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WO2016121990A1 - Feuille de matériau d'étanchéité pour module de batterie solaire, et module de batterie solaire - Google Patents

Feuille de matériau d'étanchéité pour module de batterie solaire, et module de batterie solaire Download PDF

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Publication number
WO2016121990A1
WO2016121990A1 PCT/JP2016/052826 JP2016052826W WO2016121990A1 WO 2016121990 A1 WO2016121990 A1 WO 2016121990A1 JP 2016052826 W JP2016052826 W JP 2016052826W WO 2016121990 A1 WO2016121990 A1 WO 2016121990A1
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WO
WIPO (PCT)
Prior art keywords
sealing material
material sheet
sheet
solar cell
encapsulant
Prior art date
Application number
PCT/JP2016/052826
Other languages
English (en)
Japanese (ja)
Inventor
啓晶 玉木
靖史 白髭
直博 小保内
英一郎 横地
Original Assignee
大日本印刷株式会社
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
Priority claimed from JP2015017976A external-priority patent/JP6603994B2/ja
Priority claimed from JP2015017977A external-priority patent/JP6540054B2/ja
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2016121990A1 publication Critical patent/WO2016121990A1/fr

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • 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 sealing material sheet for a solar cell module and a solar cell module.
  • a solar cell module has a configuration in which a transparent front substrate made of glass or the like, a solar cell element, and a back surface protection sheet are laminated via a sealing material sheet.
  • the sealing material sheet is required to have adhesion and durability with the transparent front substrate, solar cell element and back surface protection sheet, embedding property of the solar cell element, heat resistance, and the like.
  • the encapsulant sheet is improved in heat resistance of the encapsulant sheet by crosslinking the resin composition.
  • the encapsulant sheet is excessively crosslinked, the embedding property of the solar cell element is deteriorated.
  • Patent Document 1 A sealing material sheet having a structure in which the gel fraction is changed along the sheet thickness direction by irradiating ionizing radiation from one surface has been proposed.
  • Patent Document 1 describes a sealing material sheet excellent in the embedding property of a solar cell element, but does not consider wiring for connecting solar cells.
  • a wiring for extracting electricity from the solar cell element called a bus bar is arranged between the solar cell element and the sealing material sheet.
  • the solar cell element and the sealing material sheet are heated and laminated with a pressing pressure.
  • the bus bar has a certain thickness, the stress due to press working concentrates on the portion of the solar cell element where the bus bar overlaps. Therefore, there is a problem that cracks occur in the solar cell element portion where the bus bars overlap.
  • This invention is made
  • thermomechanical analysis (TMA) test of the sealing material sheet As a result of sincerity studies to solve the above problems, the present inventors have focused on a thermomechanical analysis (TMA) test of the sealing material sheet, and have a gradient P (indentation depth ( ⁇ m) / temperature of the TMA curve. (.Degree. C.)) It has been found that the above problem can be solved if the sealing material sheet specifies a gradient ratio at a predetermined film thickness with respect to the maximum value P max of the absolute value, and the present invention has been completed. . More specifically, the present invention provides the following.
  • TMA thermomechanical analysis
  • TMA thermomechanical analysis
  • TMA test A ⁇ 10 mm encapsulant sheet was set in a TMA apparatus, pressed into a ⁇ 1 mm needle to a constant pressure of 20 kPa, and the temperature was raised from room temperature to 150 ° C. at a heating rate of 5 ° C./min. indentation depth is measured.
  • P 80 is, when the indentation depth of the needle at 0.99 ° C. of less than 80% more than 50% of the thickness of the encapsulant sheet, P 0.99 ° C. is the slope at 0.99 ° C. Is used.
  • the pressing depth of the needle at a temperature of the melting point of the encapsulant sheet + 40 ° C. is within 85% of the film thickness of the encapsulant sheet, according to any one of (1) to (3) Sealing material sheet.
  • the content of polyethylene having a density of 0.860 g / cm 3 or more and 0.970 g / cm 3 or less is 85% or more in the entire sealing material composition (1) to (4)
  • the sealing material sheet in any one.
  • the encapsulant sheet is a multilayer sheet comprising an intermediate layer and outermost layers disposed on both sides thereof,
  • the outermost layer is the sealing material sheet according to (5), further including a silane-modified polyethylene resin.
  • a solar cell module comprising: the encapsulant sheet according to any one of (1) to (7); a solar cell element; and a bus bar that is a wiring for taking out electricity from the solar cell element, The bus bar is disposed between the encapsulant sheet and the solar cell element; A solar cell module, wherein the bus bar has a thickness of 150 ⁇ m or more and 300 ⁇ m or less.
  • a solar cell module in which a solar cell element, a bus bar that is a wiring for taking out electricity from the solar cell element, and a sealing material sheet are arranged at least in this order,
  • the encapsulant sheet has a polyethylene content with a density of 0.860 g / cm 3 or more and 0.970 g / cm 3 or less of 85% or more in the total encapsulant composition,
  • the degree of cross-linking has changed along the thickness direction of the sealing material sheet,
  • the solar cell module in which the surface by the side of the said high degree of bridge
  • the sealing material sheet is irradiated with ionizing radiation from only one side of the front and back surfaces, or is irradiated with ionizing radiation of different intensity from the front and back surfaces (9).
