WO2016043235A1 - 太陽電池用封止材及び太陽電池モジュール - Google Patents

太陽電池用封止材及び太陽電池モジュール Download PDF

Info

Publication number
WO2016043235A1
WO2016043235A1 PCT/JP2015/076347 JP2015076347W WO2016043235A1 WO 2016043235 A1 WO2016043235 A1 WO 2016043235A1 JP 2015076347 W JP2015076347 W JP 2015076347W WO 2016043235 A1 WO2016043235 A1 WO 2016043235A1
Authority
WO
WIPO (PCT)
Prior art keywords
solar cell
mass
ethylene
layer
volume resistivity
Prior art date
Application number
PCT/JP2015/076347
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
礒川　素朗
一関　主税
結 遠藤
紀彦 佐藤
宏志 内山
Original Assignee
三井・デュポンポリケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井・デュポンポリケミカル株式会社 filed Critical 三井・デュポンポリケミカル株式会社
Priority to JP2016548920A priority Critical patent/JP6542782B2/ja
Publication of WO2016043235A1 publication Critical patent/WO2016043235A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • 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

  • One embodiment of the present invention relates to a solar cell sealing material for fixing a solar cell element in a solar cell module, and a solar cell module in which the solar cell element is sealed with the solar cell sealing material.
  • JP-A-2009-298046 discloses an ethylene / (meth) acrylic acid copolymer or a multilayer sheet having improved fracture strength, impact resistance and puncture resistance while maintaining transparency and noise level.
  • a three-layer sheet comprising an intermediate layer composed of the (A) layer mainly composed of the ionomer, and an outer layer composed of the (B) layer composed mainly of the ethylene / vinyl acetate copolymer formed on both surfaces thereof.
  • Japanese Patent Application Laid-Open No. 2014-27034 includes a crosslinked cured film of a composition containing an ethylene-polar monomer copolymer and a crosslinking agent as a solar cell encapsulant film capable of suppressing the generation of PID,
  • a solar cell sealing film having a volume resistivity at 25 ° C. of 5.0 ⁇ 10 13 or more is disclosed.
  • the three-layer sheet described in JP-A-2009-298046 and the solar cell sealing material described in JP-A-2014-27034 are both EVA as a main component of the layer forming the outermost layer, Since the volume resistivity is low, the occurrence of PID may not be sufficiently suppressed.
  • One embodiment of the present invention has been made in view of the above, and it is an object to achieve the following object. That is, one embodiment of the present invention aims to provide a solar cell sealing material excellent in PID resistance and a solar cell module using the solar cell sealing material.
  • the solar cell sealing material according to ⁇ 1> wherein the outermost layer includes an ethylene / (meth) acrylic acid copolymer, and the intermediate layer includes an ethylene / vinyl acetate copolymer.
  • the solar cell encapsulant according to ⁇ 1> or ⁇ 2> in which three layers of the outermost layer of the two layers and the intermediate layer are laminated.
  • the volume resistivity of the whole sealing material is 1.0 ⁇ 10 15 ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less, according to any one of ⁇ 1> to ⁇ 3> Solar cell encapsulant.
  • ⁇ 5> The solar cell sealing according to any one of ⁇ 1> to ⁇ 4>, wherein the ratio of the thickness of one of the outermost layers of the two layers to the intermediate layer is 1/2 to 1/8 Wood.
  • a solar cell module comprising the solar cell sealing material according to any one of ⁇ 1> to ⁇ 5>.
  • a solar cell sealing material excellent in PID resistance and a solar cell module using the solar cell sealing material are provided.
  • FIG. It is a photograph which shows the state of the sheet
  • FIG. It is a photograph which shows the state of the sheet
  • the solar cell encapsulant according to an embodiment of the present invention has two outermost layers having a volume resistivity of 1.0 ⁇ 10 15 ⁇ ⁇ cm to 1.0 ⁇ 10 18 ⁇ ⁇ cm, At least three layers including an intermediate layer having a volume resistivity of 1.0 ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm provided between the two outermost layers are laminated. Is done.
  • the volume resistivity of the entire encapsulant is 1.0 ⁇ 10 15 ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less. preferable.
  • the solar cell encapsulant has at least a three-layer structure, and the volume resistivity of the outermost layer is 1.0 ⁇ 10 15 ⁇ ⁇ cm or more, whereby the solar cell module is Even when operated at a high voltage, it is considered that the sealing material can maintain high insulation and the occurrence of leakage current is suppressed. Thereby, it is thought that the sealing material for solar cells will be excellent in PID tolerance. Below, the sealing material for solar cells which is one Embodiment of this invention is demonstrated in detail.
  • the sealing material for solar cells includes an outermost layer having a volume resistivity of 1.0 ⁇ 10 15 ⁇ ⁇ cm to 1.0 ⁇ 10 18 ⁇ ⁇ cm.
  • the outermost layer is a layer located on the outermost side of the solar cell encapsulant, and the solar cell encapsulant having at least a three-layer structure has two outermost layers.
  • the sealing material for solar cells has an intermediate layer described later between one outermost layer (for example, a layer on which sunlight is incident) and the other outermost layer (for example, a layer on the solar cell element side). .
