６］に記載の太陽電池モジュールにおいて、
　上記表面側透明保護部材および上記裏面側保護部材がそれぞれガラス板であり、
　当該太陽電池モジュールが合わせガラス型太陽電池モジュールである太陽電池モジュール。
［１８］
　上記［１５］乃至［１７］のいずれか一つに記載の太陽電池モジュールを製造するための製造方法であって、
　上記太陽電池素子を太陽電池受光面側封止シートと太陽電池裏面側封止シートとで挟んだ状態で加熱し、上記太陽電池素子を上記太陽電池受光面側封止シートと上記太陽電池裏面側封止シートとの間に封止する工程を含み、
　上記太陽電池裏面側封止シートが上記［１］乃至［１４］のいずれか一つに記載の太陽電池裏面側封止シートセットを含み、
　上記透明封止シートと上記着色封止シートとを別々に準備し、上記太陽電池素子を封止する上記工程において、上記透明封止シートと上記着色封止シートとを積層する太陽電池モジュールの製造方法。 [1]
Solar cell back side sealing provided with a transparent sealing sheet and a colored sealing sheet, which is used for sealing the non-light-receiving surface side of the solar cell element disposed between the solar cell element and the back surface side protective member. Stop sheet set,
The transparent encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer, and is disposed on the solar cell element side. Yes,
The colored encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer, and a colorant, and on the back side protective member side Is to be placed,
The solar cell back surface side sealing sheet set which laminates and uses the said transparent sealing sheet and the said colored sealing sheet when sealing the said solar cell element.
[2]
In the solar cell back surface side sealing sheet set according to the above [1],
The solar cell back surface side sealing sheet set whose thickness of the said transparent sealing sheet is 100 micrometers or more.
[3]
In the solar cell back surface side sealing sheet set according to [1] or [2] above,
The solar cell back surface side sealing sheet set in which the said coloring agent contained in the said colored sealing sheet contains at least 1 type selected from a titanium oxide, carbon black, and an infrared reflective pigment.
[4]
In the solar cell back side sealing sheet set according to [3] above,
The back surface of the solar cell in which the content of the colorant in the colored encapsulating sheet is 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the colored encapsulating sheet. Side sealing sheet set.
[5]
In the solar cell back surface side sealing sheet set according to any one of [1] to [4] above,
The solar cell back surface side sealing sheet set in which the said transparent sealing sheet contains a silane coupling agent.
[6]
In the solar cell back side sealing sheet set according to [5] above,
The sun whose content of the said silane coupling agent in the said transparent sealing sheet is 0.01 mass part or more and 5 mass parts or less with respect to 100 mass parts of the said ethylene-type copolymers in the said transparent sealing sheet. Battery back side sealing sheet set.
[7]
In the solar cell back surface side sealing sheet set according to any one of [1] to [6] above,
At least one of the transparent sealing sheet and the colored sealing sheet contains the ethylene / α-olefin copolymer as the ethylene copolymer, and the ethylene / α-olefin copolymer has the following requirements a1) and The solar cell back surface side sealing sheet set which satisfy | fills at least 1 among a2).
a1) The density measured according to ASTM D1505 is 0.865 to 0.895 g / cm 3 .
a2) Shore A hardness measured according to ASTM D2240 is 60-95.
[8]
In the solar cell back surface side sealing sheet set according to any one of [1] to [6] above,
At least one of the transparent sealing sheet and the colored sealing sheet includes the ethylene / polar monomer copolymer as the ethylene copolymer,
The solar cell back side sealing sheet set in which the ethylene / polar monomer copolymer contains an ethylene / vinyl acetate copolymer.
[9]
In the solar cell back side sealing sheet set according to [8] above,
The solar cell back surface side sealing sheet set whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less.
[10]
In the solar cell back surface side sealing sheet set according to any one of [1] to [9],
In accordance with ASTM D1238, the MFR of the ethylene-based copolymer contained in the colored sealing sheet measured at 190 ° C. and a load of 2.16 kg is 0.01 g / 10 min to 30 g / 10 min. A solar cell back side sealing sheet set.
[11]
In the solar cell back side sealing sheet set according to any one of [1] to [10],
The solar cell back surface side sealing sheet set in which at least one of the transparent sealing sheet and the colored sealing sheet further contains an organic peroxide.
[12]
In the solar cell back surface side sealing sheet set according to [11] above,
The solar cell back surface side sealing whose content of the said organic peroxide is 0.1 to 3 mass parts with respect to 100 mass parts of the said ethylene-type copolymer in the sheet | seat containing the said organic peroxide. Stop sheet set.
[13]
In the solar cell back side sealing sheet set according to any one of [1] to [12] above,
The solar cell back surface side sealing sheet set arrange | positioned so that the said transparent sealing sheet may contact | connect the said solar cell element, and the said colored sealing sheet may contact | connect the said back surface side protection member.
[14]
In the solar cell back surface side sealing sheet set according to any one of [1] to [13],
The solar cell back surface side sealing sheet set whose said back surface side protection member is a glass plate.
[15]
A surface-side transparent protective member;
A back side protection member;
A solar cell element;
A sealing layer for sealing the solar cell element between the front surface side transparent protective member and the back surface side protective member;
With
The sealing layer includes a light receiving surface side sealing layer disposed on the light receiving surface side and a back surface side sealing layer disposed on the non-light receiving surface side,
The back surface side sealing layer is formed by the solar cell back surface side sealing sheet set according to any one of the above [1] to [14],
The back side transparent sealing layer comprised by the said transparent sealing sheet is arrange | positioned at the said solar cell element side, and the back side colored sealing layer comprised by the said colored sealing sheet is on the said back side protection member side Solar cell module being placed.
[16]
In the solar cell module according to [15] above,
The solar cell module, wherein the back-side transparent sealing layer is in contact with the solar cell element, and the back-side colored sealing layer is in contact with the back-side protection member.
[17]
In the solar cell module according to the above [15] or [16],
Each of the front surface side transparent protective member and the back surface side protective member is a glass plate,
A solar cell module in which the solar cell module is a laminated glass solar cell module.
[18]
A manufacturing method for manufacturing the solar cell module according to any one of [15] to [17],
The solar cell element is heated in a state sandwiched between the solar cell light receiving surface side sealing sheet and the solar cell back surface side sealing sheet, and the solar cell element is heated to the solar cell light receiving surface side sealing sheet and the solar cell back surface side. Including a step of sealing between the sealing sheet,
The solar cell back surface side sealing sheet includes the solar cell back surface side sealing sheet set according to any one of the above [1] to [14],
In the above step of separately preparing the transparent sealing sheet and the colored sealing sheet and sealing the solar cell element, the solar cell module is manufactured by laminating the transparent sealing sheet and the colored sealing sheet. Method.
　本発明によれば、太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に優れた太陽電池裏面側封止シートを実現することができる。 According to the present invention, it is possible to realize a solar cell back side sealing sheet excellent in the temporal stability of adhesiveness to the solar cell element and the back side protective member.
　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.
本発明の太陽電池モジュールの代表的な実施形態を模式的に示した断面図である。It is sectional drawing which showed typically embodiment of the solar cell module of this invention typically.
　以下、本発明の実施の形態について、図面を用いて説明する。なお、数値範囲の「Ａ～Ｂ」は特に断りがなければ、Ａ以上Ｂ以下を表す。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. The numerical range “A to B” represents A or more and B or less unless otherwise specified.
１．太陽電池裏面側封止シートセットについて
　本実施形態に係る太陽電池裏面側封止シートセットは、太陽電池素子と裏面側保護部材との間に配置させて上記太陽電池素子の非受光面側を封止するために用いられ、かつ、透明封止シートと着色封止シートとを備える。
　上記透明封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体を含み、かつ、上記太陽電池素子側に配置されるものである。また、上記着色封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体と着色剤とを含み、かつ、上記裏面側保護部材側に配置されるものである。
　そして、本実施形態に係る太陽電池裏面側封止シートセットは、上記太陽電池素子を封止する際に上記透明封止シートと上記着色封止シートとを積層させて使用する。 1. About Solar Cell Back Side Sealing Sheet Set The solar cell back side sealing sheet set according to this embodiment is arranged between the solar cell element and the back side protective member to seal the non-light-receiving surface side of the solar cell element. It is used to stop and includes a transparent sealing sheet and a colored sealing sheet.
The transparent encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer, and is disposed on the solar cell element side. is there. The colored encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer, and a colorant, and the back side protective member It is arranged on the side.
And the solar cell back surface side sealing sheet set which concerns on this embodiment uses the said transparent sealing sheet and the said colored sealing sheet by laminating | stacking, when sealing the said solar cell element.
　前述したように、本発明者らの検討によれば、太陽電池素子の非受光面側に用いられ、エチレン系共重合体および着色剤を含む着色封止シートは、成形後からラミネートされるまでの間に太陽電池素子や裏面側保護部材に対する接着性が経時的に低下してしまうことが明らかになった。
　そこで、本発明者らは、太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に優れた太陽電池裏面側封止シートを実現するために鋭意検討した。その結果、本発明者らは、着色剤を含まない透明封止シートと、着色剤を含む着色封止シートと、を別々に準備し、太陽電池素子を封止する段階でこれらのシートを積層し、さらに透明封止シートを太陽電池素子側に配置し、着色封止シートを裏面側保護部材側に配置して使用することにより、太陽電池素子および裏面側保護部材に対する太陽電池裏面側封止シートの接着性の経時的安定性を向上できることを見出した。
　すなわち、本実施形態に係る太陽電池裏面側封止シートセットによれば、着色剤を含まない透明封止シートと着色封止シートとを太陽電池素子を封止する段階で積層して用いることにより、太陽電池素子および裏面側保護部材に対する太陽電池裏面側封止シートの接着性の経時的安定性を良好にすることができる。
　さらに、本実施形態に係る太陽電池裏面側封止シートセットによれば、着色封止シートを備えることにより光反射能により太陽電池モジュールの変換効率を向上させたり、封止シートの意匠性や熱伝導性等を向上させたりすることができる。 As described above, according to the study by the present inventors, the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene copolymer and the colorant is laminated after being molded. It became clear that the adhesiveness with respect to a solar cell element and a back surface side protection member fell with time in the meantime.
Then, the present inventors diligently studied in order to realize a solar cell back surface side sealing sheet excellent in temporal stability of adhesion to the solar cell element and the back surface side protection member. As a result, the present inventors separately prepared a transparent encapsulating sheet containing no colorant and a colored encapsulating sheet containing a colorant, and laminating these sheets at the stage of sealing the solar cell element. Furthermore, the transparent encapsulating sheet is disposed on the solar cell element side, and the colored encapsulating sheet is disposed on the back surface side protective member side to be used, whereby the solar cell back surface side sealing with respect to the solar cell element and the back surface side protective member is performed. It has been found that the stability over time of the adhesiveness of the sheet can be improved.
That is, according to the solar cell back surface side sealing sheet set which concerns on this embodiment, by laminating | stacking and using the transparent sealing sheet and coloring sealing sheet which do not contain a coloring agent in the step which seals a solar cell element. Moreover, the temporal stability of the adhesiveness of the solar cell back surface side sealing sheet to the solar cell element and the back surface side protection member can be improved.
Furthermore, according to the solar cell back surface side sealing sheet set which concerns on this embodiment, the conversion efficiency of a solar cell module is improved by light reflectivity by providing a colored sealing sheet, or the designability and heat of a sealing sheet Conductivity and the like can be improved.