  • the solar cell module described.
  • the sealing material sheet is a multilayer sheet comprising an intermediate layer and outermost layers disposed on both sides thereof, One outermost layer of the multilayer sheet on the side opposite to the bus bar side further contains a silane-modified polyethylene resin,
  • the encapsulant sheet is In a TMA curve obtained in a thermomechanical analysis (TMA) test under the following conditions and showing a relationship between a predetermined temperature range (° C.) and the depth of pressing of the needle into the sealing material sheet ( ⁇ m), A needle is pushed in from the surface of the sealing material sheet having the higher degree of crosslinking, and the gradient P (indentation depth ( ⁇ m) / temperature (° C.)) of the TMA curve in the predetermined temperature range (° C.) is obtained.
  • the value of P 80 is the slope at 80% of the thickness of the sealing material sheet, and a 1 [mu] m / ° C. or higher 10 [mu] m / ° C.
  • the value of P 50 is the gradient at 50% of the sealing material sheet having a thickness of solar cell module according to any one of 13 .mu.m / ° C. or higher 23 .mu.m / ° C. or less (9) from (11).
  • TMA test A 10 mm diameter sealing material sheet is set in the TMA apparatus, the pressure is set to a constant pressure of 20 kPa with a ⁇ 1 mm needle, the temperature is raised from room temperature to 150 ° C. at a temperature rising rate of 5 ° C./min, and the needle at that time The indentation depth is measured, provided that when P 80 has an indentation depth of the needle at 150 ° C. of more than 50% and less than 80% of the thickness of the encapsulant sheet, P 150 ° C. is a gradient at 150 ° C. Is used.
  • thermomechanical analysis test TMA test of the encapsulant sheet
  • P max the maximum value of the absolute value of the gradient P (indentation depth ( ⁇ m) / temperature (° C.)) of the TMA curve.
  • the encapsulant sheet that specifies the gradient ratio in film thickness is an encapsulant sheet for solar cell modules that has sufficient heat resistance, but can prevent the occurrence of cracks in the solar cell elements due to the bus bars. It is a stopping material sheet.
  • thermomechanical analysis test which concerns on the sealing material sheet
  • thermomechanical analysis test TMA test concerning the sealing material sheets of Examples and Comparative Examples, the relationship between the temperature (° C.) and the absolute value of the gradient of the TMA curve (indentation depth ( ⁇ m) / temperature (° C.)). It is the graph which showed.
  • the sealing material sheet of the present invention may be expressed as a thermomechanical analysis test (hereinafter referred to as a TMA test) showing a relationship between a predetermined temperature range (° C.) and a needle pressing depth ( ⁇ m) into the sealing material sheet.
  • the gradient P indentation depth ( ⁇ m) / temperature (° C.)
  • P MAX that is the maximum absolute value of the gradient P is obtained.
  • the TMA test in the present invention means that a sealing material sheet of ⁇ 10 mm is set in a TMA apparatus, a pressure of 20 kPa is applied to a ⁇ 1 mm needle, a predetermined temperature range (° C.) at a temperature rising rate of 5 ° C./min, For example, it refers to a test in which the temperature is raised from room temperature to 150 ° C., and the indentation depth of the needle at that time is measured.
  • TMA thermomechanical analysis
  • P MAX in the TMA test is the maximum absolute value of the gradient P (indentation depth ( ⁇ m) / temperature (° C)) obtained by differentiating the indentation depth ( ⁇ m) in the TMA curve with temperature (° C). is there.
  • P MAX is the maximum value of the pushing speed of the needle in the TMA test, and is a parameter indicating the flexibility of the sealing material sheet.
  • An encapsulant sheet having a large P MAX indicates that the encapsulant sheet has high flexibility in press processing of the laminate. Therefore, in the case of a sealing material sheet having a large P MAX , the bus bar can be easily embedded in the pressing process of the laminate, and the stress of the pressing process applied to the place where the bus bar and the solar cell element overlap is reduced. Can do.
  • Lamination in the laminating process is divided into a vacuuming process and a pressing process, and is performed at a set temperature of about 110 ° C. to 150 ° C.
  • the temperature reaches 70 ° C. to 90 ° C. in the vacuuming process, and the temperature is raised to the set temperature in the pressing process. Therefore generally the temperature at P MAX for loads of the solar cell element during the pressing process starts is the highest is desirably 70 °C ⁇ 90 °C.
  • the value of P MAX (indentation depth ( ⁇ m) / temperature (° C.)) is preferably 10 ⁇ m / ° C.
  • the temperature is set to from 30 ° C. to 30 ⁇ m / ° C.
  • P MAX indentation depth ( ⁇ m) / temperature (° C.)
  • the generation of cracks in the solar cell element due to the overlapping of the bus bars can be more effectively suppressed.
  • P MAX indentation depth ( ⁇ m) / temperature (° C.)
  • the P 80 of TMA test a gradient at 80% of the thickness of the sealing material sheet (indentation depth ([mu] m) / Temperature (° C.)).
  • the gradient at 80% of the film thickness of the encapsulant sheet refers to the gradient (indentation depth ( ⁇ m) / temperature) when the needle indentation depth is 80% of the film thickness of the encapsulant sheet. ° C)).