  • the volume resistivity of the outermost layer is less than 1.0 ⁇ 10 15 ⁇ ⁇ cm, the insulating material of the sealing material is inferior and leakage current during high voltage operation cannot be suppressed. Moreover, when the volume resistivity of the outermost layer is 1.0 ⁇ 10 18 ⁇ ⁇ cm or less, it becomes easy to obtain a material for forming the outermost layer.
  • the volume resistivity of the outermost layer is preferably 1.0 ⁇ 10 16 ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less from the above viewpoint.
  • the volume resistivity can be measured according to JIS C 2139: 2008. The volume resistivity can be adjusted by the material forming the outermost layer.
  • the material forming the outermost layer can be selected from those having a volume resistivity of 1.0 ⁇ 10 15 ⁇ ⁇ cm to 1.0 ⁇ 10 18 ⁇ ⁇ cm. Moreover, if the volume resistivity of the outermost layer to be formed satisfies 1.0 ⁇ 10 15 ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less, the volume resistivity in another range as a material for forming the outermost layer. You may use the material which has.
  • the materials of the two outermost layers present in the solar cell encapsulant may be the same or different.
  • the outermost layer preferably contains an ethylene / (meth) acrylic acid copolymer as a main component from the viewpoint of easily adjusting the volume resistivity to the above range.
  • the “main component” here means a component contained in the outermost layer in an amount of 70% by mass or more based on the total mass of the outermost layer.
  • the outermost layer preferably contains 80% by mass or more, and 90% by mass or more of the ethylene / (meth) acrylic acid copolymer with respect to the total mass of the outermost layer. More preferably. Within the above range, it is preferable that the outermost layer contains an ethylene / (meth) acrylic acid copolymer because good transparency and good PID resistance can be obtained.
  • the content of structural units derived from ethylene is preferably 75% by mass to 95% by mass with respect to the total mass of the copolymer, 75% by mass to More preferably, it is 92 mass%.
  • the content of the structural unit derived from ethylene is 75% by mass or more, the heat resistance, mechanical strength, and the like of the copolymer are further improved.
  • the content of the structural unit derived from ethylene is 95% by mass or less, the transparency, flexibility, and adhesiveness of the copolymer are further improved.
  • the content of structural units derived from (meth) acrylic acid is preferably 5% by mass to 25% by mass with respect to the total mass of the copolymer. More preferred is from 25% by weight.
  • the structural unit derived from (meth) acrylic acid in the copolymer plays an important role in adhesion to a substrate such as glass, and if the content is 5% by mass or more, it is transparent and flexible. When the content is 25% by mass or less, the stickiness is suppressed and the workability is good.
  • the content of the structural unit derived from (meth) acrylic acid in the ethylene / (meth) acrylic acid copolymer is determined from the viewpoint of workability. 8 mass% or more and 18 mass% or less are preferable with respect to the total mass. Further, the content of the structural unit derived from (meth) acrylic acid is most preferably 13% by mass or more and 18% by mass or less with respect to the total mass of the copolymer from the viewpoint of processability and optical properties.
  • the ethylene / (meth) acrylic acid copolymer includes structural units derived from other copolymerizable monomers. It may be.
  • the content of structural units derived from other copolymerizable monomers is more than 0% by mass and 30% by mass with respect to a total of 100% by mass of structural units derived from ethylene and structural units derived from (meth) acrylic acid. % Or less, more preferably 0% by mass to 25% by mass or less.
  • copolymerizable monomers include, for example, unsaturated esters.
  • unsaturated esters include vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and isobutyl methacrylate.
  • (meth) acrylic acid alkyl esters It is preferable that an unsaturated ester is contained in the above range as another copolymerizable monomer because the flexibility of the ethylene / (meth) acrylic acid copolymer is improved.
  • the ethylene / (meth) acrylic acid copolymer can be obtained by radical copolymerization of each polymerization component at high temperature and high pressure.
  • melt flow rate (MFR) JIS K 7210: 1999
  • 150 g / 10 min is preferable, and 30 g / 10 min to 100 g / 10 min is particularly preferable.
  • the outermost layer can contain various additives within a range that does not impair the object of the present invention.
  • additives include a crosslinking agent, a crosslinking aid, a silane coupling agent, an ultraviolet absorber, a light stabilizer, and an antioxidant.
  • an organic peroxide having a decomposition temperature of half-life of 1 hour is usually 90 ° C. to 180 ° C., more preferably 100 ° C. to 150 ° C.
  • organic peroxides include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohe
  • the content of the crosslinking agent in the outermost layer is preferably 0.1 parts by mass to 5 parts by mass and more preferably 0.5 parts by mass to 3 parts by mass with respect to 100 parts by mass of the ethylene / (meth) acrylic acid copolymer. preferable.