　また、本発明者らの検討によれば、太陽電池素子の非受光面側に用いられ、エチレン系共重合体および着色剤を含む着色封止シートは、太陽電池モジュールを作製するときに、着色封止シートが太陽電池素子や配線等の表面へ回り込んでしまう場合があることが明らかになった。
　着色封止シートが太陽電池素子や配線等の表面側に回り込むことによって、太陽電池モジュールの歩留まりが悪化してしまったり、太陽電池素子に入射する光を遮る結果、太陽電池素子の発電性能が低下してしまったりする懸念がある。
　そこで、本発明者らは、太陽電池素子や配線等の表面への回り込みが抑制された着色封止層を実現するために鋭意検討した。その結果、本発明者らは、透明封止シートを太陽電池素子側に配置し、着色封止シートを裏面側保護部材側に配置することにより、太陽電池素子や配線等の表面への回り込みが抑制された裏面側封止層が得られることを見出した。
　すなわち、本実施形態に係る太陽電池裏面側封止シートセットによれば、透明封止シートを太陽電池素子側に配置し、着色封止シートを裏面側保護部材側に配置して用いることにより、太陽電池素子や配線等の表面への裏面側封止層の回り込みをより抑制することができる。 Further, according to the study of the present inventors, the colored sealing sheet used on the non-light-receiving surface side of the solar cell element and containing the ethylene copolymer and the colorant is colored when the solar cell module is produced. It has been clarified that the sealing sheet may wrap around the surface of the solar cell element or the wiring.
When the colored encapsulating sheet wraps around the surface side of the solar cell element or wiring, the yield of the solar cell module is deteriorated or the light incident on the solar cell element is blocked, resulting in a decrease in the power generation performance of the solar cell element. There is a concern that it may.
Then, the present inventors diligently studied in order to realize a colored sealing layer in which wraparound to the surface of a solar cell element, wiring, or the like is suppressed. As a result, the present inventors arrange the transparent sealing sheet on the solar cell element side, and arrange the colored sealing sheet on the back surface side protective member side, so that the wraparound to the surface of the solar cell element or wiring is prevented. It has been found that a suppressed back side sealing layer is obtained.
That is, according to the solar cell back side sealing sheet set according to the present embodiment, the transparent sealing sheet is disposed on the solar cell element side, and the colored sealing sheet is disposed and used on the back surface side protection member side. It is possible to further suppress the back surface side sealing layer from wrapping around the surface of the solar cell element or the wiring.
　本実施形態に係る太陽電池裏面側封止シートセットにおいて、例えば、透明封止シートが太陽電池素子に接するように配置され、着色封止シートが裏面側保護部材に接するように配置されることが好ましい。 In the solar cell back surface side sealing sheet set according to the present embodiment, for example, the transparent sealing sheet is disposed so as to be in contact with the solar cell element, and the colored sealing sheet is disposed so as to be in contact with the back surface side protection member. preferable.
　本実施形態に係る透明封止シートおよび着色封止シートの合計の厚みは特に限定されないが、２００μｍ以上２０００μｍ以下が好ましく、３００μｍ以上１２００μｍ以下がより好ましい。厚みがこの範囲内であると、ラミネート工程における、裏面側保護部材、太陽電池素子、薄膜電極等の破損が抑制できる。さらには、低温での太陽電池モジュールのラミネート成形ができるので好ましい。 The total thickness of the transparent sealing sheet and the colored sealing sheet according to this embodiment is not particularly limited, but is preferably 200 μm or more and 2000 μm or less, and more preferably 300 μm or more and 1200 μm or less. When the thickness is within this range, damage to the back surface side protective member, the solar cell element, the thin film electrode, etc. in the laminating step can be suppressed. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
　また、本実施形態に係る透明封止シートの厚みは、着色封止シートが太陽電池素子や配線等の表面へ回り込むことをより良好に抑制できる観点から、１００μｍ以上が好ましく、１３０μｍ以上がより好ましく、１８０μｍ以上がさらに好ましく、２２０μｍ以上がさらにより好ましく、２８０μｍ以上が特に好ましい。
　また、本実施形態に係る着色封止シートの厚みは、着色封止シートが太陽電池素子や配線等の表面へ回り込むことをより一層良好に抑制できる観点から、２００μｍ以下が好ましく、１５０μｍ以下がより好ましく、１２０μｍ以下が特に好ましい。 In addition, the thickness of the transparent sealing sheet according to the present embodiment is preferably 100 μm or more, more preferably 130 μm or more, from the viewpoint that the colored sealing sheet can better suppress the wrapping around the surface of the solar cell element or the wiring. 180 μm or more is more preferable, 220 μm or more is even more preferable, and 280 μm or more is particularly preferable.
In addition, the thickness of the colored sealing sheet according to the present embodiment is preferably 200 μm or less, more preferably 150 μm or less, from the viewpoint that the colored sealing sheet can more effectively prevent the colored sealing sheet from wrapping around the surface of the solar cell element or the wiring. 120 μm or less is particularly preferable.
　すなわち、透明封止シートの厚みを上記下限値以上とすることにより、太陽電池モジュールを作製するときに、着色封止シートが太陽電池素子や配線等の表面へ回り込むことをより良好に抑制することができる。
　さらに、着色封止シートの厚みを上記上限値以下とすることにより、太陽電池モジュールを作製するときに、着色封止シートが太陽電池素子や配線等の表面へ回り込むことをより一層良好に抑制することができる。 That is, by making the thickness of the transparent encapsulating sheet equal to or more than the above lower limit value, it is possible to better suppress the colored encapsulating sheet from wrapping around the surface of the solar cell element or the wiring when the solar cell module is manufactured. Can do.
Furthermore, by making the thickness of the colored encapsulating sheet equal to or less than the above upper limit value, the colored encapsulating sheet can be further suppressed from wrapping around the surface of the solar cell element, the wiring or the like when the solar cell module is manufactured. be able to.
　以下、本実施形態に係る透明封止シートおよび着色封止シートを構成する各成分について説明する。 Hereinafter, each component which comprises the transparent sealing sheet and colored sealing sheet which concern on this embodiment is demonstrated.
＜エチレン系共重合体＞
　本実施形態に係る透明封止シートおよび着色封止シートは必須成分としてエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体を含む。 <Ethylene copolymer>
The transparent sealing sheet and the colored sealing sheet according to this embodiment contain at least one ethylene-based copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer as essential components.
　本実施形態に係る透明封止シートおよび着色封止シートにおいて、上記エチレン系共重合体の含有量は、当該透明封止シートおよび着色封止シートにそれぞれ含まれる樹脂成分の全体を１００質量％としたとき、それぞれ、好ましくは８０質量％以上、より好ましくは９０質量％以上、さらに好ましくは９５質量％以上、そして、特に好ましくは１００質量％である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた封止シートを得ることができる。 In the transparent sealing sheet and the colored sealing sheet according to the present embodiment, the content of the ethylene copolymer is 100% by mass of the entire resin component contained in the transparent sealing sheet and the colored sealing sheet, respectively. Respectively, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass. Thereby, the sealing sheet excellent in the balance of various characteristics, such as transparency, adhesiveness, heat resistance, a softness | flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
　本実施形態に係る透明封止シートにおいて、上記樹脂成分の含有量は、当該透明封止シートの全体を１００質量％としたとき、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上、特に好ましくは９５質量％以上である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた透明封止シートを得ることができる。
　また、本実施形態に係る着色封止シートにおいて、上記樹脂成分の含有量は、当該着色封止シートの全体を１００質量％としたとき、好ましくは４０質量％以上、より好ましくは５０質量％以上、さらに好ましくは６０質量％以上、特に好ましくは７０質量％以上である。これにより、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた着色封止シートを得ることができる。 In the transparent encapsulating sheet according to the present embodiment, the content of the resin component is preferably 70% by mass or more, more preferably 80% by mass or more, further when the entire transparent encapsulating sheet is 100% by mass. Preferably it is 90 mass% or more, Most preferably, it is 95 mass% or more. Thereby, the transparent sealing sheet excellent in balance of various characteristics, such as transparency, adhesiveness, heat resistance, a softness | flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
Moreover, in the colored sealing sheet according to the present embodiment, the content of the resin component is preferably 40% by mass or more, more preferably 50% by mass or more when the entire colored sealing sheet is 100% by mass. More preferably, it is 60% by mass or more, and particularly preferably 70% by mass or more. Thereby, the coloring sealing sheet excellent in the balance of various characteristics, such as adhesiveness, heat resistance, a softness | flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
　本実施形態に係る透明封止シートにおいて、ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定されるエチレン系共重合体のメルトフローレ－ト（ＭＦＲ）は、例えば０．１ｇ／１０分以上５０ｇ／１０分以下であり、好ましくは１ｇ／１０分以上４０ｇ／１０分以下であり、より好ましくは２ｇ／１０分以上３０ｇ／１０分以下であり、さらに好ましくは５ｇ／１０分以上１０ｇ／１０分以下である。 In the transparent encapsulating sheet according to the present embodiment, the melt flow rate (MFR) of the ethylene copolymer measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238 is, for example, 0.1 g / It is 10 minutes or more and 50 g / 10 minutes or less, preferably 1 g / 10 minutes or more and 40 g / 10 minutes or less, more preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less, and further preferably 5 g / 10 minutes or more. It is 10 g / 10 minutes or less.
　また、本実施形態に係る着色封止シートにおいて、ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定されるエチレン系共重合体のメルトフローレ－ト（ＭＦＲ）は、例えば０．０１ｇ／１０分以上３０ｇ／１０分以下、より好ましくは０．０５ｇ／１０分以上１０ｇ／１０分以下、特に好ましくは０．５ｇ／１０分以上５．０ｇ／１０分未満である。
　また、本実施形態に係る着色封止シートにおいて、ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定されるエチレン系共重合体のＭＦＲの下限値は、着色封止シートの加工性の観点から、好ましくは０．０５ｇ／１０分以上、より好ましくは０．１ｇ／１０分以上、さらに好ましくは０．２ｇ／１０分以上、特に好ましくは０．５ｇ／１０分以上である。
　また、本実施形態に係る着色封止シートにおいて、ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定されるエチレン系共重合体のＭＦＲの上限値は、着色封止シートが太陽電池素子や配線等の表面へ回り込むことをより良好に抑制できる観点から、好ましくは５．０ｇ／１０分未満、より好ましくは４．０ｇ／１０分未満、さらに好ましくは３．０ｇ／１０分未満、特に好ましくは２．０ｇ／１０分未満である。 Further, in the colored sealing sheet according to the present embodiment, the melt flow rate (MFR) of the ethylene-based copolymer measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238 is, for example, 0.8. The amount is from 01 g / 10 min to 30 g / 10 min, more preferably from 0.05 g / 10 min to 10 g / 10 min, particularly preferably from 0.5 g / 10 min to less than 5.0 g / 10 min.
Further, in the colored encapsulating sheet according to the present embodiment, the lower limit value of the MFR of the ethylene copolymer measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238 is the processing of the colored encapsulating sheet. From the viewpoint of properties, it is preferably 0.05 g / 10 min or more, more preferably 0.1 g / 10 min or more, further preferably 0.2 g / 10 min or more, particularly preferably 0.5 g / 10 min or more.
Further, in the colored encapsulating sheet according to the present embodiment, the upper limit value of the MFR of the ethylene copolymer measured under the conditions of 190 ° C. and 2.16 kg load is based on ASTM D1238. From the viewpoint of better suppressing the wrapping around the surface of the battery element, wiring, etc., it is preferably less than 5.0 g / 10 minutes, more preferably less than 4.0 g / 10 minutes, and even more preferably less than 3.0 g / 10 minutes. Particularly preferably, it is less than 2.0 g / 10 minutes.
　エチレン系共重合体のＭＦＲは、重合反応の際の重合温度、重合圧力、並びに重合系内のエチレンのモノマー濃度と水素濃度のモル比率等を調整することにより、調整することができる。 The MFR of the ethylene copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, the molar ratio of the ethylene monomer concentration to the hydrogen concentration in the polymerization system, and the like.