  • P 80 is a parameter indicating the heat resistance of the sealing material sheet. Higher P 80 is smaller sealing material sheet, which means to include many areas highly crosslinked during sealing material sheet. Therefore, it has a high heat resistance as small encapsulant sheet P 80. If less sealing material sheet P 80 is the heat resistance of the sealing material sheet is further improved.
  • the value of P 80 (indentation depth ( ⁇ m) / temperature (° C.)) is preferably from 1 ⁇ m / ° C. to 10 ⁇ m / ° C., more preferably from 2 ⁇ m / ° C. to 6 ⁇ m / ° C.
  • a sealing material sheet having sufficient heat resistance can be obtained.
  • P 80 (indentation depth ( ⁇ m) / temperature (° C.) is set to 1 ⁇ m / ° C. or more, the generation of cracks in the solar cell element due to the overlapping of the bus bars can be more effectively suppressed.
  • P 80 has a pressing depth of the needle at 150 ° C. of 50% or more and less than 80% of the film thickness of the encapsulant sheet
  • P 150 ° C. which is a gradient at 150 ° C. is used.
  • the ratio of the P 80 is the slope at 80% of the thickness of the sealing material sheet.
  • the melting point of the sealing material sheet in the TMA test + the needle indentation depth at a temperature of 40 ° C. is preferably within 85% of the film thickness of the sealing material sheet, more preferably within 80%, more preferably 75%. More preferably, it is within.
  • seat can be made more preferable by making the indentation depth of the needle
  • the gradient P 50 at 50% is preferably 13 ⁇ m / ° C. or more and 23 ⁇ m / ° C. or less.
  • the gradient at 50% of the film thickness of the encapsulant sheet refers to the gradient (indentation depth ( ⁇ m) / temperature) when the needle indentation depth is 50% of the film thickness of the encapsulant sheet. ° C)).
  • P 50 is a parameter indicating the property narrowing filling of the sealing material sheet. If large sealing material sheet P 50, of narrowing filled encapsulant sheet or irregularities followability is further improved.
  • the value of P 50 (indentation depth ( ⁇ m) / temperature (° C.)) is preferably 13 ⁇ m / ° C. to 23 ⁇ m / ° C., more preferably 15 ⁇ m / ° C. to 20 ⁇ m / ° C.
  • P 50 (indentation depth ( ⁇ m) / temperature (° C.)) By setting the value of P 50 (indentation depth ( ⁇ m) / temperature (° C.)) to 23 ⁇ m / ° C. or less, sufficient
  • the thickness of the sealing material sheet is more preferably 300 ⁇ m or more and 600 ⁇ m or less. By setting it as such a range, an impact can fully be eased and it can be set as a highly productive sealing material sheet.
  • the sealing material sheet used in the solar cell module of the present invention preferably has a different degree of crosslinking along the thickness direction of the sealing material sheet.
  • the method of crosslinking so that the degree of crosslinking of the encapsulant sheet changes along the thickness direction of the encapsulant sheet is not particularly limited.
  • crosslinking can be used by irradiating ionizing radiation from only one surface side of the front and back surfaces of a sealing material sheet, or by irradiating ionizing radiation of different intensity
  • ionizing radiation was irradiated from only one surface side of the front and back surfaces of the encapsulant sheet so that the surface on the side having a high degree of crosslinking is disposed on the bus bar side.
  • the solar cell element bus bar is placed on the irradiation surface irradiated with strong ionizing radiation. Good.
  • the degree of cross-linking of the encapsulant sheet refers to the rate of cross-linking of the encapsulant sheet as specified by parameters such as gel fraction and MFR, and the lower the degree of cross-linking, the less cross-linking reaction has occurred. It means that there are many resin component regions.
  • the gel fraction (%) means that 0.1 g of sealing material is put in a resin mesh, extracted with toluene at 60 ° C. for 4 hours, taken out together with the resin mesh, weighed after drying treatment, and mass comparison before and after extraction. The mass% of residual insoluble matter was measured and this was used as the gel fraction.
  • the MFR (g / 10 minutes) can be determined by measuring at 190 ° C. and a load of 2.16 kg measured according to JIS-K6922-2.
  • the sealing material sheet of the present invention preferably contains, for example, 85% or more of a polyethylene resin having a density of 0.860 g / cm 3 or more and 0.970 g / cm 3 or less in the total sealing material composition.
  • a polyethylene resin having a density of 0.860 g / cm 3 or more and 0.970 g / cm 3 or less in the total sealing material composition.
  • the polyethylene resin low density polyethylene (LDPE) can be more preferably used, and linear low density polyethylene (LLDPE) or metallocene linear low density polyethylene (M-LLDPE) can be particularly preferably used.
  • the density of the polyethylene resin is preferably 0.860 g / cm 3 or more and 0.970 g / cm 3 or less, and particularly preferably 0.865 g / cm 3 or more and 0.930 g / cm 3 or less.
  • the polyethylene resin preferably has a melting point of 40 ° C. or higher and 90 ° C. or lower, and more preferably has a melting point of 55 ° C. or higher and 80 ° C. or lower.