  • crosslinking aid examples include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds.
  • polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate and diallyl maleate; poly (meta) such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate ) Acryloxy compounds; divinylbenzene and the like.
  • the content of the crosslinking aid in the outermost layer is preferably 5 parts by mass or less, more preferably 0.1 part by mass to 3 parts by mass with respect to 100 parts by mass of the ethylene / (meth) acrylic acid copolymer.
  • silane coupling agent examples include a silane coupling agent having a vinyl group, an amino group or an epoxy group, and a hydrolyzing group such as an alkoxy group, and a titanate coupling agent.
  • Specific examples of the silane coupling agent include vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltrimethoxy.
  • Silane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyl
  • Examples include diethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
  • the content of the silane coupling agent in the outermost layer is preferably 5 parts by mass or less, more preferably 0.02 parts by mass to 3 parts by mass, when the total mass of the outermost layer is 100 parts by mass.
  • the outermost layer contains the silane coupling agent in the above range, the adhesion between the solar cell sealing material and the transparent protective material or solar cell element is improved.
  • Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone and 2-hydroxy-4-n- Benzophenone ultraviolet absorbers such as octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole and Examples include benzotriazole ultraviolet absorbers such as 2- (2′-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid ester ultraviolet absorbers such as phenyl salicylate and p-octylphenyl salicylate.
  • Examples of the light stabilizer include hindered amine light stabilizers.
  • Specific examples of the hindered amine light stabilizer include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2.
  • antioxidants examples include various hindered phenol-based antioxidants and phosphite-based antioxidants.
  • Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethy
  • phosphite antioxidants include 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate dimethyl ester, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid) Examples thereof include ethyl and tris (2,4-di-t-butylphenyl) phosphinate.
  • the contents of the ultraviolet absorber, light stabilizer and antioxidant in the outermost layer are each preferably 5 parts by mass or less, and 0.1 to 3 parts by mass, respectively, when the total mass of the outermost layer is 100 parts by mass. Part is more preferred.
  • the sealing material When using the sealing material on the side opposite to the light-receiving surface side, it may contain additives such as a colorant, a light diffusing agent, a flame retardant, and a metal deactivator in addition to the above-described additives as necessary. Can do.
  • the colorant include pigments (inorganic pigments, organic pigments), dyes, and the like. These colorants can be appropriately selected from various known ones.
  • inorganic pigments include white inorganic pigments such as titanium oxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, and precipitated silica, carbon black, lamp black, titanium black, synthetic Black inorganic pigments such as iron black, gray inorganic pigments such as zinc powder, lead suboxide, slate powder, red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, red rose, molybten red, red lead, amber, iron oxide tea Brown inorganic pigments such as cadmium yellow, zinc yellow, ocher, sienna, synthetic ocher, yellow inorganic pigments such as yellow lead, titanium yellow, green inorganic pigments such as chromium oxide green, cobalt green, chromium green, ultramarine blue, bitumen, iron Examples include blue inorganic pigments such as blue and cobalt blue, and metal powder inorganic pigments.
  • organic pigments include Permanent Red 4R, Para Red, First Yellow G, First Yellow 10G, Disazo Yellow G, Disazo Yellow GR, Disazo Orange, Pyrazolone Orange, Brilliant Carmine 3B, Brilliant Carmine 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmine FB, Risole Red R, Risole Red B, Rake Red C, Rake Red D, Brilliant Fast ⁇ Azo pigments such as Scarlet, Pyrazolone Red, Bon Maroon Light, Bon Maroon Medium, Fire Red, Nitroso Pigments such as Naphthol Green B, Nito such as Naphthol Yellow S Pigments, basic dyes such as rhodamine B lake and rhodamine 6G lake, mordant dyes such as alizarin and lake, vat dyes such as indanthrene blue, phthalocyanine blue, phthalocyanine green, fast Examples thereof include phthalocyanine pigments such as sky blue and dioxazine pigments such as
  • a solar cell sealing material containing these additives When a solar cell sealing material containing these additives is used as a sealing material on the light receiving side of a solar cell element, transparency may be impaired, but sealing on the surface opposite to the light receiving side of the solar cell element may occur. When used as a material, it is preferably used.
  • Examples of the light diffusing agent include inorganic beads such as glass beads, silica beads, silicon alkoxide beads, and hollow glass beads.