（エチレン・α－オレフィン共重合体）
　本実施形態に係るエチレン・α－オレフィン共重合体は、例えば、エチレンと、炭素数３～２０のα－オレフィンとを共重合することによって得られる。α－オレフィンとしては、通常、炭素数３～２０のα－オレフィンを１種類単独でまたは２種類以上を組み合わせて用いることができる。
　炭素数３～２０のα－オレフィンとしては、直鎖状または分岐状のα－オレフィン、例えば、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、３－メチル－１－ブテン、３，３－ジメチル－１－ブテン、４－メチル－１－ペンテン、１－オクテン、１－デセン、１－ドデセン等を挙げることができる。これらの中でも好ましいのは、炭素数が１０以下であるα－オレフィンであり、特に好ましいのは炭素数が３～８のα－オレフィンである。入手の容易さからプロピレン、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテンおよび１－オクテンが好ましい。なお、エチレン・α－オレフィン共重合体はランダム共重合体であっても、ブロック共重合体であってもよいが、柔軟性の観点からランダム共重合体が好ましい。 (Ethylene / α-olefin copolymer)
The ethylene / α-olefin copolymer according to this embodiment can be obtained, for example, by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin, α-olefins having 3 to 20 carbon atoms can be used singly or in combination of two or more.
Examples of the α-olefin having 3 to 20 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3, 3 -Dimethyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Among these, α-olefins having 10 or less carbon atoms are preferable, and α-olefins having 3 to 8 carbon atoms are particularly preferable. Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred because of their availability. The ethylene / α-olefin copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferred from the viewpoint of flexibility.
　さらに、上記エチレン・α－オレフィン共重合体は、エチレンと、炭素数３～２０のα－オレフィンと非共役ポリエンとを含む共重合体であってもよい。α－オレフィンは前述と同様であって、非共役ポリエンとしては、５－エチリデン－２－ノルボルネン（ＥＮＢ）、５－ビニル－２－ノルボルネン（ＶＮＢ）、ジシクロペンタジエン（ＤＣＰＤ）等が挙げられる。これら非共役ポリエンを１種単独、または２種以上を組み合わせて用いることができる。 Furthermore, the ethylene / α-olefin copolymer may be a copolymer containing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. The α-olefin is the same as described above, and examples of the non-conjugated polyene include 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and dicyclopentadiene (DCPD). These non-conjugated polyenes can be used alone or in combination of two or more.
　上記エチレン・α－オレフィン共重合体は、例えば、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｏ，ｐ－ジメチルスチレン、メトキシスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルベンジルアセテート、ヒドロキシスチレン、ｐ－クロロスチレン、ジビニルベンゼン、３－フェニルプロピレン、４－フェニルプロピレン、α－メチルスチレン等の芳香族ビニル化合物；シクロペンテン、シクロヘプテン、ノルボルネン、５－メチル－２－ノルボルネン等の炭素数が３～２０の環状オレフィン類等を併用してもよい。 Examples of the ethylene / α-olefin copolymer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinyl benzoic acid, methyl vinylbenzoate, and vinyl. Aromatic vinyl compounds such as benzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, etc. Cyclic olefins having 3 to 20 carbon atoms may be used in combination.
　ここで、エチレン・α－オレフィン共重合体としては、例えば、三井化学社製のタフマー（商標登録）、ＤＯＷ社製のＥＮＧＡＧＥ（商標登録）、エクソンモービル社製のＥＸＡＣＴ（商標登録）、日本ポリエチレン社製のカーネル（商標登録）等が挙げられる。 Here, examples of the ethylene / α-olefin copolymer include Tafmer (registered trademark) manufactured by Mitsui Chemicals, ENGAGE (registered trademark) manufactured by DOW, EXACT (registered trademark) manufactured by ExxonMobil, and Nippon Polyethylene. Kernel (trademark registration) manufactured by the company, etc. may be mentioned.
　上記エチレン・α－オレフィン共重合体は、以下の要件ａ１）およびａ２）のうち少なくとも１つを満たすことが好ましい。 The ethylene / α-olefin copolymer preferably satisfies at least one of the following requirements a1) and a2).
（要件ａ１）
　ＡＳＴＭ　Ｄ１５０５に準拠して測定されるエチレン・α－オレフィン共重合体の密度は好ましくは０．８６５～０．８９５ｇ／ｃｍ３であり、より好ましくは０．８６６～０．８９０ｇ／ｃｍ３、さらに好ましくは０．８６６～０．８８４ｇ／ｃｍ３、特に好ましくは０．８６７～０．８８０ｇ／ｃｍ３である。
　エチレン・α－オレフィン共重合体の密度は、エチレン単位の含有割合とα－オレフィン単位の含有割合とのバランスにより調整することができる。すなわち、エチレン単位の含有割合を高くすると結晶性が高くなり、密度の高いエチレン・α－オレフィン共重合体を得ることができる。一方、エチレン単位の含有割合を低くすると結晶性が低くなり、密度の低いエチレン・α－オレフィン共重合体を得ることができる。 (Requirement a1)
The density of the ethylene / α-olefin copolymer measured according to ASTM D1505 is preferably 0.865 to 0.895 g / cm 3 , more preferably 0.866 to 0.890 g / cm 3 , It is preferably 0.866 to 0.884 g / cm 3 , particularly preferably 0.867 to 0.880 g / cm 3 .
The density of the ethylene / α-olefin copolymer can be adjusted by a balance between the content ratio of ethylene units and the content ratio of α-olefin units. That is, when the content ratio of the ethylene unit is increased, the crystallinity is increased and a high density ethylene / α-olefin copolymer can be obtained. On the other hand, when the content ratio of the ethylene unit is lowered, the crystallinity is lowered and an ethylene / α-olefin copolymer having a low density can be obtained.
　エチレン・α－オレフィン共重合体の密度が上記上限値以下であると、結晶性がより適度となり、得られる封止シートの透明性をより高くすることができる。さらに、架橋性をより良好なものとすることができる。また柔軟性により優れ、ラミネート成形をする際に太陽電池素子の割れや、薄膜電極のカケ等が発生することをより抑制することができる。
　一方、エチレン・α－オレフィン共重合体の密度が上記下限値以上であると、エチレン・α－オレフィン共重合体の結晶化速度を速くできるため、押出機より押し出されたシートがベタつきにくく、冷却ロールでの剥離が容易になり、封止シートを容易に得ることができる。また、シートにベタツキが発生しにくくなるのでブロッキングの発生を抑制し、シートの繰り出し性を向上させることができる。また、十分に架橋させられるため、封止シートの耐熱性の低下を抑制することができる。 When the density of the ethylene / α-olefin copolymer is not more than the above upper limit, the crystallinity becomes more appropriate, and the transparency of the resulting sealing sheet can be further increased. Furthermore, the crosslinkability can be made better. Moreover, it is excellent in a softness | flexibility and it can suppress more that the crack of a solar cell element, the crack of a thin film electrode, etc. generate | occur | produce when laminate-molding.
On the other hand, if the density of the ethylene / α-olefin copolymer is not less than the above lower limit, the crystallization speed of the ethylene / α-olefin copolymer can be increased, so that the sheet extruded from the extruder is not sticky, and cooling Peeling with a roll becomes easy and a sealing sheet can be obtained easily. Further, since stickiness is less likely to occur in the sheet, the occurrence of blocking can be suppressed, and the sheet feedability can be improved. Moreover, since it is made to fully bridge | crosslink, the fall of the heat resistance of a sealing sheet can be suppressed.
（要件ａ２）
　ＡＳＴＭ　Ｄ２２４０に準拠して測定される、エチレン・α－オレフィン共重合体のショアＡ硬度は好ましくは６０～９５であり、より好ましくは６２～９０、さらに好ましくは６２～８５、特に好ましくは６５～８０である。エチレン・α－オレフィン共重合体のショアＡ硬度は、エチレン・α－オレフィン共重合体のエチレン単位の含有割合や密度を上述の数値範囲に制御することにより、調整することができる。すなわち、エチレン単位の含有割合が高く、密度が高いエチレン・α－オレフィン共重合体は、ショアＡ硬度が高くなる。一方、エチレン単位の含有割合が低く、密度が低いエチレン・α－オレフィン共重合体は、ショアＡ硬度が低くなる。 (Requirement a2)
The Shore A hardness of the ethylene / α-olefin copolymer, measured according to ASTM D2240, is preferably 60 to 95, more preferably 62 to 90, still more preferably 62 to 85, and particularly preferably 65 to 95. 80. The Shore A hardness of the ethylene / α-olefin copolymer can be adjusted by controlling the content and density of the ethylene units in the ethylene / α-olefin copolymer within the above-mentioned numerical range. That is, an ethylene / α-olefin copolymer having a high ethylene unit content and a high density has a high Shore A hardness. On the other hand, an ethylene / α-olefin copolymer having a low content of ethylene units and a low density has a low Shore A hardness.
　ショアＡ硬度が上記下限値以上であると、シート化しやすく耐ブロッキング性が良好なシートが得られ、さらに耐熱性も向上させることができる。
　一方、ショアＡ硬度が上記上限値以下であると、透明性および柔軟性を向上させるとともに、シート成形を容易にすることができる。 When the Shore A hardness is not less than the above lower limit, a sheet that is easily formed into a sheet and has good blocking resistance can be obtained, and heat resistance can also be improved.
On the other hand, when the Shore A hardness is not more than the above upper limit, the transparency and flexibility can be improved and sheet molding can be facilitated.
（エチレン・極性モノマー共重合体）
　本実施形態に係るエチレン・極性モノマー共重合体としては、例えば、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸プロピル共重合体、エチレン・（メタ）アクリル酸ブチル共重合体、エチレン・（メタ）アクリル酸ヘキシル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシエチル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシプロピル共重合体、エチレン・（メタ）アクリル酸グリシジル共重合体、エチレン・マレイン酸ジメチル共重合体、エチレン・マレイン酸ジエチル共重合体、エチレン・フマル酸ジメチル共重合体、エチレン・フマル酸ジエチル共重合体等のエチレン・不飽和カルボン酸エステル共重合体；エチレン・（メタ）アクリル酸共重合体、エチレン・マレイン酸共重合体、エチレン・フマル酸共重合体、エチレン・クロトン酸共重合体等のエチレン・不飽和カルボン酸共重合体およびそれらの塩；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のエチレン・ビニルエステル共重合体：エチレン・スチレン共重合体等から選択される一種または二種以上を挙げることができる。
　これらの中でも、上記エチレン・極性モノマー共重合体としては、その入手容易性と性能とのバランスからエチレン・ビニルエステル共重合体、エチレン・不飽和カルボン酸エステ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特に好ましい。 (Ethylene / polar monomer copolymer)
Examples of the ethylene / polar monomer copolymer according to the present embodiment include an ethylene / (meth) ethyl acrylate copolymer, an ethylene / (meth) methyl acrylate copolymer, and an ethylene / (meth) acrylate propyl copolymer. Polymer, ethylene / (meth) butyl acrylate copolymer, ethylene / (meth) acrylic acid hexyl copolymer, ethylene / (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene / (meth) acrylic acid -2-Hydroxypropyl copolymer, ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / dimethyl maleate copolymer, ethylene / diethyl maleate copolymer, ethylene / dimethyl fumarate copolymer, ethylene / Ethylene / unsaturated carboxylic acid ester copolymer such as diethyl fumarate copolymer; ) Acrylic acid copolymers, ethylene / maleic acid copolymers, ethylene / fumaric acid copolymers, ethylene / unsaturated carboxylic acid copolymers such as ethylene / crotonic acid copolymers and their salts; ethylene / vinyl acetate Copolymer, ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl ester copolymer such as ethylene / vinyl stearate copolymer: selected from ethylene / styrene copolymer, etc. One type or two or more types can be mentioned.
Among these, the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
　上記エチレン・酢酸ビニル共重合体は、エチレンと酢酸ビニルとの共重合体であり、通常はランダム共重合体である。
　上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合は、好ましくは１０質量％以上４７質量％以下、より好ましくは１３質量％以上３５質量％以下である。酢酸ビニルの含有量がこの範囲にあると、封止シートの接着性、耐候性、透明性、機械的性質のバランスにより一層優れる。また、封止シートを成膜する際にも、成膜性が良好となる。
　酢酸ビニル含有量は、ＪＩＳ　Ｋ６７３０に準拠して測定可能である。 The ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
The content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass. When the content of vinyl acetate is in this range, the balance of adhesion, weather resistance, transparency, and mechanical properties of the sealing sheet is further improved. In addition, when the sealing sheet is formed, the film forming property is improved.