  • the sealing material sheet of the present invention is preferably a multilayer sheet comprising an intermediate layer and outermost layers disposed on both sides thereof, and the outermost layer further contains a silane-modified polyethylene resin. It is preferable to do.
  • the silane-modified polyethylene resin is a resin obtained by graft polymerizing low-density polyethylene (LDPE) serving as a main chain, preferably linear low-density polyethylene (LLDPE) with an ethylenically unsaturated silane compound as a side chain. Since such a graft copolymer has a high degree of freedom of silanol groups that contribute to the adhesive force, it can improve the adhesion of the sealing material sheet to other members in the solar cell module.
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • the sealing material sheet of the present invention is arranged so that the outermost layer containing the silane-modified polyethylene resin is on the surface opposite to the bus bar side.
  • the sealing material sheet of the present invention is arranged so that the outermost layer containing the silane-modified polyethylene resin is on the surface opposite to the bus bar side.
  • the encapsulant composition for forming the encapsulant sheet may contain a necessary minimum amount of cross-linking agent, but it is more preferable not to add a cross-linking agent. While the addition of a crosslinking aid allows adequate crosslinking to proceed sufficiently, the addition of a crosslinking agent such as an organic peroxide during the heat laminating process for integration with the solar cell module This is because the risk of problems such as foaming due to degas is increased.
  • a crosslinking agent a well-known thing can be used and it does not specifically limit, For example, a well-known radical polymerization initiator can be used.
  • the sealing material composition for molding the sealing material sheet may contain other components such as a crosslinking aid, a light stabilizer, an ultraviolet absorber, and a heat stabilizer as necessary.
  • the other components are preferably in the range of 0.001% by mass to 5% by mass with respect to the total amount of the sealing material composition.
  • the sealing material sheet of this invention can be manufactured by passing through the sheet-forming process which melt-molds each composition and obtains a sealing material sheet, for example. Molding is performed by various molding methods such as injection molding, extrusion molding, hollow molding, compression molding, and rotational molding, which are usually used in ordinary thermoplastic resins. As an example of the method for forming the encapsulant sheet as the multilayer sheet, a method of forming by co-extrusion using two or more melt-kneading extruders can be given.
  • the sealing material sheet of this invention can be manufactured by passing through the bridge
  • a cross-linking step of performing a cross-linking treatment with ionizing radiation on an uncross-linked encapsulant sheet is a solar cell module integration step in which the encapsulant sheet is integrated with other members after completion of the sheeting step. Do before you start. It is set as the sealing material sheet from which the crosslinking degree of the sealing material sheet changed along the thickness direction of the sealing material sheet by this crosslinking process.
  • the cross-linking treatment may be performed continuously in-line following the sheet forming step, or may be performed off-line.
  • the surface of the sealing material sheet which is in contact with the bus bar in a solar cell module has a low bridge
  • the surface and the bus bar 7 may be arranged so as to be in contact with each other, and the surface of the sealing material sheet in contact with the bus bar is arranged so that the surface of the sealing material sheet having a high degree of crosslinking and the bus bar 7 are in contact with each other. Also good. It is preferable that the surface of the sealing material sheet in contact with the bus bar is arranged so that the bus bar 7 is in contact with the surface of the sealing material sheet having a high degree of crosslinking.
  • individual crosslinking conditions are not particularly limited. Although it can carry out by ionizing radiations, such as an electron beam (EB), an alpha ray, a beta ray, a gamma ray, a neutron beam, it is preferable to use an electron beam especially.
  • EB electron beam
  • alpha ray a beta ray
  • beta ray a gamma ray
  • neutron beam it is preferable to use an electron beam especially.
  • the ionizing radiation can mention the method of irradiating the ionizing radiation of different intensity
  • the degree of crosslinking of the encapsulant composition can be changed along the thickness direction of the encapsulant sheet. .
  • the acceleration voltage is determined by the thickness of the sheet that is the object to be irradiated, and a thicker sheet requires a larger acceleration voltage.
  • irradiation is performed at 100 kV to 250 kV.
  • the acceleration voltage is less than 100 kV, crosslinking is insufficient, and the heat resistance of the encapsulant sheet is insufficient.
  • the irradiation dose ranges from 30 kGy to 50 kGy, preferably from 35 kGy to 45 kGy. Irradiation may be in an air atmosphere or a nitrogen atmosphere.
  • the irradiation direction of the ionizing radiation may be applied from the solar cell side where the bus bar is disposed or from the opposite direction of the solar cell side. That is, the maximum value of the degree of crosslinking may be on the solar cell side of the encapsulant sheet or in the opposite direction to the solar cell side.
  • Manufacturing a sealing material sheet having a preferable value of P 1 (P 1 100 ⁇ (P 80 / P MAX )) in a TMA test by irradiating ionizing radiation with a predetermined acceleration voltage and dose. Can do.
  • ionizing radiation with different intensities may be irradiated from the front and back surfaces.
  • this crosslinking process may be performed continuously in-line following the sheet forming step, or may be performed off-line.
  • the crosslinking treatment is a general heat treatment
  • the content of the crosslinking agent is 0.5 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of all components of the sealing material sheet.