  • Examples of the organic spherical material include plastic beads such as acrylic beads and vinylbenzene beads.
  • the flame retardant examples include metal hydrates such as halogen flame retardant such as bromide, phosphorus flame retardant, silicone flame retardant, magnesium hydroxide and aluminum hydroxide.
  • metal deactivators include those well known as compounds that suppress metal damage of thermoplastic resins. Two or more metal deactivators may be used in combination.
  • the metal deactivator include hydrazide derivatives or triazole derivatives.
  • examples of the hydrazide derivative include decamethylene dicarboxyl-disalicyloyl hydrazide, 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionate.
  • the triazole derivative include 3- (N-salicyloyl) amino-1,2,4-triazole.
  • the sealing material for solar cells includes an intermediate layer having a volume resistivity of 1.0 ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm.
  • the intermediate layer is a layer disposed between the two outermost layers, and the solar cell encapsulant includes at least one intermediate layer, and the intermediate layer may be composed of two or more layers.
  • the volume resistivity of the intermediate layer is preferably 1.0 ⁇ 10 12 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm.
  • the volume resistivity can be measured by the method described above.
  • the volume resistivity can be adjusted by the material forming the intermediate layer.
  • the material forming the intermediate layer can be selected from those having a volume resistivity of 1.0 ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm. It is also possible to use a general-purpose material with low PID resistance, such as ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm. Moreover, if the volume resistivity of the intermediate layer to be formed satisfies 1.0 ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 15 ⁇ ⁇ cm, the volume resistivity in another range as a material for forming the intermediate layer You may use the material which has.
  • the intermediate layer preferably contains an ethylene / vinyl acetate copolymer as a main component from the viewpoint of easily adjusting the volume resistivity to the above range.
  • the “main component” as used herein means a component contained in the intermediate layer in an amount of 70% by mass or more based on the total mass of the intermediate layer.
  • the intermediate layer preferably contains 80% by mass or more of ethylene / vinyl acetate copolymer, and more preferably 90% by mass or more.
  • the ethylene / vinyl acetate copolymer includes a structural unit derived from ethylene and a structural unit derived from vinyl acetate.
  • the ethylene / vinyl acetate copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.
  • the content of structural units derived from ethylene is preferably 60% by mass to 85% by mass, and 65% by mass to 82% by mass with respect to the total mass of the copolymer. More preferably.
  • the structural unit derived from ethylene is 60% by mass or more, the impact resistance and puncture resistance of the intermediate layer are further improved.
  • the structural unit derived from ethylene is 85% by mass or less, the transparency and flexibility of the intermediate layer are further improved.
  • the content of the structural unit derived from vinyl acetate is preferably 15% by mass to 40% by mass with respect to the total mass of the copolymer, and 18% by mass to 35% by mass. More preferably.
  • the structural unit derived from vinyl acetate is 15% by mass or more, the transparency and flexibility of the intermediate layer are further improved.
  • the structural unit derived from vinyl acetate is 40% by mass or less, stickiness is suppressed and workability is good.
  • the ethylene / vinyl acetate copolymer may further include a structural unit derived from another monomer, but in one embodiment of the present invention, It is preferable that an ethylene / vinyl acetate copolymer is formed by a structural unit derived from vinyl acetate and a structural unit derived from ethylene without including a structural unit derived from another monomer.
  • the ethylene / vinyl acetate copolymer may be produced by a conventionally known method, or a commercially available product may be used.
  • the melt flow rate at 190 ° C. under a load of 2160 g (JIS K 7210: 1999) of the ethylene / vinyl acetate copolymer is preferably 0.1 g / 10 min to 150 g / 10 min from the viewpoint of workability and mechanical strength. More preferably, it is 0.1 g / 10 min to 50 g / 10 min.
  • the intermediate layer may contain various additives within a range that does not impair the object of the present invention.
  • this additive the same thing as what was mentioned above as an additive which can be contained in an outermost layer is mentioned.
  • the preferred range of the additive content in the intermediate layer is the same as the preferred range of the additive content in the outermost layer.
  • the solar cell encapsulant has at least a three-layer structure including the outermost layer described above and the intermediate layer described above, and the intermediate layer is located between the two outermost layers.