The vinyl acetate content can be measured according to JIS K6730.
　なお、エチレン・酢酸ビニル共重合体は、エチレンおよび酢酸ビニルのみからなる二元共重合体が好ましいが、エチレンおよび酢酸ビニルの他に、例えばギ酸ビニル、グリコール酸ビニル、プロピオン酸ビニル、安息香酸ビニル等のビニルエステル系単量体；アクリル酸、メタクリル酸、エタクリル酸、或いはこれらの塩もしくはアルキルエステル等のアクリル系単重体；等から選択される一種または二種以上を共重合成分として含んでもよい。上記エチレンおよび酢酸ビニル以外の共重合成分を含む場合、エチレン・酢酸ビニル共重合体中の上記エチレンおよび酢酸ビニル以外の共重合成分の量を０．５質量％以上５質量％以下とすることが好ましい。 The ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate. In addition to ethylene and vinyl acetate, for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate. One or two or more selected from a vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof may be included as a copolymerization component. . When a copolymer component other than ethylene and vinyl acetate is included, the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
　上記エチレン・極性モノマー共重合体の製造方法は特に限定されず、公知の方法により製造することができる。例えば、ラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で溶媒や連鎖移動剤の存在下または不存在下で、エチレン、極性モノマー、必要に応じて他の共重合成分を共重合させることにより製造することができる。 The method for producing the ethylene / polar monomer copolymer is not particularly limited, and can be produced by a known method. For example, in the presence of a radical generator, copolymerization of ethylene, polar monomers, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
＜シランカップリング剤＞
　本実施形態に係る透明封止シートは、シランカップリング剤をさらに含有することが好ましい。また、本実施形態に係る着色封止シートは、シランカップリング剤をさらに含有してもよい。 <Silane coupling agent>
The transparent sealing sheet according to this embodiment preferably further contains a silane coupling agent. Moreover, the colored sealing sheet which concerns on this embodiment may further contain a silane coupling agent.
　シランカップリング剤としては、例えば、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（β－メトキシエトキシシラン）、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、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、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクロキシプロピルメチルジメトキシシラン、３－メタクロキシプロピルトリエトキシシラン、３－メタクロキシプロピルメチルジエトキシシラン、３－アクロキシプロピルトリメトキシシラン等を使用することができる。３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－アミノプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクロキシプロピルトリエトキシシラン、３－アクロキシプロピルトリメトキシシラン、ビニルトリエトキシシランは、接着性が向上するためより好ましい。 Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- ( 1,3-jime Ru-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be used. 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane and vinyltriethoxysilane are more preferable because the adhesion is improved.
　本実施形態に係る透明封止シートおよび着色封止シート中のシランカップリング剤の含有量は、上記シランカップリング剤を含むシート中のエチレン系共重合体１００質量部に対して、それぞれ０．０１質量部以上５質量部以下であることが好ましく、０．０５質量部以上２質量部以下であることがより好ましく、０．１質量部以上１質量部以下であることがさらに好ましく、０．１質量部以上０．６質量部以下であることが特に好ましい。
　シランカップリング剤の含有量が上記下限値以上であると、封止シートと他の部材との接着強度をより良好なものとすることができる。一方、シランカップリング剤の含有量が上記上限値以下であると、コストと性能のバランスがよく、透湿性の低下も防止できる。また、太陽電池素子や電極、裏面側保護部材との密着性が良好となり、接着性も向上する。また、シランカップリング剤自体が縮合反応を起こし、封止シートに白い筋として存在し、製品外観が悪化することを抑制できる。 The content of the silane coupling agent in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 0. 100 parts by mass with respect to 100 parts by mass of the ethylene copolymer in the sheet containing the silane coupling agent. It is preferably 01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 2 parts by mass or less, further preferably 0.1 parts by mass or more and 1 part by mass or less. The amount is particularly preferably 1 part by mass or more and 0.6 part by mass or less.
When the content of the silane coupling agent is not less than the above lower limit value, the adhesive strength between the sealing sheet and the other member can be further improved. On the other hand, when the content of the silane coupling agent is not more than the above upper limit value, the balance between cost and performance is good, and deterioration of moisture permeability can be prevented. Moreover, adhesiveness with a solar cell element, an electrode, and a back surface side protection member becomes favorable, and adhesiveness also improves. Moreover, it can suppress that a silane coupling agent itself raise | generates a condensation reaction, exists as a white stripe | line on a sealing sheet, and a product external appearance deteriorates.
＜着色剤＞
　本実施形態に係る着色封止シートは必須成分として着色剤を含む。
　着色剤を含むことにより、光反射能により太陽電池モジュールの変換効率を向上させたり、着色封止シートの意匠性や熱伝導性等を向上させたりすることができる。 <Colorant>
The colored sealing sheet according to the present embodiment contains a colorant as an essential component.
By including the colorant, the conversion efficiency of the solar cell module can be improved by the light reflectivity, and the designability and thermal conductivity of the colored sealing sheet can be improved.
　着色剤としては、例えば、天然マイカ（雲母）、合成マイカ、酸化チタン、酸化アルミニウム、炭酸カルシウム、タルク、クレー、炭酸マグネシウム、カオリナイト、珪藻土、カーボンブラック、赤外線反射顔料等が挙げられる。これらは一種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。これらの中でも、酸化チタン、酸化アルミニウム、炭酸カルシウム、タルク、クレー、炭酸マグネシウム、カーボンブラック、赤外線反射顔料が好ましく、酸化チタン、酸化アルミニウム、炭酸カルシウム、カーボンブラック、赤外線反射顔料がより好ましく、酸化チタン、カーボンブラック、赤外線反射顔料がさらに好ましく、酸化チタンが特に好ましい。
　ここで、赤外線反射顔料としては、例えば、銅／クロム／マンガンの複合酸化物、鉄／クロムの複合酸化物、マンガン／ビスマスの複合酸化物、カルシウム／チタン／マンガンの複合酸化物等が挙げられる。 Examples of the colorant include natural mica (mica), synthetic mica, titanium oxide, aluminum oxide, calcium carbonate, talc, clay, magnesium carbonate, kaolinite, diatomaceous earth, carbon black, infrared reflective pigment, and the like. These may be used alone or in combination of two or more. Among these, titanium oxide, aluminum oxide, calcium carbonate, talc, clay, magnesium carbonate, carbon black, and infrared reflecting pigment are preferable, and titanium oxide, aluminum oxide, calcium carbonate, carbon black, and infrared reflecting pigment are more preferable, and titanium oxide. Carbon black and infrared reflecting pigment are more preferable, and titanium oxide is particularly preferable.
Here, examples of the infrared reflecting pigment include copper / chromium / manganese composite oxide, iron / chromium composite oxide, manganese / bismuth composite oxide, calcium / titanium / manganese composite oxide, and the like. .
　本実施形態に係る着色封止シート中の着色剤の含有量は、着色封止シート中のエチレン系共重合体１００質量部に対して０．５質量部以上５０質量部以下が好ましく、１質量部以上５０質量部以下がより好ましく、１質量部以上３０質量部以下がさらに好ましく、１質量部以上２０質量部以下が特に好ましい。 The content of the colorant in the colored sealing sheet according to the present embodiment is preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the colored sealing sheet. Part to 50 parts by weight is more preferable, 1 part to 30 parts by weight is more preferable, and 1 part to 20 parts by weight is particularly preferable.
＜架橋剤＞
　本実施形態に係る透明封止シートは、架橋剤（有機過酸化物）をさらに含有することが好ましい。また、本実施形態に係る着色封止シートは、架橋剤をさらに含有してもよい。
　封止シートに有機過酸化物を含有させることによって、上記エチレン系共重合体にシランカップリング剤をグラフトすることができ、また上記エチレン系共重合体を架橋することができる。これにより、得られる封止シートの耐熱性および耐候性がより良好となる。
　また、封止シートに有機過酸化物を含有させることによって、封止後の太陽電池素子の位置がずれてしまうことを抑制できる。 <Crosslinking agent>
It is preferable that the transparent sealing sheet which concerns on this embodiment further contains a crosslinking agent (organic peroxide). Moreover, the colored sealing sheet which concerns on this embodiment may further contain a crosslinking agent.
By containing an organic peroxide in the sealing sheet, a silane coupling agent can be grafted to the ethylene copolymer, and the ethylene copolymer can be crosslinked. Thereby, the heat resistance and weather resistance of the obtained sealing sheet become better.
Moreover, it can suppress that the position of the solar cell element after sealing shift | deviates by making an sealing sheet contain an organic peroxide.
　上記有機過酸化物は、太陽電池モジュールの生産性を考慮すると、有機過酸化物としては、半減期が１０時間以下であり、かつ分解温度が１０５℃以下であるものが好ましい。また安全性の面から、最高保存温度が１０℃以上であるものが好ましい。
　また、上記有機過酸化物は、押出成形、カレンダ成形等のシート成形での生産性と太陽電池モジュールのラミネート成形時の架橋速度のバランスから、有機過酸化物の１分間半減期温度が１００℃以上１７０℃以下であるものが好ましい。有機過酸化物の１分間半減期温度が１００℃以上であると、シート成形を容易にし、かつ、封止シートの外観をより良好にすることができる。また、得られる封止シートの絶縁破壊電圧の低下を防ぐことができ、透湿性の低下も防止でき、さらに接着性も向上する。有機過酸化物の１分間半減期温度が１７０℃以下であると、太陽電池モジュールのラミネート成形時の架橋速度の低下を抑制できるため、太陽電池モジュールの生産性の低下を防ぐことができる。また、封止シートの耐熱性や接着性の低下を防ぐこともできる。 In consideration of the productivity of the solar cell module, the organic peroxide preferably has a half-life of 10 hours or less and a decomposition temperature of 105 ° C. or less. From the viewpoint of safety, it is preferable that the maximum storage temperature is 10 ° C. or higher.
In addition, the organic peroxide has a one-minute half-life temperature of 100 ° C. due to the balance between productivity in sheet molding such as extrusion molding and calender molding and the crosslinking rate at the time of laminate molding of the solar cell module. A temperature of 170 ° C. or lower is preferable. When the one-minute half-life temperature of the organic peroxide is 100 ° C. or more, sheet molding can be facilitated and the appearance of the sealing sheet can be improved. Moreover, the fall of the dielectric breakdown voltage of the sealing sheet obtained can be prevented, the fall of moisture permeability can also be prevented, and adhesiveness also improves. When the one-minute half-life temperature of the organic peroxide is 170 ° C. or lower, it is possible to suppress a decrease in the crosslinking rate when the solar cell module is laminated, and thus it is possible to prevent a decrease in the productivity of the solar cell module. Moreover, the heat resistance of a sealing sheet and the fall of adhesiveness can also be prevented.
　上記有機過酸化物の例としては、ジラウロイルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジベンゾイルパーオキサイド、シクロヘキサノンパーオキサイド、ジ－ｔ－ブチルパーフタレート、クメンヒドロパーオキシド、ｔ－ブチルヒドロパーオキシド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキセン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシマレイン酸、１，１－ジ（ｔ－アミルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン、ｔ－アミルパーオキシイソノナノエート、ｔ－アミルパーオキシノルマルオクトエート、１，１－ジ（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－アミル－パーオキシベンゾエート、ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシイソノナノエート、ｔ－ブチルパーオキシベンゾエート、２，２－ジ（ブチルパーオキシ）ブタン、ｎ－ブチル－４，４－ジ（ｔ－ブチルパーオキシ）ブチレート、メチルエチルケトンパーオキサイド、エチル－３，３－ジ（ｔ－ブチルパーオキシ）ブチレート、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジ－ｔ－ブチルパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、アセチルアセトンパーオキサイド等が挙げられる。上記有機過酸化物は、一種単独で用いてもよく、二種以上を混合して用いてもよい。
　これらのうち好ましくは、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキセン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート、ｔ－ブチルパーオキシベンゾエートである。 Examples of the organic peroxide include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, and di-t-butyl. Perphthalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1, 1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-amylpero) C) Cyclohexane, t-amylperoxyisononanoate, t-amylperoxynormal octoate, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di ( t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-amyl-par Oxybenzoate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxybenzoate, 2,2-di (butylperoxy) butane, n-butyl-4,4-di (t- Butyl peroxy) butyrate, methyl ethyl ketone peroxide, ethyl , 3-Di (t-butylperoxy) butyrate, dicumyl peroxide, t-butylcumyl peroxide, t-butylperoxybenzoate, di-t-butyl peroxide, 1,1,3,3-tetramethyl Examples include butyl hydroperoxide and acetylacetone peroxide. The said organic peroxide may be used individually by 1 type, and may mix and use 2 or more types.
Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylper Oxy-2-ethylhexyl carbonate, t-butyl peroxybenzoate.
　本実施形態に係る透明封止シートおよび着色封止シート中の上記有機過酸化物の含有量は、上記有機過酸化物を含むシート中の上記エチレン系共重合体１００質量部に対して、それぞれ０．１質量部以上３質量部以下が好ましく、０．２質量部以上２質量部以下がより好ましい。
　有機過酸化物の含有量が上記下限値以上であると、封止シートの架橋特性がより良好となり、封止シートの耐熱性がより一層向上する。また、シランカップリング剤のエチレン系共重合体の主鎖へのグラフト反応をより良好にして、耐熱性や接着性がより一層良好となる。
　また、有機過酸化物の含有量が上記上限値以下であると、上記の架橋特性、耐熱性、接着性がより良好な上に、シート成形時のゲル化をより一層抑制でき、外観がより良好な封止シートを得ることができる。さらに、有機過酸化物の分解生成物等の発生量が一層低下し、封止シート中に気泡が発生するのをより一層抑制することができる。 Content of the said organic peroxide in the transparent sealing sheet and colored sealing sheet which concerns on this embodiment is respectively with respect to 100 mass parts of said ethylene-type copolymers in the sheet | seat containing the said organic peroxide. 0.1 parts by mass or more and 3 parts by mass or less are preferable, and 0.2 parts by mass or more and 2 parts by mass or less are more preferable.
When the content of the organic peroxide is not less than the above lower limit value, the cross-linking property of the sealing sheet becomes better, and the heat resistance of the sealing sheet is further improved. In addition, the graft reaction of the silane coupling agent to the main chain of the ethylene-based copolymer is further improved, and the heat resistance and adhesiveness are further improved.
Further, when the content of the organic peroxide is not more than the above upper limit value, the above cross-linking characteristics, heat resistance, and adhesiveness are better, and further gelation during sheet molding can be further suppressed, and the appearance is more A good sealing sheet can be obtained. Furthermore, the generation amount of the decomposition product of the organic peroxide is further reduced, and the generation of bubbles in the sealing sheet can be further suppressed.
＜架橋助剤＞
　本実施形態に係る透明封止シートおよび着色封止シートは、架橋性を向上させる観点から、架橋助剤を含有してもよい。
　上記架橋助剤としては、例えばジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、アクリレート化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上を用いることができる。 <Crosslinking aid>
The transparent sealing sheet and the colored sealing sheet according to the present embodiment may contain a crosslinking aid from the viewpoint of improving the crosslinkability.
As said crosslinking adjuvant, the 1 type (s) or 2 or more types selected from the group which consists of a divinyl aromatic compound, a cyanurate compound, a diallyl compound, an acrylate compound, a triallyl compound, an oxime compound, and a maleimide compound can be used, for example.
　本実施形態に係る透明封止シートおよび着色封止シート中の架橋助剤の含有量は、上記架橋助剤を含むシート中のエチレン系共重合体１００質量部に対して、それぞれ３．０質量部以下であることが好ましく、２．０質量部以下であることがより好ましく、１．５質量部以下であることが特に好ましい。
　また、本実施形態に係る透明封止シートおよび着色封止シート中の架橋助剤の含有量は、上記架橋助剤を含むシート中のエチレン系共重合体１００質量部に対して、それぞれ０．１質量部以上であることが好ましく、０．３質量部以上であることがより好ましく、０．５質量部以上であることが特に好ましい。これにより、適度な架橋構造とすることができ、封止シートの耐熱性、機械物性、および接着性を向上できる。 The content of the crosslinking aid in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 3.0 masses per 100 parts by mass of the ethylene copolymer in the sheet containing the crosslinking aid. It is preferably no greater than 2.0 parts, more preferably no greater than 2.0 parts by mass, and particularly preferably no greater than 1.5 parts by mass.
In addition, the content of the crosslinking aid in the transparent sealing sheet and the colored sealing sheet according to the present embodiment is 0. 100 parts by mass with respect to 100 parts by mass of the ethylene copolymer in the sheet containing the crosslinking aid. The amount is preferably 1 part by mass or more, more preferably 0.3 part by mass or more, and particularly preferably 0.5 part by mass or more. Thereby, it can be set as a moderate crosslinked structure and can improve the heat resistance of a sealing sheet, a mechanical physical property, and adhesiveness.
　ジビニル芳香族化合物としては、例えば、ジビニルベンゼン、ジ－ｉ－プロペニルベンゼン等が挙げられる。
　シアヌレート化合物としては、例えば、トリアリルシアヌレート、トリアリルイソシアヌレート等が挙げられる。
　ジアリル化合物としては、例えば、ジアリルフタレート等が挙げられる。
　トリアリル化合物としては、例えば、ペンタエリスリトールトリアリルエーテル等が挙げられる。
　アクリレート化合物としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート等が挙げられる。
　オキシム化合物としては、例えば、ｐ－キノンジオキシム、ｐ－ｐ'－ジベンゾイルキノンジオキシム等が挙げられる。
　マレイミド化合物としては、例えば、ｍ－フェニレンジマレイミド等が挙げられる。 Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
Examples of diallyl compounds include diallyl phthalate.
Examples of the triallyl compound include pentaerythritol triallyl ether.
Examples of the acrylate compound include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and tetramethylolmethane. Examples include tetra (meth) acrylate and tetramethylolmethane tetra (meth) acrylate.
Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
Examples of the maleimide compound include m-phenylene dimaleimide.
　架橋助剤としてはビニル基等の架橋性不飽和結合を１分子中に３官能以上有する化合物が好ましく、中でも、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレートが、架橋性が良好で好ましい。 As the crosslinking aid, a compound having at least three functional crosslinkable unsaturated bonds such as a vinyl group is preferable. Among them, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane tri (meth) acrylate, ditrimethylol. Propane tetra (meth) acrylate is preferred because it has good crosslinkability.
＜紫外線吸収剤、光安定剤、耐熱安定剤＞
　本実施形態に係る透明封止シートおよび着色封止シートは、紫外線吸収剤、光安定剤および耐熱安定剤から選択される少なくとも一種の添加剤をさらに含有してもよい。これらの添加剤の合計配合量は、これらの添加剤を含むシート中のエチレン系共重合体１００質量部に対して、０．００５質量部以上５質量部以下であることが好ましい。上記三種から選ばれる少なくとも二種の添加剤を含有することがより好ましく、上記三種の全てが含有されていることが特に好ましい。上記添加剤の配合量が上記範囲にあると、耐候安定性および耐熱安定性を向上する効果を十分に確保し、かつ、太陽電池素子や裏面側保護部材との接着性の低下を防ぐことができるので好ましい。 <Ultraviolet absorber, light stabilizer, heat stabilizer>
The transparent sealing sheet and the colored sealing sheet according to this embodiment may further contain at least one additive selected from an ultraviolet absorber, a light stabilizer, and a heat resistance stabilizer. The total amount of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the sheet containing these additives. It is more preferable to contain at least two types of additives selected from the above three types, and it is particularly preferable that all the three types are included. When the blending amount of the additive is within the above range, it is possible to sufficiently ensure the effect of improving weather resistance stability and heat stability, and to prevent a decrease in adhesion to the solar cell element and the back surface side protection member. It is preferable because it is possible.
　紫外線吸収剤としては、例えば、２－ヒドロキシ－４－ノルマル－オクチルオキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，２－ジヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－２－カルボキシベンゾフェノン、２－ヒドロキシ－４－Ｎ－オクトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤；２－（２－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔ－オクチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤；フェニルサリチレート、ｐ－オクチルフェニルサリチレート等のサリチル酸エステル系紫外線吸収剤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 ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2- Benzophenone ultraviolet absorbers such as carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate Select from UV absorbers, etc. It is the one or may be used two or more.
　光安定剤としては、例えば、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］等のヒンダードアミン系化合物、ヒンダードピペリジン系化合物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 light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3. , 5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino }] Or the like selected from hindered amine compounds, hindered piperidine compounds and the like can be used.
　耐熱安定剤としては、例えば、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ビス［２，４－ビス（１，１－ジメチルエチル）－６－メチルフェニル］エチルエステル亜リン酸、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）［１，１－ビフェニル］－４，４'－ジイルビスホスフォナイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト等のホスファイト系酸化防止剤；３－ヒドロキシ－５，７－ジ－ｔｅｒｔ－ブチル－フラン－２－オンとｏ－キシレンとの反応生成物等のラクトン系酸化防止剤；３，３'，３"，５，５'，５"－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ'，ａ"－（メチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）ベンジルベンゼン、ペンタエリス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）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］等のヒンダードフェノール系酸化防止剤；硫黄系酸化防止剤；アミン系酸化防止剤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。これらの中でも、ホスファイト系酸化防止剤、およびヒンダードフェノール系酸化防止剤が好ましい。 Examples of heat stabilizers include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phosphite-based antioxidants such as phites; Lactone-based antioxidants such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′ , 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-cresol, 1,3,5-trimethyl -2, 4, 6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3 Hindered phenolic oxidation of-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. One or two or more selected from an antioxidant, a sulfur-based antioxidant, an amine-based antioxidant, etc. Among these, a phosphite-based antioxidant and a hindered phenol-based antioxidant can be used. preferable.
＜透明封止シートおよび着色封止シートの製造方法＞
　本実施形態に係る透明封止シートおよび着色封止シートの製造方法は特に限定されないが、公知の各種の成形方法（キャスト成形、押出シート成形、インフレーション成形、射出成形、圧縮成形、カレンダ成形等）を採用することが可能である。特に、押出成形とカレンダ成形が好ましい。 <Method for producing transparent sealing sheet and colored sealing sheet>
The manufacturing method of the transparent sealing sheet and the colored sealing sheet according to this embodiment is not particularly limited, but various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) Can be adopted. In particular, extrusion molding and calendar molding are preferable.
　本実施形態に係る透明封止シートおよび着色封止シートの製造方法は特に限定されないが、例えば、以下の方法が挙げられる。まず、エチレン系共重合体と、必要に応じて、シランカップリング剤と、着色剤と、架橋剤と、架橋助剤と、紫外線吸収剤と、光安定剤と、耐熱安定剤と、その他添加剤とを、例えば、ポリ袋等の袋の中で人力でのブレンドや、ヘンシェルミキサー、タンブラー、スーパーミキサー等の攪拌混合機を用いてブレンドする。次いで、得られた樹脂組成物を、例えば、押出シート成形機のホッパーに投入し、溶融混練を行いつつ押出シート成形機のＴダイから樹脂組成物をシート状に押出して封止シートを得る。
　なお、押出シート成形機に投入後、溶融混練の途中に添加剤の一部を添加することもできる。またシート成形法としてはカレンダ成形を採用してもよい。
　成形は、Ｔ－ダイ押出機、カレンダ成形機、インフレーション成形機等を使用する公知の方法によって行なうことができる。 Although the manufacturing method of the transparent sealing sheet and colored sealing sheet which concern on this embodiment is not specifically limited, For example, the following methods are mentioned. First, ethylene copolymer, silane coupling agent, colorant, cross-linking agent, cross-linking aid, UV absorber, light stabilizer, heat stabilizer, and other additives as required For example, the agent is blended manually in a bag such as a plastic bag or by using a stirring mixer such as a Henschel mixer, a tumbler, or a super mixer. Subsequently, the obtained resin composition is put into, for example, a hopper of an extrusion sheet molding machine, and the resin composition is extruded into a sheet form from a T-die of the extrusion sheet molding machine while performing melt kneading to obtain a sealing sheet.