  • the content of the crosslinking agent may be 0, and even if it is contained, it is preferably less than 0.5 parts by mass. Thereby, the risk of the productivity fall by gelatinization of the sealing material composition in the sheeting process of a sealing material composition can be reduced.
  • FIG. 1 is a cross-sectional view showing a layer structure of a solar cell module 10 using the sealing material sheet of the present invention.
  • the transparent front substrate 2, the front sealing material layer 3, the solar cell element 4, the back sealing material layer 5, and the back surface protection sheet 6 are laminated in order from the incident light receiving surface side. ing.
  • a bus bar 7 that is a wiring for taking out electricity from the solar cell element is disposed.
  • the solar cell module 10 of the present invention can use the sealing material sheet of the present invention for at least one of the front sealing material layer 3 and the back sealing material layer 5.
  • the bus bar is disposed between the sealing material sheet of the present invention and the solar cell element. Although it is a sealing material sheet having sufficient heat resistance, the occurrence of cracks in the solar cell element due to the bus bar can be suppressed.
  • the sealing material sheet of this invention for the front sealing material layer 3 which is the side by which the bus-bar 7 is arrange
  • the sealing material sheet of the present invention for the back surface sealing material layer (not shown). Although it is a sealing material sheet having sufficient heat resistance, the occurrence of cracks in the solar cell element due to the bus bar can be suppressed.
  • the surface of the encapsulant sheet in contact with the bus bar in the solar cell module is cross-linked with the encapsulant sheet.
  • position so that it may become a surface with a low degree
  • position so that the surface of the sealing material sheet
  • the surface of the sealing material sheet in contact with the bus bar is disposed so that the surface of the sealing material sheet has a high degree of crosslinking.
  • the surface of the encapsulant sheet in contact with the bus bar has heat resistance equivalent to that when the encapsulant sheet is disposed such that the surface of the encapsulant sheet has a low degree of crosslinking.
  • positioning since it will be arrange
  • the thickness of the bus bar is preferably 150 ⁇ m or more and 300 ⁇ m or less. By setting it as such a range, it can have favorable electroconductivity as wiring which takes out electricity from a solar cell element.
  • the thickness of the solar cell element is preferably 150 ⁇ m or more and 300 ⁇ m or less. By setting it as 150 micrometers or more, the risk of the crack generation of a solar cell element can be suppressed. Productivity can be made favorable by setting it as 300 micrometers or less.
  • the solar cell module 10 is formed by sequentially laminating a member composed of the transparent front substrate 2, the front sealing material layer 3, the solar cell element 4 including the bus bar 7, the back sealing material layer 5, and the back surface protection sheet 6, for example. Then, they can be integrated by vacuum suction or the like, and then manufactured by thermocompression-bonding the above-mentioned member as an integral molded body by a molding method such as a lamination method.
  • the ionizing radiation irradiation surface is irradiated with ionizing radiation of different strength from the front and back surfaces. If the solar cell module is laminated so that the bus bar of the solar cell element is disposed on the irradiation surface irradiated with ionizing radiation, the solar cell module in which the surface on the side with the high degree of crosslinking of the encapsulant sheet is disposed on the bus bar side Can be manufactured.
  • the solar cell module 10 conventionally known materials can be used for the transparent front substrate 2, the solar cell element 4, and the back surface protective sheet 6 without particular limitation.
  • the solar cell module 10 of this invention may also contain members other than the said members, such as a heat dissipation sheet, for example.
  • Metallocene-based linear low density polyethylene (M-LLDPE): density of 0.880 g / cm 3 , melting point 60 ° C., MFR at 190 ° C. of 3.5 g / 10 min.
  • Metallocene linear low-density polyethylene 96.5 mass %, Density 0.884 g / cm 3 , MFR at 190 ° C.
  • Metallocene-based linear low density polyethylene (M-LLDPE): density 0.885 g / cm 3 , melting point 66 ° C., MFR at 190 ° C. of 18 g / 10 min.
  • Metallocene linear low-density polyethylene 86.0% by mass, Silane modification with a metallocene linear low density polyethylene of 96.5% by mass at 190 ° C. of 3.5 g / 10 min, a density of 0.884 g / cm 3 , and an MFR at 190 ° C. of 1.8 g / 10 min.
  • Polyethylene resin 13.6% by mass, light stabilizer (KEMISTAB62) 0.0545% by mass, UV absorber (KEMISORB12) 0.318% by mass, UV absorber (KEMISORB79) 0.0545% by mass, UV absorber (KEMISORB202) It mixes so that it may become 0.00636 mass%, the sealing material sheet
  • Each sealing material composition was produced using a 30 mm extruder and a film molding machine having a 200 mm wide T-die to produce an inner layer and an outer layer sealing material sheet at an extrusion temperature of 210 ° C. and a take-off speed of 1.1 m / min. These inner-layer and outer-layer sealing material sheets were laminated to obtain a three-layer solar cell module sealing material sheet (Example and Comparative Example). All of these encapsulant sheets had a thickness of 550 ⁇ m, and the outer layer: inner layer: outer layer thickness ratio was 1: 5: 1.
  • seat is laminated
  • fusing point of the sealing material sheet was 60 degreeC.