  • the solar cell encapsulant preferably has a three-layer structure in which the outermost layer includes an ethylene / (meth) acrylic acid copolymer and the intermediate layer includes an ethylene / vinyl acetate copolymer. That is, the structure of the solar cell encapsulant is preferably an ethylene / (meth) acrylic acid copolymer / ethylene / vinyl acetate copolymer / ethylene / (meth) acrylic acid copolymer.
  • the solar cell encapsulant has the above three-layer structure, it has excellent PID resistance, as well as excellent shrinkage resistance and storage stability when exposed to high-temperature environments, and can be extruded. Excellent moldability.
  • the thickness ratio (outermost layer / intermediate layer) of the outermost layer and the intermediate layer of the solar cell encapsulant is preferably 1/1 to 1/10, more preferably 1/2 to 1/8, Most preferably, it is 1/2 to 1/5.
  • the thickness ratio (outermost layer / intermediate layer) is within the above range, the volume resistivity of the entire solar cell encapsulant can be maintained, and a higher PID resistance can be imparted to the solar cell encapsulant. Can do.
  • the thickness of the outermost layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 20 ⁇ m to 300 ⁇ m.
  • the thickness of the outermost layer here means the thickness of each of the two outermost layers (the protective material side layer and the solar cell element side layer).
  • the thickness of the layer on the protective material side and the thickness of the layer on the solar cell element side may be the same or different.
  • PID resistance and adhesiveness are further improved.
  • the outermost layer thickness is 500 ⁇ m or less, it is excellent in transparency and uneven follow-up property with respect to the transparent protective material.
  • the thickness of the intermediate layer is preferably 50 ⁇ m or more and 1000 ⁇ m or less, and more preferably 50 ⁇ m or more and 700 ⁇ m or less.
  • the thickness of the intermediate layer here means the total thickness of the intermediate layer having a specific volume resistivity. When the intermediate layer is formed of two layers, the total thickness of the two layers is shown. If the thickness of the intermediate layer is 100 ⁇ m or more, the workability can be further improved. Further, when the thickness of the intermediate layer is 1000 ⁇ m or less, the transparency is more excellent. When the intermediate layer is composed of two or more layers, the thickness of each layer may be the same or different.
  • the total thickness of the solar cell encapsulant is not particularly limited, but the total thickness is preferably in the range of 5 ⁇ m to 2000 ⁇ m (0.005 mm to 2 mm), and 100 ⁇ m to 2000 ⁇ m (0.1 mm to 2 mm). Is more preferable, and a range of 100 ⁇ m to 1500 ⁇ m (0.1 mm to 1.5 mm) is even more preferable.
  • the total thickness is in the range of 5 ⁇ m to 2000 ⁇ m, it is excellent in economic efficiency (that is, at an appropriate cost as a product), and is excellent in PID resistance, adhesiveness and transparency.
  • the encapsulant for solar cell preferably has a volume resistivity of 1.0 ⁇ 10 15 ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less, and 1.0 ⁇ 10 16 or less. More preferably, it is ⁇ ⁇ cm or more and 1.0 ⁇ 10 18 ⁇ ⁇ cm or less.
  • the volume resistivity of the whole sealing material here means a value obtained by measuring the volume resistivity of the whole laminate laminated in at least three layers. The volume resistivity can be measured by the above method.
  • the solar cell encapsulant is bonded with a double vacuum chamber laminating machine in a state where the solar cell encapsulant is sandwiched between two 3.2 mm thick white glass (conditions: 150 ° C., 13 minutes), and then cooling in the atmosphere at 23 ° C. (ie, cooling), the total light transmittance according to JIS K 7361-1: 1997 can be 83% or more.
  • the total light transmittance after cooling is as high as 83% or more, showing very good transparency.
  • the total light transmittance is more preferably 85% or more.
  • the total light transmittance is a value measured according to JIS K 7136: 2000 using a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
  • the term “cooling (removal)” refers to cooling at a rate of temperature decrease of 15 ° C./min or less (calculated from the temperature 5 minutes after the start of cooling).
  • the solar cell encapsulant can be molded by a known method using a multilayer T-die molding machine, a calendar molding machine, a multilayer inflation molding machine, or the like.
  • the molding of a solar cell encapsulant having a three-layer structure in which two outermost layers and an intermediate layer are laminated is performed, for example, on an ethylene / (meth) acrylic acid copolymer for outermost layer formation.
  • a dry-blended mixture with additives such as cross-linking agents, cross-linking aids, adhesion-imparting agents, antioxidants, light stabilizers and UV absorbers, and ethylene / vinyl acetate for intermediate layer formation.
  • a multi-layer T-die from a hopper with a mixture obtained by adding a cross-linking agent, a cross-linking aid, an adhesion-imparting agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like as necessary to the polymer and dry blending. It can supply by supplying to the main extruder and a subextruder of an extruder, and can carry out by carrying out multilayer extrusion molding to a sheet form.