In addition, a part of additive can also be added in the middle of melt-kneading after throwing into an extrusion sheet molding machine. As the sheet forming method, calendar forming may be employed.
The molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
２．太陽電池モジュールについて
　本実施形態に係る太陽電池裏面側封止シートセットは、太陽電池モジュールにおいて、太陽電池素子の非受光面側を封止するために用いられる。
　太陽電池モジュールの構成としては、例えば表面側透明保護部材／受光面側封止層／太陽電池素子／裏面側封止層／裏面側保護部材（バックシート）をこの順に積層した構成が挙げられるが、特に限定されない。
　本実施形態に係る太陽電池裏面側封止シートセットは上記裏面側封止層に用いられる。 2. About solar cell module The solar cell back surface side sealing sheet set which concerns on this embodiment is used in order to seal the non-light-receiving surface side of a solar cell element in a solar cell module.
As a structure of a solar cell module, the structure which laminated | stacked the surface side transparent protective member / light-receiving surface side sealing layer / solar cell element / back surface side sealing layer / back surface side protective member (back sheet | seat) in this order, for example is mentioned. There is no particular limitation.
The solar cell back surface side sealing sheet set which concerns on this embodiment is used for the said back surface side sealing layer.
　図１に、本実施形態に係る太陽電池モジュール１０の断面図の一例を示す。
　太陽電池モジュール１０は、表面側透明保護部材１４と、裏面側保護部材（バックシート）１５と、太陽電池素子１３と、太陽電池素子１３を表面側透明保護部材１４と裏面側保護部材１５との間に封止する封止層１と、を備える。封止層１が受光面側に配置される受光面側封止層１１と非受光面側に配置される裏面側封止層１２とを含み、裏面側封止層１２が本実施形態に係る太陽電池裏面側封止シートセットにより形成されている。そして、本実施形態に係る透明封止シートにより構成された裏面側透明封止層１２Ａが太陽電池素子１３側に配置されており、本実施形態に係る着色封止シートにより構成された裏面側着色封止層１２Ｂが裏面側保護部材１５側に配置されている。 In FIG. 1, an example of sectional drawing of the solar cell module 10 which concerns on this embodiment is shown.
The solar cell module 10 includes a front surface side transparent protective member 14, a back surface side protective member (back sheet) 15, a solar cell element 13, and the solar cell element 13 formed of a front surface side transparent protective member 14 and a back surface side protective member 15. And a sealing layer 1 for sealing between them. The sealing layer 1 includes a light receiving surface side sealing layer 11 arranged on the light receiving surface side and a back surface side sealing layer 12 arranged on the non-light receiving surface side, and the back surface side sealing layer 12 is related to the present embodiment. It is formed by a solar cell back side sealing sheet set. And the back side transparent sealing layer 12A comprised by the transparent sealing sheet which concerns on this embodiment is arrange | positioned at the solar cell element 13 side, and the back side coloring comprised by the colored sealing sheet which concerns on this embodiment The sealing layer 12B is disposed on the back surface side protection member 15 side.
　ここで、本実施形態に係る太陽電池モジュール１０において、裏面側封止層１２の太陽電池素子１３および裏面側保護部材１５に対する接着性を良好にする観点から、裏面側透明封止層１２Ａが太陽電池素子１３に接しており、裏面側着色封止層１２Ｂが裏面側保護部材１５に接していることが好ましい。 Here, in the solar cell module 10 according to the present embodiment, the back side transparent sealing layer 12 </ b> A is formed from the viewpoint of improving the adhesion of the back side sealing layer 12 to the solar cell element 13 and the back side protection member 15. It is preferably in contact with the battery element 13 and the back side colored sealing layer 12B is in contact with the back side protection member 15.
（太陽電池素子）
　太陽電池素子１３としては、例えば、単結晶シリコン、多結晶シリコン、アモルファスシリコン等のシリコン系、ガリウム－砒素、銅－インジウム－セレン、カドミウム－テルル等のＩＩＩ－Ｖ族やＩＩ－ＶＩ族化合物半導体系等の各種太陽電池素子を用いることができる。
　太陽電池モジュール１０においては、複数の太陽電池素子１３は、導線および半田接合部を備えたインターコネクタ１６を介して電気的に直列に接続されている。 (Solar cell element)
Examples of the solar cell element 13 include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductors such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium. Various solar cell elements such as a system can be used.
In the solar cell module 10, the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
（表面側透明保護部材）
　表面側透明保護部材１４としては、例えば、ガラス板；アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂等により形成された樹脂板等が挙げられる。 (Front side transparent protective member)
Examples of the surface-side transparent protective member 14 include a glass plate; a resin plate formed of acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
（裏面側保護部材）
　裏面側保護部材（バックシート）１５としては、例えば、金属や各種熱可塑性樹脂フィルム等の単体もしくは多層のシートが挙げられる。例えば、錫、アルミ、ステンレススチール等の金属；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、ポリオレフィン等により形成された各種熱可塑性樹脂フィルム等が挙げられる。
　裏面側保護部材１５は、単層であってもよく、多層であってもよい。 (Back side protection member)
Examples of the back surface side protection member (back sheet) 15 include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
The back surface side protection member 15 may be a single layer or a multilayer.
　ここで、表面側透明保護部材１４および裏面側保護部材１５にガラス板を用いた合わせガラス型太陽電池モジュールは防湿性に優れるため、裏面側保護部材１５に樹脂シート等を用いた一般的な太陽電池モジュールに比べて長期信頼性に優れている。
　一方で、ガラス板は光透過性に優れるものの光反射能に劣るため、合わせガラス型太陽電池モジュールは一般的に発電効率に劣っているという課題を有する。しかし、本実施形態に係る太陽電池裏面側封止シートセットを用いることによって、着色封止シートの光反射能により太陽電池モジュールの変換効率を向上できるため、合わせガラス型太陽電池モジュールは発電効率の上記課題を解決することが可能である。
　以上から、本実施形態に係る太陽電池裏面側封止シートセットによれば、長期信頼性および発電効率のバランスに優れた本実施形態に係る合わせガラス型太陽電池モジュールを実現することができる。すなわち、太陽電池裏面側封止シートセットは、表面側透明保護部材１４および裏面側保護部材１５にガラス板を用いた合わせガラス型太陽電池モジュールに対して好適に用いることができる。
　また、表面側透明保護部材１４および裏面側保護部材１５に用いられるガラス板としては、合わせガラス型太陽電池モジュールや合わせガラスに一般的に用いられているガラス板を用いることができる。 Here, since the laminated glass type solar cell module using a glass plate for the front surface side transparent protective member 14 and the back surface side protective member 15 is excellent in moisture resistance, a general sun using a resin sheet or the like for the back surface side protective member 15. Long-term reliability is superior to battery modules.
On the other hand, since a glass plate is excellent in light transmittance but inferior in light reflectivity, a laminated glass type solar cell module generally has a problem that it is inferior in power generation efficiency. However, since the conversion efficiency of the solar cell module can be improved by the light reflectivity of the colored encapsulating sheet by using the solar cell back surface side sealing sheet set according to the present embodiment, the laminated glass solar cell module has a power generation efficiency. It is possible to solve the above problems.
As mentioned above, according to the solar cell back surface side sealing sheet set which concerns on this embodiment, the laminated glass type solar cell module which concerns on this embodiment excellent in the balance of long-term reliability and electric power generation efficiency is realizable. That is, the solar cell back surface side sealing sheet set can be suitably used for a laminated glass solar cell module using glass plates for the front surface side transparent protective member 14 and the back surface side protective member 15.
Moreover, as a glass plate used for the surface side transparent protection member 14 and the back surface side protection member 15, the glass plate generally used for the laminated glass type solar cell module or laminated glass can be used.
（太陽電池モジュールの製造方法）
　本実施形態に係る太陽電池モジュール１０の製造方法は特に限定されないが、例えば、以下の方法が挙げられる。
　まず、インターコネクタ１６を用いて電気的に接続した複数の太陽電池素子１３を太陽電池受光面側封止シートと太陽電池裏面側封止シートとで挟み、さらにこれら太陽電池受光面側封止シートと太陽電池裏面側封止シートを表面側透明保護部材１４と裏面側保護部材１５とで挟んで積層体を作製する。次いで、太陽電池素子１３を太陽電池受光面側封止シートと太陽電池裏面側封止シートとで挟んだ状態で加熱し、太陽電池素子１３を太陽電池受光面側封止シートと太陽電池裏面側封止シートとの間に封止する。すなわち、得られた積層体を加熱して太陽電池受光面側封止シートおよび太陽電池裏面側封止シートをそれぞれ架橋して受光面側封止層１１および裏面側封止層１２をそれぞれ形成することにより太陽電池素子１３を受光面側封止層１１と裏面側封止層１２との間に封止する。さらに、受光面側封止層１１と裏面側封止層１２、受光面側封止層１１と表面側透明保護部材１４、裏面側封止層１２と裏面側保護部材１５とを接着する。ここで、本実施形態に係る太陽電池裏面側封止シートセットは太陽電池裏面側封止シートに用いられ、裏面側封止層１２を形成する。
　より具体的には、太陽電池受光面側封止シートおよび太陽電池裏面側封止シートに含まれる架橋剤が実質的に分解せず、かつ、エチレン系共重合体が溶融するような温度に太陽電池受光面側封止シートおよび太陽電池裏面側封止シートを加熱し、受光面側封止層１１と裏面側封止層１２、受光面側封止層１１と表面側透明保護部材１４、裏面側封止層１２と裏面側保護部材１５とをそれぞれ仮接着する。次いで昇温して、充分な接着を行い、さらに封止層内のエチレン系共重合体の架橋を行う。接着および架橋の温度は、満足すべき架橋速度が得られ、かつ膨れが発生しないような温度であればよく、例えば１００～１８０℃程度の温度範囲とすることができる。 (Method for manufacturing solar cell module)
Although the manufacturing method of the solar cell module 10 which concerns on this embodiment is not specifically limited, For example, the following method is mentioned.
First, a plurality of solar cell elements 13 electrically connected using the interconnector 16 are sandwiched between a solar cell light-receiving surface side sealing sheet and a solar cell back surface side sealing sheet, and further, these solar cell light-receiving surface side sealing sheets A solar cell back surface side sealing sheet is sandwiched between the front surface side transparent protective member 14 and the back surface side protective member 15 to produce a laminate. Next, the solar cell element 13 is heated while being sandwiched between the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet, and the solar cell element 13 is heated to the solar cell light-receiving surface side sealing sheet and the solar cell back surface side. It seals between sealing sheets. That is, the obtained laminate is heated to cross-link the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet, respectively, to form the light-receiving surface side sealing layer 11 and the back surface side sealing layer 12, respectively. Thus, the solar cell element 13 is sealed between the light receiving surface side sealing layer 11 and the back surface side sealing layer 12. Further, the light receiving surface side sealing layer 11 and the back surface side sealing layer 12, the light receiving surface side sealing layer 11 and the front surface side transparent protective member 14, and the back surface side sealing layer 12 and the back surface side protective member 15 are bonded. Here, the solar cell back surface side sealing sheet set which concerns on this embodiment is used for a solar cell back surface side sealing sheet, and forms the back surface side sealing layer 12. FIG.
More specifically, the solar cell is heated to a temperature at which the crosslinking agent contained in the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet does not substantially decompose and the ethylene copolymer melts. The battery light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet are heated, the light receiving surface side sealing layer 11 and the back surface side sealing layer 12, the light receiving surface side sealing layer 11 and the surface side transparent protective member 14, and the back surface. The side sealing layer 12 and the back surface side protection member 15 are temporarily bonded to each other. Next, the temperature is raised, sufficient adhesion is performed, and the ethylene copolymer in the sealing layer is further crosslinked. The bonding and crosslinking temperature may be any temperature at which a satisfactory crosslinking rate can be obtained and swelling does not occur, and can be in the temperature range of about 100 to 180 ° C., for example.