  • the acceleration voltage (kV) means the acceleration voltage (kV) of electron beam irradiation.
  • Illuminance (kGy) means the illuminance (kGy) of electron beam irradiation.
  • the gel fraction of the encapsulant sheet 1 was measured by the following method, the gel fraction of the encapsulant sheet obtained by collecting a part from the surface on the electron beam irradiation side of the encapsulant sheet to a depth of 100 ⁇ m is It was 20%, and the gel fraction of the encapsulant sheet obtained by collecting a portion from the surface opposite to the electron beam irradiation surface of the encapsulant sheet to a depth of 100 ⁇ m was 0%. From this result, it was confirmed that the cross-linking degree of the encapsulant sheet 1 changed along the thickness direction of the encapsulant sheet, and the surface on the electron beam irradiation side was a surface having a high degree of crosslinking.
  • the gel fraction is measured by collecting 0.1 g of each part from the both sides of the encapsulant sheet 1 to a depth of 100 ⁇ m, putting it in a resin mesh, extracting it with toluene at 60 ° C. for 4 hours, taking out the resin mesh and drying it. After weighing, it was measured by comparing the mass before and after extraction and measuring the mass% of the remaining insoluble matter.
  • a sealing material sheet was prepared in the same manner as the sealing material sheet 1 except that the electron beam was not irradiated.
  • the gel fraction on both sides of the encapsulant sheet 3 was measured in the same manner as the encapsulant sheet 1, the gel fraction of the part from the surface to 100 ⁇ m on both sides was 0%, and in the thickness direction of the encapsulant sheet It was confirmed that the degree of cross-linking did not change.
  • a sealing material sheet 4 was prepared in the same manner as the sealing material sheet 1 except that both surfaces of the sealing material sheet were irradiated with an electron beam.
  • the gel fraction on both sides of the encapsulant sheet 4 was measured in the same manner as the encapsulant sheet 1, the gel fraction of the part from the surface to 100 ⁇ m on both sides was 20%, and in the thickness direction of the encapsulant sheet It was confirmed that the degree of cross-linking did not change.
  • TMA tests were performed on the sealing material sheets 1 to 5. Specifically, the sealing material sheet is cut out to ⁇ 10 mm, set in a TMA apparatus (TMA / SS7100 manufactured by SII Nanotechnology), the temperature of the sealing material sheet is increased, and the pressure of 20 kPa is applied from the surface of the sealing material sheet. A needle having a diameter of 1 mm was pushed in and the depth of pushing was measured. The heating rate was 5 ° C./min, and the temperature was raised from room temperature to 150 ° C.
  • Table 2 shows P 80 which is the gradient of the TMA curve at 80% of the film thickness of the encapsulant sheet (indicated as P 80 in Table 2) and P MAX which is the maximum absolute value of the gradient P of the TMA curve (
  • P MAX (denoted as P MAX )
  • 100 ⁇ (P 80 / P MAX )
  • P 1 (denoted as P 1 in Table 2)
  • the ratio of the indentation depth of the needle with respect to is shown.
  • Table 2 shows the direction of pushing the needle in the TMA test (in Table 2, indicated as the measurement direction), and “EB irradiation surface” means that measurement was performed by pushing the needle from the electron beam irradiation surface.
  • the “opposite surface” means that the measurement was performed by pushing the needle from the opposite surface as viewed from the electron beam irradiation surface.
  • the sealing material sheet 3 is unirradiated and the sealing material sheet 4 is double-sided irradiation, the special measurement direction is not described.
  • FIG. 2 is a graph showing the relationship between the temperature (° C.) in the TMA test of the encapsulant sheets 1 to 5 and the depth ( ⁇ m) of pushing the needle into the encapsulant sheet.
  • FIG. 3 is a graph showing the relationship between the temperature (° C.) and the gradient of the TMA curve (indentation depth ( ⁇ m) / temperature (° C.)) of the sealing material sheets 1 to 5 in the TMA test.
  • the electron beam irradiation surface of the sealing material sheet 1 (Example 1), the surface opposite to the electron beam irradiation surface of the sealing material sheet 1 (Example 1), the sealing material sheet 2 (Example 2) electron beam irradiation surface, P 1 showed 30% or less.
  • the electron beam irradiation surface of the sealing material sheet 1 (Example 1) (the surface of the high degree of cross-linking side) is, P 50 showed 13 .mu.m / ° C. or higher 23 .mu.m / ° C. or less.
  • the surface opposite to the electron beam irradiation surface of the encapsulant sheet 1 (Example 1) (the surface on the side having a low degree of cross-linking) and the cross-linked encapsulant sheet 4 irradiated with the electron beam from both sides are both used.
  • P 50 was less than 13 ⁇ m / ° C.
  • the uncrosslinked sealing material sheet 3 that was not irradiated with the electron beam had P 50 of more than 23 ⁇ m / ° C.
  • the bus bar connected to the solar battery cell is disposed on the light receiving surface side.
  • the “sealing material sheet surface in contact with the bus bar” represents the surface of the light receiving surface side sealing material in contact with the bus bar
  • the “EB irradiation surface” represents the electron beam irradiation surface.
  • the “opposite surface” means that the opposite surface as viewed from the electron beam irradiation surface is laminated so as to contact the bus bar.