  • the molding of the solar cell encapsulant having a three-layer structure is performed by, for example, adding a cross-linking agent and a cross-linking aid to a melt obtained by melting an ethylene / (meth) acrylic acid copolymer for forming the outermost layer.
  • Mixture obtained by melt blending an agent or various additives and a melt obtained by melting an ethylene / vinyl acetate copolymer for forming an intermediate layer and, if necessary, a mixture obtained by melt blending a crosslinking agent, a crosslinking aid or various additives. Can also be supplied to the extruder from the hopper and multilayer extrusion molding into a sheet shape.
  • additives such as a crosslinking agent, an antioxidant, a light stabilizer, and an ultraviolet absorber are preliminarily used as a master batch to form an ethylene / (meth) acrylic acid heavy polymer for outermost layer formation. It is also possible to add to the melt of the coalescence or the melt of the ethylene / vinyl acetate copolymer for the intermediate layer.
  • the processing temperature in the molding of the solar cell encapsulant is preferably in the range of 80 ° C. to 230 ° C., and the processing temperature can be selected according to the processability of the components used.
  • the solar cell module which is one Embodiment of this invention is equipped with the sealing material for solar cells which is one Embodiment of this invention.
  • a solar cell module can be produced by using a solar cell sealing material according to an embodiment of the present invention and fixing solar cell elements with upper and lower protective materials.
  • Examples of such solar cell modules include various types. For example, it is formed on the surface of a substrate such as glass or the like having a structure sandwiched between both sides of the solar cell element, such as upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material.
  • the solar cell element is sandwiched between both sides of the solar cell element, such as upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material.
  • the solar cell element include a solar cell element formed on the peripheral surface, for example, a structure in which an encapsulant and a lower protective material are formed on an amorphous solar cell element formed on a fluororesin-based sheet by sputtering or the like. Since the solar cell module includes the solar cell encapsulant that is one embodiment of the present invention having excellent PID resistance, the encapsulant can maintain high insulation even when operated at a high voltage. The generation of leakage current is suppressed, and the PID resistance is excellent.
  • Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, cadmium-tellurium, and II.
  • Various solar cell elements such as a group VI compound semiconductor can be used.
  • the solar cell encapsulant which is an embodiment of the present invention is particularly useful for encapsulating single crystal and polycrystalline solar cell elements.
  • the upper transparent protective material constituting the solar cell module examples include glass, acrylic resin, polycarbonate, polyester, and fluorine-containing resin.
  • a lower protective material a single-piece
  • the lower protective material include metals such as tin, aluminum, and stainless steel, inorganic materials such as glass, polyester, inorganic material-deposited polyester, fluorine-containing resins, and single-layer or multilayer sheets such as polyolefin.
  • the solar cell sealing material which is one embodiment of the present invention exhibits good adhesion to these upper protective material or lower protective material.
  • a conventional ethylene / vinyl acetate copolymer is used when laminating and bonding together with the solar cell element, the upper protective material, and the lower protective material, using the solar cell encapsulant according to an embodiment of the present invention. Even if the cross-linking step by pressurization and heating for a long time, which has been performed in the above system, is not performed, it is possible to impart adhesive strength that can withstand practical use and long-term stability of adhesive strength. However, from the viewpoint of imparting stronger adhesive strength and adhesive strength stability, it is recommended to perform pressurizing and heating treatment for a short time.
  • the solar cell encapsulant was produced using the molding machine shown below.
  • ⁇ Multi-layer T-die molding machine Tanabe Plastics Machinery Co., Ltd. Feed block type: EDI Co.
  • Extruders are all 40mm ⁇ single-screw extruder Die width 500mm
  • Single layer T-die molding machine Tanabe Plastics Machine Co., Ltd.
  • Extruder is 40mm ⁇ single screw extruder Die width 500mm
  • Example 1 The outer layer 1 and the outer layer were prepared by adding 0.2 parts by mass of a silane coupling agent (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of the ethylene / methacrylic acid copolymer. Used for 2.
  • a silane coupling agent trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a crosslinking agent (trade name: Lupazole 101, manufactured by Atofina Yoshitomi Co., Ltd.), 0.1 parts by mass of a light-resistant stabilizer (trade names: Tinuvin 770DF, BASF) Manufactured by Co., Ltd.), 0.3 part by weight of an ultraviolet absorber (trade name: Kimasorb 81FL, manufactured by BASF), 0.03 part by weight of an antioxidant (trade name: Irganox 1010, BASF) Product) and 0.5 parts by mass of a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) as an intermediate layer, a multilayer sheet (sealant for solar cells) is used.