　ここで、本実施形態に係る透明封止シートと着色封止シートとは別々に準備し、太陽電池素子１３を受光面側封止層１１と裏面側封止層１２との間に封止する上記工程において、本実施形態に係る透明封止シートと着色封止シートとを積層することが好ましい。 Here, the transparent sealing sheet and colored sealing sheet which concern on this embodiment are prepared separately, and the solar cell element 13 is sealed between the light-receiving surface side sealing layer 11 and the back surface side sealing layer 12. In the above step, it is preferable to laminate the transparent sealing sheet and the colored sealing sheet according to this embodiment.
　以上、図面を参照して本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.
　以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（１）エチレン・α－オレフィン共重合体
　エチレン・α－オレフィン共重合体としては、三井化学社製のタフマー（登録商標）Ａ－４０７０Ｓ、Ａ－４０８５Ｓ、およびＡ－１０８５Ｓを使用した。使用したエチレン・α－オレフィン共重合体の物性を表１に示す。 (1) Ethylene / α-olefin copolymer As the ethylene / α-olefin copolymer, Tafmer (registered trademark) A-4070S, A-4085S, and A-1085S manufactured by Mitsui Chemicals, Inc. were used. Table 1 shows the physical properties of the ethylene / α-olefin copolymer used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（２）透明封止シートおよび着色封止シートの作製
　実施例および比較例で使用した透明封止シートおよび着色封止シートについて、次のようにそれぞれ作製した。
　まず、表２に示す処方で配合して樹脂組成物をそれぞれ得た。
　得られた樹脂組成物をＴダイ付押出機にて封止シートにそれぞれ押出成形した。
　なお、表２中における各成分の配合割合の単位は質量部である。また、表２中におけるエチレン・α－オレフィン共重合体以外の各成分の詳細は下記のとおりである。 (2) Preparation of transparent sealing sheet and colored sealing sheet The transparent sealing sheet and the colored sealing sheet used in Examples and Comparative Examples were respectively prepared as follows.
First, each resin composition was obtained by blending with the formulation shown in Table 2.
The obtained resin composition was respectively extruded into a sealing sheet with a T-die extruder.
In addition, the unit of the mixture ratio of each component in Table 2 is a mass part. The details of each component other than the ethylene / α-olefin copolymer in Table 2 are as follows.
・エチレン・酢酸ビニル共重合体１：酢酸ビニルに由来する構成単位の含有割合：２８質量％、ＭＦＲ：１５ｇ／１０分、密度：０．９５０ｇ／ｃｍ３
・シランカップリング剤１：３－メタクリロキシプロピル トリメトキシシラン
・着色剤１：酸化チタン
・架橋剤１：ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート
・架橋助剤１：トリアリルイソシアヌレート -Ethylene / vinyl acetate copolymer 1: content ratio of structural units derived from vinyl acetate: 28% by mass, MFR: 15 g / 10 min, density: 0.950 g / cm 3
Silane coupling agent 1: 3-methacryloxypropyl trimethoxysilane Colorant 1: Titanium oxide Crosslinking agent 1: t-butylperoxy-2-ethylhexyl carbonate Crosslinking aid 1: Triallyl isocyanurate
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（３）評価
＜接着強度の経時安定性＞
　得られた封止シートを４０℃９０％ＲＨの条件で２ヶ月保管した。初期と２ヶ月保管後の封止シートセットの接着強度を以下の方法で測定し、評価は初期に対する２ヶ月保管後の接着強度の保持率で行った。
　〇：２ヶ月後の接着強度保持率が８０％以上
　×：２ヶ月後の接着強度保持率が８０％未満 (3) Evaluation <Stability of adhesive strength over time>
The obtained sealing sheet was stored for 2 months at 40 ° C. and 90% RH. The adhesive strength of the sealing sheet set after the initial and two-month storage was measured by the following method, and the evaluation was performed based on the retention rate of the adhesive strength after the initial two-month storage.
○: Adhesive strength retention after 2 months is 80% or more ×: Adhesive strength retention after 2 months is less than 80%
＜太陽電池素子に対する接着強度＞
　表３に示す封止シートを太陽電池素子上に積層し、真空ラミネーター内の１５０℃に温調したホットプレート上に載せて、３分間真空減圧した後、１０分間加熱した。これにより、太陽電池素子／封止シートの積層体を作製した。ここで、各封止シートは太陽電池素子上に積層する際に互いに積層した（ただし、比較例２は除く）。
　この積層体上にある封止シートを１０ｍｍ幅に切断し、被着体である太陽電池素子に対する１８０度ピールによる剥離強度を測定した。１８０度ピールによる剥離強度は、島津社製引張試験機を用いて、２３℃、引張速度３００ｍｍ／分で測定し、３回の測定の平均値を採用して、「太陽電池素子に対する接着強度」とした。
　ここで、封止シートとして、透明封止シートと着色封止シートのシートセットを使用する場合は、透明封止シートを太陽電池素子側にした。 <Adhesive strength to solar cell element>
The sealing sheet shown in Table 3 was laminated on the solar cell element, placed on a hot plate adjusted to 150 ° C. in a vacuum laminator, vacuumed for 3 minutes, and then heated for 10 minutes. Thereby, the laminated body of the solar cell element / sealing sheet was produced. Here, each sealing sheet was laminated | stacked mutually when laminating | stacking on a solar cell element (however, except the comparative example 2).
The sealing sheet on this laminated body was cut into a width of 10 mm, and the peel strength by 180 degree peeling with respect to the solar cell element as the adherend was measured. The peel strength by 180 degree peel was measured at 23 ° C. and a tensile speed of 300 mm / min using a tensile tester manufactured by Shimadzu Corporation, and the average value of three measurements was adopted, and “adhesive strength to solar cell element” It was.
Here, when using the sheet set of a transparent sealing sheet and a coloring sealing sheet as a sealing sheet, the transparent sealing sheet was made into the solar cell element side.
＜裏面側保護部材に対する接着強度＞
　表３に示す封止シートを裏面側保護部材（ガラス）上に積層し、真空ラミネーター内の１５０℃に温調したホットプレート上に載せて、３分間真空減圧した後、１０分間加熱した。これにより、裏面側保護部材／封止シートの積層体を作製した。ここで、各封止シートは裏面側保護部材上に積層する際に互いに積層した（ただし、比較例２は除く）。
　この積層体上にある封止シートを１０ｍｍ幅に切断し、被着体である裏面側保護部材に対する１８０度ピールによる剥離強度を測定した。１８０度ピールによる剥離強度は、島津社製引張試験機を用いて、２３℃、引張速度３００ｍｍ／分で測定し、３回の測定の平均値を採用して、「裏面側保護部材に対する接着強度」とした。
　ここで、封止シートとして、透明封止シートと着色封止シートのシートセットを使用する場合は、着色封止シートを裏面側保護部材側にした。 <Adhesive strength to back side protection member>
The sealing sheet shown in Table 3 was laminated on the back-side protective member (glass), placed on a hot plate adjusted to 150 ° C. in a vacuum laminator, vacuum-reduced for 3 minutes, and then heated for 10 minutes. Thereby, the laminated body of the back surface side protection member / sealing sheet was produced. Here, each sealing sheet was laminated | stacked mutually when laminating | stacking on a back surface side protection member (however, except the comparative example 2).
The sealing sheet on this laminated body was cut into a width of 10 mm, and the peel strength by 180 degree peeling with respect to the back surface side protective member as the adherend was measured. The peel strength by 180 degree peel was measured at 23 ° C. with a tensile speed of 300 mm / min using a Shimadzu tensile tester, and the average value of three measurements was adopted. "
Here, when using the sheet set of a transparent sealing sheet and a coloring sealing sheet as a sealing sheet, the coloring sealing sheet was made into the back surface side protection member side.
＜回り込み試験＞
　エンボスガラス板／太陽電池受光面側封止シート（厚み：４５０μｍ）／アルミ板および金属板からなる疑似太陽電池素子／透明封止シート／着色封止シート／エンボスガラス板の構成で、真空ラミネーター内に仕込み、１５０℃で、３分間真空減圧した後、１０分間加熱し、積層体を得た。その後、積層体における疑似太陽電池素子への着色封止シートの回り込みを観察した。回り込みの評点は、以下の通りとした。
　◎：疑似太陽電池素子上への回り込みなし
　○：疑似太陽電池素子上への回り込みがわずかにあるが実用上問題なし
　×：疑似太陽電池素子上への回り込みがあり、実用上問題あり <Wraparound test>
Inside the vacuum laminator with the configuration of embossed glass plate / solar cell light receiving surface side sealing sheet (thickness: 450 μm) / pseudo solar cell element consisting of aluminum plate and metal plate / transparent sealing sheet / colored sealing sheet / embossed glass plate And vacuum depressurization at 150 ° C. for 3 minutes, followed by heating for 10 minutes to obtain a laminate. Then, the wraparound of the colored sealing sheet to the pseudo solar cell element in the laminate was observed. The wraparound score was as follows.
A: There is no wraparound on the pseudo solar cell element. ○: There is a slight wraparound on the pseudo solar cell element, but there is no practical problem. X: There is a wraparound on the pseudo solar cell element.
［実施例１～１０および比較例１］
　表３に示す封止シートセットを用いて上記評価をおこなった。
　得られた評価結果を表３に示す。 [Examples 1 to 10 and Comparative Example 1]
The said evaluation was performed using the sealing sheet set shown in Table 3.
The obtained evaluation results are shown in Table 3.
［比較例２］
　表２に示す透明封止シート１および着色封止シート３を積層し、１５０℃、０．１ＭＰａで各封止シートを圧着し、多層封止シート１を得た。
　封止シートセットの代わりにこの多層封止シート１を用いた以外は実施例１と同様にして上記評価をおこなった。
　得られた評価結果を表３に示す。 [Comparative Example 2]
The transparent sealing sheet 1 and the colored sealing sheet 3 shown in Table 2 were laminated, and each sealing sheet was pressure-bonded at 150 ° C. and 0.1 MPa to obtain a multilayer sealing sheet 1.
The above evaluation was performed in the same manner as in Example 1 except that this multilayer sealing sheet 1 was used instead of the sealing sheet set.
The obtained evaluation results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３から明らかなように、透明封止シートおよび着色封止シートを含む実施例の太陽電池裏面側封止シートセットは太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に優れていた。
　一方、着色封止シートのみを用いた比較例１の太陽電池裏面側封止シートセットや、透明封止シートおよび着色封止シートを事前に積層して作製した比較例２の多層封止シートは太陽電池素子および裏面側保護部材に対する接着性の経時的安定性に劣っていた。 As is clear from Table 3, the solar cell back surface side sealing sheet set of the example including the transparent sealing sheet and the colored sealing sheet is excellent in the temporal stability of the adhesiveness to the solar cell element and the back surface side protection member. It was.
On the other hand, the solar cell back side sealing sheet set of Comparative Example 1 using only the colored sealing sheet, and the multilayer sealing sheet of Comparative Example 2 prepared by previously laminating a transparent sealing sheet and a colored sealing sheet are: It was inferior to the temporal stability of the adhesiveness to the solar cell element and the back surface side protective member.
　この出願は、２０１６年１１月１０日に出願された日本出願特願２０１６－２１９８６４号、２０１６年１１月２２日に出願された日本出願特願２０１６－２２６８６７号、および２０１７年３月２９日に出願された日本出願特願２０１７－０６４６９９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 includes Japanese application Japanese Patent Application No. 2016-212864 filed on November 10, 2016, Japanese Application No. 2016-226867 filed on November 22, 2016, and March 29, 2017. Claiming priority based on Japanese Patent Application No. 2017-064699 for which application has been filed, the entire disclosure of which is incorporated herein.