  • the electron beam irradiation surface of the sealing material sheet 1 P 1 showed less than 30% (Example 1), the opposite surface of the electron beam irradiation surface of the sealing material sheet 1 (Example 1), sealing In the module 1 to 3 in which the electron beam irradiation surface of the material sheet 2 (Example 2) was laminated so as to be in contact with the bus bar, the crack of the solar cell element at the lamination temperature of 150 ° C. was not confirmed in the cell crack test. On the other hand, the module 5 by laminating a sealing material sheet 4 P 1 showed more than 30% (Comparative Example 2), the crack of the solar cell element was confirmed.
  • the module 1 laminated so that the electron beam irradiation surface (surface with a high degree of crosslinking) of the encapsulant sheet was in contact with the bus bar did not show any cracks in the solar cell element under any lamination temperature condition.
  • the module 3 laminated so that the surface opposite to the electron beam irradiation surface (the surface having a low degree of crosslinking) of the encapsulant sheet is in contact with the bus bar is a solar cell element in a cell crack test at a lamination temperature condition of 110 ° C. Cracks were confirmed.
  • the module 1 in which the surface on the side with a high degree of cross-linking of the encapsulant sheet is arranged on the bus bar side is the module 3 in which the surface on the side with a low degree of cross-linking of the encapsulant sheet is arranged on the bus bar side. It can be seen that the generation of cracks in the solar cell element due to the bus bar can be further suppressed as compared with.
  • ⁇ Heat resistance test> A heat resistance test was performed on the sealing material sheets 1 to 5 (Examples 1 and 2 and Comparative Examples 1 to 3). Specifically, a sealing material sheet cut out to 5 ⁇ 7.5 cm is placed vertically on a large-sized glass plate on a large-sized glass plate that has been subjected to graining, and left at 80 ° C. for 12 hours. The moving distance of 5 ⁇ 7.5 grain glass after being left was measured and evaluated. The measured values were evaluated according to the following evaluation criteria. The evaluation results (shown as heat resistance in Table 4) are shown in Table 4.
  • EB irradiated surface means that the electron beam irradiated surface was tested so as to come into contact with the textured glass
  • opposite surface means that the opposite surface is in contact with the textured glass as viewed from the electron beam irradiated surface. It means that it was tested.
  • the evaluation criteria are as follows.
  • the electron beam irradiation surface of the sealing material sheet 1 P 1 showed less than 30% (Example 1), the opposite surface of the electron beam irradiation surface of the sealing material sheet 1 (Example 1), sealing Shibogarasu travel distance of the electron beam irradiation surface was measured contact facing the Shibogarasu of wood sheets 2 (example 2), the surface and sealing of the sealing material sheet 3 P 1 showed more than 30% (Comparative example 1) It can be seen that it is smaller than the movement distance of the textured glass measured by using the textured glass sheet 5 (Comparative Example 3) as the contact surface of the textured glass. Sealing material sheet 1, 2 Therefore P 1 is 30% or less (Examples 1 and 2) is presumed to be a sealing material sheet having excellent heat resistance as a sealing material sheet for a solar cell module .
  • Glass adhesion test Glass adhesion of the sealing material sheet 1 with respect to the electron beam irradiation surface (surface with a high degree of crosslinking) and the surface opposite to the electron beam irradiation surface (surface with a low degree of crosslinking) and the sealing material sheets 3 and 4 A test was conducted.
  • Each of the sealing material sheets 4 is brought into close contact with a glass substrate (white plate float semi-tempered glass JPT3.2 75 mm ⁇ 50 mm ⁇ 3.2 mm), heating temperature 150 ° C., vacuum heating (0 kPa) time 5 minutes, atmospheric pressure press (100 kPa) Lamination was performed in 7 minutes to prepare a sample for evaluating adhesion.
  • the surface of the encapsulant sheet 1 is contacted with the embossed glass on the electron beam irradiated surface (the surface on the side having a high degree of crosslinking) and the surface opposite the electron beam irradiated surface on the encapsulant sheet 1 (the surface on the side having a low degree of crosslinking). It can be seen that the moving distance measured by the facing glass is equal to or greater than that of the encapsulant sheet 3.
  • the encapsulant sheet having a P 1 (%) value of 30% or less of the encapsulant sheet is good in both the cell crack test and the heat resistance test. From this, in the TMA indentation test of the sealing material sheet, the gradient ratio P 1 at a predetermined film thickness with respect to the maximum value P max of the absolute value of the gradient P (indentation depth ( ⁇ m) / temperature (° C.)) of the TMA curve.
  • the encapsulant sheet that specifies (%) has excellent heat resistance as an encapsulant sheet, and is an excellent solar cell that can suppress the occurrence of cracks in the solar cell element due to the bus bar. It was confirmed that it was a sealing material sheet for modules.
  • the surface on the side with the higher degree of crosslinking of the encapsulant sheet faces the bus bar side of the solar cell element.