  • a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Example 2 A multilayer sheet (solar cell sealing material) was produced in the same manner as in Example 1 except that the layer ratio in Example 1 was set to 1/7/1.
  • volume resistivity A sample for volume resistivity measurement in which the total thickness of the sealing material was 3 mm was prepared so that the layer ratio was the same as that of each sheet of the example and the comparative example.
  • the volume resistivity of the produced sample was measured according to JIS C 2139: 2008.
  • the sample for optical property evaluation is a 3.2 mm thick white plate embossed glass (75 mm ⁇ 120 mm) and each sheet of the example or the comparative example, vacuumed by a vacuum heating bonding machine (LMPC, LM-50 ⁇ 50S).
  • the samples were bonded in this order under the conditions of a degree of 75 kPa, 150 ° C., and 13 minutes, and a sample having a configuration of 3.2 mm thick white plate embossed glass / Example or Comparative Example sheet / 3.2 mm thick white plate embossed glass was prepared.
  • the total light transmittance and haze of the sample were measured according to JIS K 7136: 2000 with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and used as an index for evaluating the optical characteristics of the solar cell sealing material.
  • the multilayer sheet (solar cell sealing material) of the examples has the volume resistivity of the outermost layer and the intermediate layer within a predetermined range, and such a solar cell sealing material is used for the solar cell module. If applied to the production, it is expected that a solar cell module excellent in PID resistance will be obtained.
  • FIG. 1 A photograph of the state of the sheet after the shrinkage resistance evaluation is performed on the multilayer sheet of Example 2 (sealant for solar cell) is shown in FIG. 1, and the single-layer sheet of comparative example 1 (sealant for solar cell) FIG. 2 shows photographs of the state of the sheet after the shrinkage resistance evaluation is performed on the sheet.
  • Example 2 As shown in FIG. 1, it can be seen that the change in appearance is small and the shrinkage resistance of the solar cell encapsulant is good.
  • Comparative Example 1 As shown in FIG. 2, it can be seen that the sheet is wrinkled and the shrinkage resistance is poor.
  • Example 3 to Example 5 Comparative Example 2 to Comparative Example 3
  • a resin composition in which 0.2 parts by mass of a silane coupling agent (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of the ethylene / methacrylic acid copolymer was used.
  • a crosslinking agent (trade name: Lupazole 101, manufactured by Atofina Yoshitomi Co., Ltd.), 0.1 parts by mass of a light-resistant stabilizer (trade names: Tinuvin 770DF, BASF) Manufactured by Co., Ltd.), 0.3 part by weight of an ultraviolet absorber (trade name: Kimasorb 81FL, manufactured by BASF), 0.03 part by weight of an antioxidant (trade name: Irganox 1010, BASF) Manufactured) and 0.5 parts by mass of a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) were used to produce a multilayer sheet or a single layer sheet described in Table 2.
  • a crosslinking agent trade name: Lupazole 101, manufactured by Atofina Yoshitomi Co., Ltd.
  • a light-resistant stabilizer trade names: Tinuvin 770DF, BASF
  • an ultraviolet absorber trade name: Kimasorb 81FL, manufactured by BA
  • the multilayer sheet was produced by stacking the sheets and heat-pressing them.
  • a sample for PID resistance test was produced by the following method using the obtained sealing material sheet. On the glass surface of 3.2 mm thickness, the produced sealing material sheet
  • the outer layer 1 and the outer layer were prepared by adding 0.2 parts by mass of a silane coupling agent (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of the ethylene / methacrylic acid copolymer. Used for 2.
  • a silane coupling agent trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a crosslinking agent (trade name: Lupazole 101, manufactured by Atofina Yoshitomi Co., Ltd.), 0.1 parts by mass of a light-resistant stabilizer (trade names: Tinuvin 770DF, BASF) Manufactured by Co., Ltd.), 0.3 part by weight of an ultraviolet absorber (trade name: Kimasorb 81FL, manufactured by BASF), 0.03 part by weight of an antioxidant (trade name: Irganox 1010, BASF) Product) and 0.5 parts by mass of a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) as an intermediate layer, a multilayer sheet (sealant for solar cells) is used. Produced. The multilayer sheet was produced by stacking the sheets and heat-pressing them. The following long-term storage stability was evaluated with respect to the produced multilayer sheet. The evaluation results are shown in Table 3.
  • Example 6 Long-term storage
  • Comparative Example 4 The sheets of Example 6 and Comparative Example 4 were exposed to a room fluorescent lamp for 3 months (light irradiation), and the rate of change in gel fraction was measured.
  • Table 3 shows that the storage stability is better when the outermost layer has the E-MAA layer compared to the EVA single layer. This is presumed to be because the outermost layer can suppress the cross-linking agent contained in the EVA1 layer from volatilizing, degrading, and the like.