Claims (18)

  1. 　太陽電池素子と裏面側保護部材との間に配置させて前記太陽電池素子の非受光面側を封止するために用いられ、透明封止シートと着色封止シートとを備える太陽電池裏面側封止シートセットであって、
    　前記透明封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体を含み、かつ、前記太陽電池素子側に配置されるものであり、
    　前記着色封止シートがエチレン・α－オレフィン共重合体およびエチレン・極性モノマー共重合体から選択される少なくとも一種のエチレン系共重合体と着色剤とを含み、かつ、前記裏面側保護部材側に配置されるものであり、
    　前記太陽電池素子を封止する際に前記透明封止シートと前記着色封止シートとを積層させて使用する太陽電池裏面側封止シートセット。     A solar cell back side sealing provided with a transparent sealing sheet and a colored sealing sheet, which is used for sealing the non-light-receiving surface side of the solar cell element by being disposed between the solar cell element and the back side protective member. Stop sheet set,
    The transparent encapsulating sheet contains at least one ethylene-based copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer, and is disposed on the solar cell element side. Yes,
    The colored encapsulating sheet contains at least one ethylene copolymer selected from an ethylene / α-olefin copolymer and an ethylene / polar monomer copolymer and a colorant, and on the back side protective member side Is to be placed,
    The solar cell back surface side sealing sheet set which laminates | stacks and uses the said transparent sealing sheet and the said colored sealing sheet when sealing the said solar cell element.
  2. 　請求項１に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートの厚みが１００μｍ以上である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set of Claim 1,
    The solar cell back surface side sealing sheet set whose thickness of the said transparent sealing sheet is 100 micrometers or more.
  3. 　請求項１または２に記載の太陽電池裏面側封止シートセットにおいて、
    　前記着色封止シートに含まれる前記着色剤が酸化チタン、カーボンブラックおよび赤外線反射顔料から選択される少なくとも一種を含む太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set of Claim 1 or 2,
    The solar cell back surface side sealing sheet set in which the said coloring agent contained in the said colored sealing sheet contains at least 1 type selected from a titanium oxide, carbon black, and an infrared reflective pigment.
  4. 　請求項３に記載の太陽電池裏面側封止シートセットにおいて、
    　前記着色封止シート中の前記着色剤の含有量が、前記着色封止シート中の前記エチレン系共重合体１００質量部に対して、０．５質量部以上５０質量部以下である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set of Claim 3,
    The back surface of the solar cell in which the content of the colorant in the colored encapsulating sheet is 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer in the colored encapsulating sheet. Side sealing sheet set.
  5. 　請求項１乃至４のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートがシランカップリング剤を含む太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 4,
    The solar cell back surface side sealing sheet set in which the said transparent sealing sheet contains a silane coupling agent.
  6. 　請求項５に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シート中の前記シランカップリング剤の含有量が、前記透明封止シート中の前記エチレン系共重合体１００質量部に対して、０．０１質量部以上５質量部以下である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set according to claim 5,
    The sun whose content of the said silane coupling agent in the said transparent sealing sheet is 0.01 mass part or more and 5 mass parts or less with respect to 100 mass parts of the said ethylene-type copolymers in the said transparent sealing sheet. Battery back side sealing sheet set.
  7. 　請求項１乃至６のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートおよび前記着色封止シートの少なくとも一方が前記エチレン系共重合体として前記エチレン・α－オレフィン共重合体を含み、前記エチレン・α－オレフィン共重合体が以下の要件ａ１）およびａ２）のうち少なくとも１つを満たす太陽電池裏面側封止シートセット。
    　ａ１）ＡＳＴＭ　Ｄ１５０５に準拠して測定される密度が０．８６５～０．８９５ｇ／ｃｍ３である。
    　ａ２）ＡＳＴＭ　Ｄ２２４０に準拠して測定されるショアＡ硬度が６０～９５である。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 6,
    At least one of the transparent sealing sheet and the colored sealing sheet contains the ethylene / α-olefin copolymer as the ethylene copolymer, and the ethylene / α-olefin copolymer has the following requirements a1) and The solar cell back surface side sealing sheet set which satisfy | fills at least 1 among a2).
    a1) The density measured according to ASTM D1505 is 0.865 to 0.895 g / cm 3 .
    a2) Shore A hardness measured according to ASTM D2240 is 60-95.
  8. 　請求項１乃至６のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートおよび前記着色封止シートの少なくとも一方が前記エチレン系共重合体として前記エチレン・極性モノマー共重合体を含み、
    　前記エチレン・極性モノマー共重合体がエチレン・酢酸ビニル共重合体を含む太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 6,
    At least one of the transparent sealing sheet and the colored sealing sheet includes the ethylene / polar monomer copolymer as the ethylene copolymer,
    The solar cell back side sealing sheet set in which the ethylene / polar monomer copolymer contains an ethylene / vinyl acetate copolymer.
  9. 　請求項８に記載の太陽電池裏面側封止シートセットにおいて、
    　前記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合が１０質量％以上４７質量％以下である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set of Claim 8,
    The solar cell back surface side sealing sheet set whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less.
  10. 　請求項１乃至９のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定される、前記着色封止シートに含まれる前記エチレン系共重合体のＭＦＲが０．０１ｇ／１０分以上３０ｇ／１０分以下である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 9,
    According to ASTM D1238, the MFR of the ethylene-based copolymer contained in the colored sealing sheet measured at 190 ° C. and a load of 2.16 kg is 0.01 g / 10 min or more and 30 g / 10 min or less. A solar cell back side sealing sheet set.
  11. 　請求項１乃至１０のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートおよび前記着色封止シートの少なくとも一方が有機過酸化物をさらに含む太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 10,
    The solar cell back surface side sealing sheet set in which at least one of the transparent sealing sheet and the colored sealing sheet further contains an organic peroxide.
  12. 　請求項１１に記載の太陽電池裏面側封止シートセットにおいて、
    　前記有機過酸化物の含有量が、前記有機過酸化物を含むシート中の前記エチレン系共重合体１００質量部に対して、０．１質量部以上３質量部以下である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set of Claim 11,
    The solar cell back side sealing whose content of the said organic peroxide is 0.1 to 3 mass parts with respect to 100 mass parts of the said ethylene-type copolymer in the sheet | seat containing the said organic peroxide. Stop sheet set.
  13. 　請求項１乃至１２のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記透明封止シートが前記太陽電池素子に接するように配置され、前記着色封止シートが前記裏面側保護部材に接するように配置される太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 12,
    The solar cell back surface side sealing sheet set arrange | positioned so that the said transparent sealing sheet may contact | connect the said solar cell element, and the said colored sealing sheet may contact | connect the said back surface side protection member.
  14. 　請求項１乃至１３のいずれか一項に記載の太陽電池裏面側封止シートセットにおいて、
    　前記裏面側保護部材がガラス板である太陽電池裏面側封止シートセット。     In the solar cell back surface side sealing sheet set as described in any one of Claims 1 thru | or 13,
    The solar cell back surface side sealing sheet set whose said back surface side protection member is a glass plate.
  15. 　表面側透明保護部材と、
    　裏面側保護部材と、
    　太陽電池素子と、
    　前記太陽電池素子を前記表面側透明保護部材と前記裏面側保護部材との間に封止する封止層と、
    を備え、
    　前記封止層が受光面側に配置される受光面側封止層と非受光面側に配置される裏面側封止層とを含み、
    　前記裏面側封止層が請求項１乃至１４のいずれか一項に記載の太陽電池裏面側封止シートセットにより形成されており、
    　前記透明封止シートにより構成された裏面側透明封止層が前記太陽電池素子側に配置されており、前記着色封止シートにより構成された裏面側着色封止層が前記裏面側保護部材側に配置されている太陽電池モジュール。     A surface-side transparent protective member;
    A back side protection member;
    A solar cell element;
    A sealing layer for sealing the solar cell element between the front surface side transparent protective member and the back surface side protective member;
    With
    The light-receiving surface side sealing layer disposed on the light-receiving surface side and the back-side sealing layer disposed on the non-light-receiving surface side,
    The back surface side sealing layer is formed by the solar cell back surface side sealing sheet set according to any one of claims 1 to 14,
    The back side transparent sealing layer comprised by the said transparent sealing sheet is arrange | positioned at the said solar cell element side, and the back side colored sealing layer comprised by the said colored sealing sheet is on the said back side protection member side Solar cell module being placed.
  16. 　請求項１５に記載の太陽電池モジュールにおいて、
    　前記裏面側透明封止層が前記太陽電池素子に接しており、前記裏面側着色封止層が前記裏面側保護部材に接している太陽電池モジュール。     The solar cell module according to claim 15,
    The solar cell module in which the back side transparent sealing layer is in contact with the solar cell element, and the back side colored sealing layer is in contact with the back side protective member.
  17. 　請求項１５または１６に記載の太陽電池モジュールにおいて、
    　前記表面側透明保護部材および前記裏面側保護部材がそれぞれガラス板であり、
    　当該太陽電池モジュールが合わせガラス型太陽電池モジュールである太陽電池モジュール。     The solar cell module according to claim 15 or 16,
    The front surface side transparent protective member and the back surface side protective member are each glass plates,
    A solar cell module in which the solar cell module is a laminated glass solar cell module.
  18. 　請求項１５乃至１７のいずれか一項に記載の太陽電池モジュールを製造するための製造方法であって、
    　前記太陽電池素子を太陽電池受光面側封止シートと太陽電池裏面側封止シートとで挟んだ状態で加熱し、前記太陽電池素子を前記太陽電池受光面側封止シートと前記太陽電池裏面側封止シートとの間に封止する工程を含み、
    　前記太陽電池裏面側封止シートが請求項１乃至１４のいずれか一項に記載の太陽電池裏面側封止シートセットを含み、
    　前記透明封止シートと前記着色封止シートとを別々に準備し、前記太陽電池素子を封止する前記工程において、前記透明封止シートと前記着色封止シートとを積層する太陽電池モジュールの製造方法。     A manufacturing method for manufacturing the solar cell module according to any one of claims 15 to 17,
    The solar cell element is heated in a state sandwiched between the solar cell light-receiving surface side sealing sheet and the solar cell back surface side sealing sheet, and the solar cell element is heated to the solar cell light-receiving surface side sealing sheet and the solar cell back surface side. Including a step of sealing between the sealing sheet,
    The solar cell back side sealing sheet includes the solar cell back side sealing sheet set according to any one of claims 1 to 14,
    The transparent encapsulating sheet and the colored encapsulating sheet are separately prepared, and in the step of encapsulating the solar cell element, the solar cell module is manufactured by laminating the transparent encapsulating sheet and the colored encapsulating sheet. Method.
PCT/JP2017/039714 2016-11-10 2017-11-02 Solar cell rear surface sealant sheet set, solar cell module and method for producing solar cell module WO2018088322A1 (en)

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JP2013229410A (en) * 2012-04-25 2013-11-07 Mitsui Chemicals Tohcello Inc Solar cell sealing material and solar cell module
WO2014020708A1 (en) * 2012-07-31 2014-02-06 三洋電機株式会社 Solar cell module
WO2014033802A1 (en) * 2012-08-27 2014-03-06 三洋電機株式会社 Solar cell module
US20150027516A1 (en) * 2012-03-12 2015-01-29 Renolit Belgium N.V. Backsheet and photovoltaic modules comprising it
WO2016047054A1 (en) * 2014-09-26 2016-03-31 パナソニックＩｐマネジメント株式会社 Solar cell module

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JP2011216804A (en) * 2010-04-02 2011-10-27 Bridgestone Corp Sealing film for solar cell, solar cell using the same, and method of manufacturing solar cell
US20150027516A1 (en) * 2012-03-12 2015-01-29 Renolit Belgium N.V. Backsheet and photovoltaic modules comprising it
JP2013229410A (en) * 2012-04-25 2013-11-07 Mitsui Chemicals Tohcello Inc Solar cell sealing material and solar cell module
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