  • the arranged solar cell module has the same heat resistance as that of the solar cell module whose surface on the side having a low degree of crosslinking is arranged on the bus bar side of the solar cell element, and is embedded at or above the same level. It is a solar cell module that can suppress the occurrence of cracks in the solar cell element due to the bus bar, and is an excellent solar cell module with high adhesion to the glass used for the transparent front substrate. I understand.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de matériau d'étanchéité pour un module de batterie solaire qui, en dépit du fait d'être une feuille de matériau d'étanchéité pour un module de batterie solaire ayant une résistance à la chaleur suffisante, est capable de supprimer le développement de fissures dans un élément de batterie solaire dû à une barre omnibus, et un module de batterie solaire. Une feuille de matériau d'étanchéité dans laquelle, dans une courbe TMA obtenue dans un essai d'analyse de machine thermique (TMA) et indiquant la relation entre une plage de température prédéterminée (°C) et une profondeur de poussée d'aiguille (µm) dans la feuille de matériau d'étanchéité, un gradient P (profondeur de poussée (μm)/température (°C)) de la courbe TMA dans la plage de température prédéterminée (°C) est déterminé, et la valeur de P1 (P1 = 100 × (P80/PMAX)), qui est le rapport de P80 indiquant le gradient à 80 % de l'épaisseur de film de la feuille de matériau d'étanchéité, sur PMAX, qui est la valeur maximale de la valeur absolue du gradient P, n'est pas supérieure à 30 %.
PCT/JP2016/052826 2015-01-30 2016-01-29 Feuille de matériau d'étanchéité pour module de batterie solaire, et module de batterie solaire WO2016121990A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015017976A JP6603994B2 (ja) 2015-01-30 2015-01-30 太陽電池モジュール用の封止材シート及び太陽電池モジュール
JP2015-017977 2015-01-30
JP2015-017976 2015-01-30
JP2015017977A JP6540054B2 (ja) 2015-01-30 2015-01-30 太陽電池モジュール

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3319130A4 (fr) * 2015-07-03 2019-01-16 Dai Nippon Printing Co., Ltd. Feuille de matériau d'étanchéité pour modules de cellule solaire, et feuille de protection arrière à matériau d'étanchéité intégré qui l'utilise
US12015094B2 (en) 2019-04-11 2024-06-18 Dai Nippon Printing Co., Ltd. Sealing material sheet for solar-cell module and solar-cell module using the same

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WO2010140384A1 (fr) * 2009-06-05 2010-12-09 三井化学株式会社 Corps d'emballage pour stocker ou transporter un film d'étanchéité de cellule solaire et procédé pour stocker ou transporter un film d'étanchéité de cellule solaire
JP2011031601A (ja) * 2008-10-23 2011-02-17 Mitsubishi Chemicals Corp 熱線反射膜及びその積層体ならびに熱線反射層形成用塗布液
WO2011059009A1 (fr) * 2009-11-13 2011-05-19 三井・デュポンポリケミカル株式会社 Module de pile solaire à silicium amorphe
JP2012164962A (ja) * 2011-01-18 2012-08-30 Mitsubishi Plastics Inc 太陽電池封止材及びそれを用いて作製された太陽電池モジュール
WO2013027284A1 (fr) * 2011-08-24 2013-02-28 旭化成イーマテリアルズ株式会社 Feuille de résine d'encapsulation et module de photopile
JP2014072422A (ja) * 2012-09-28 2014-04-21 Dainippon Printing Co Ltd 封止材シートの製造方法
JP2014241391A (ja) * 2014-02-17 2014-12-25 大日本印刷株式会社 太陽電池モジュール用の封止材組成物の組合せセット、封止材シート、及び封止材シートの製造方法

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Publication number Priority date Publication date Assignee Title
JP2011031601A (ja) * 2008-10-23 2011-02-17 Mitsubishi Chemicals Corp 熱線反射膜及びその積層体ならびに熱線反射層形成用塗布液
WO2010140384A1 (fr) * 2009-06-05 2010-12-09 三井化学株式会社 Corps d'emballage pour stocker ou transporter un film d'étanchéité de cellule solaire et procédé pour stocker ou transporter un film d'étanchéité de cellule solaire
WO2011059009A1 (fr) * 2009-11-13 2011-05-19 三井・デュポンポリケミカル株式会社 Module de pile solaire à silicium amorphe
JP2012164962A (ja) * 2011-01-18 2012-08-30 Mitsubishi Plastics Inc 太陽電池封止材及びそれを用いて作製された太陽電池モジュール
WO2013027284A1 (fr) * 2011-08-24 2013-02-28 旭化成イーマテリアルズ株式会社 Feuille de résine d'encapsulation et module de photopile
JP2014072422A (ja) * 2012-09-28 2014-04-21 Dainippon Printing Co Ltd 封止材シートの製造方法
JP2014241391A (ja) * 2014-02-17 2014-12-25 大日本印刷株式会社 太陽電池モジュール用の封止材組成物の組合せセット、封止材シート、及び封止材シートの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3319130A4 (fr) * 2015-07-03 2019-01-16 Dai Nippon Printing Co., Ltd. Feuille de matériau d'étanchéité pour modules de cellule solaire, et feuille de protection arrière à matériau d'étanchéité intégré qui l'utilise
US12015094B2 (en) 2019-04-11 2024-06-18 Dai Nippon Printing Co., Ltd. Sealing material sheet for solar-cell module and solar-cell module using the same

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