Landscapes

  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
PCT/JP2015/076347 2014-09-18 2015-09-16 太陽電池用封止材及び太陽電池モジュール WO2016043235A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016548920A JP6542782B2 (ja) 2014-09-18 2015-09-16 太陽電池用封止材及び太陽電池モジュール

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014190239 2014-09-18
JP2014-190239 2014-09-18

Publications (1)

Publication Number Publication Date
WO2016043235A1 true WO2016043235A1 (ja) 2016-03-24

Family

ID=55533271

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/076347 WO2016043235A1 (ja) 2014-09-18 2015-09-16 太陽電池用封止材及び太陽電池モジュール

Country Status (3)

Country Link
JP (1) JP6542782B2 (zh)
TW (1) TWI553894B (zh)
WO (1) WO2016043235A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004815A (zh) * 2021-03-09 2021-06-22 浙江中聚材料有限公司 一种太阳能电池用封装胶膜及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019187175A1 (ja) * 2018-03-29 2019-10-03 日新製鋼株式会社 被覆金属板およびそれを有するジョイナー

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005129925A (ja) * 2003-10-03 2005-05-19 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材用シート
JP2008311537A (ja) * 2007-06-15 2008-12-25 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材用シート
WO2012043708A1 (ja) * 2010-09-29 2012-04-05 日本ゼオン株式会社 アルコキシシリル基を有するブロック共重合体水素化物及びその利用
WO2014017282A1 (ja) * 2012-07-25 2014-01-30 株式会社ブリヂストン 太陽電池用封止膜、太陽電池モジュール及び太陽電池用封止膜の選定方法
JP2014103369A (ja) * 2012-10-24 2014-06-05 Dainippon Printing Co Ltd 封止材シート

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5089497B2 (ja) * 2008-06-13 2012-12-05 三井・デュポンポリケミカル株式会社 多層シート
CN104334631B (zh) * 2012-06-14 2017-06-13 三井化学东赛璐株式会社 太阳能电池密封材及太阳能电池模块
JP6054664B2 (ja) * 2012-07-25 2016-12-27 株式会社ブリヂストン 太陽電池用封止膜、及びその選定方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005129925A (ja) * 2003-10-03 2005-05-19 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材用シート
JP2008311537A (ja) * 2007-06-15 2008-12-25 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材用シート
WO2012043708A1 (ja) * 2010-09-29 2012-04-05 日本ゼオン株式会社 アルコキシシリル基を有するブロック共重合体水素化物及びその利用
WO2014017282A1 (ja) * 2012-07-25 2014-01-30 株式会社ブリヂストン 太陽電池用封止膜、太陽電池モジュール及び太陽電池用封止膜の選定方法
JP2014103369A (ja) * 2012-10-24 2014-06-05 Dainippon Printing Co Ltd 封止材シート

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004815A (zh) * 2021-03-09 2021-06-22 浙江中聚材料有限公司 一种太阳能电池用封装胶膜及其制备方法
CN113004815B (zh) * 2021-03-09 2021-09-21 浙江中聚材料有限公司 一种太阳能电池用封装胶膜及其制备方法

Also Published As

Publication number Publication date
TWI553894B (zh) 2016-10-11
JP6542782B2 (ja) 2019-07-10
TW201618320A (zh) 2016-05-16
JPWO2016043235A1 (ja) 2017-07-06

Similar Documents

Publication Publication Date Title
JP4884575B2 (ja) 多層材料、太陽電池用封止材、安全（合わせ）ガラス用中間膜、太陽電池モジュール及び安全（合わせ）ガラス
JP4783865B2 (ja) 多層シート、太陽電池素子用封止材、及び太陽電池モジュール
JP5594959B2 (ja) 太陽電池素子封止材
JP4619451B2 (ja) エチレン共重合体組成物、太陽電池素子封止用シート及び太陽電池モジュール
KR20190085174A (ko) 태양 전지 모듈 및 그의 제조 방법
WO2012140897A1 (ja) 太陽電池封止用樹脂シート、これを用いた太陽電池モジュール、及びその製造方法
JP6660671B2 (ja) 太陽電池用封止材及び太陽電池モジュール
TW201307403A (zh) 太陽電池用密封膜及使用其之太陽電池
JP2015162498A (ja) 太陽電池封止材用積層体、太陽電池封止材及び太陽電池モジュール
JP2016117891A (ja) エチレングリコールジ（メタ）アクリレート化合物を含む封止膜用共架橋剤系
JP5209540B2 (ja) 太陽電池封止用シート及び太陽電池モジュール
WO2016043235A1 (ja) 太陽電池用封止材及び太陽電池モジュール
JP6747474B2 (ja) 太陽電池モジュール
JP6155680B2 (ja) 太陽電池モジュールの製造方法及び該製造方法によって製造された太陽電池モジュール
JP6035001B1 (ja) 封止シートおよび太陽電池モジュール
JP2014063815A (ja) 太陽電池モジュール用封止材組成物、及び封止材シートの製造方法
JP6163396B2 (ja) 太陽電池封止材用シート及び太陽電池モジュール
WO2019159852A1 (ja) 合わせガラス中間膜または太陽電池封止材用樹脂組成物、合わせガラス中間膜、合わせガラス、太陽電池封止材および太陽電池モジュール
JP6117582B2 (ja) 太陽電池封止材用シート及び太陽電池モジュール
WO2016158009A1 (ja) 封止シートおよび太陽電池モジュール
JP2020100552A (ja) 積層体及び合わせガラス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15841307

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016548920

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15841307

Country of ref document: EP

Kind code of ref document: A1