WO2017094354A1 - Procédé de fabrication de matériau d'étanchéité de cellule solaire et composition pour la fabrication de matériau d'étanchéité de cellule solaire - Google Patents

Procédé de fabrication de matériau d'étanchéité de cellule solaire et composition pour la fabrication de matériau d'étanchéité de cellule solaire Download PDF

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WO2017094354A1
WO2017094354A1 PCT/JP2016/080103 JP2016080103W WO2017094354A1 WO 2017094354 A1 WO2017094354 A1 WO 2017094354A1 JP 2016080103 W JP2016080103 W JP 2016080103W WO 2017094354 A1 WO2017094354 A1 WO 2017094354A1
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ethylene
solar cell
olefin copolymer
sealing material
kpa
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PCT/JP2016/080103
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English (en)
Japanese (ja)
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晃 吉武
央尚 片岡
欣将 深川
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株式会社ブリヂストン
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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

  • the present invention relates to a method for producing a solar cell encapsulant, a composition for producing a solar cell encapsulant, a solar cell encapsulant formed using the solar cell encapsulant, and a solar cell module.
  • a surface side transparent protective member 11 made of a glass substrate or the like, a surface side sealing material 13A, a solar cell element 14 such as a silicon crystal cell, a back side sealing
  • a stopper 13B and a back surface side protection member (back cover) 12 are laminated in this order and bonded and integrated.
  • connection tabs 15 in order to obtain a high electric output. Therefore, in order to ensure the insulation of the solar cell element 14, the solar cell element 14 is sealed using the insulating sealing materials 13A and 13B.
  • an ethylene-vinyl acetate copolymer (EVA) film having high transparency and adhesiveness has been conventionally used.
  • EVA film for the sealing material is blended with a crosslinking agent such as an organic peroxide in addition to EVA, and the EVA in the EVA film is manufactured at the time of manufacturing the solar cell module. Is generally crosslinked.
  • EVA contains vinyl acetate as a constituent component
  • acid is generated in the solar cell sealing material and corrosion of the electrodes of the solar cell module occurs. Therefore, an ethylene / ⁇ -olefin copolymer that does not generate an acid has recently attracted attention as a polymer that can replace EVA (for example, Patent Document 1).
  • an object of the present invention is to provide a solar cell encapsulant capable of producing a solar cell encapsulant having good workability during production of the solar cell encapsulant and having a good surface appearance. It is to provide a manufacturing method. Moreover, the objective of this invention is providing the composition for solar cell sealing material manufacture with favorable workability and the external appearance of the surface of the solar cell sealing material manufactured.
  • Another object of the present invention is to provide a solar cell encapsulant formed by molding the composition for producing a solar cell encapsulant and a solar cell obtained by encapsulating a solar cell element with the solar cell encapsulant. To provide a module.
  • the above object is a method for producing a sealing film for a solar cell comprising a mixture of two ethylene / ⁇ -olefin copolymers A and B having different melt flow rates (MFR),
  • MFR melt flow rates
  • the gel fraction of the ethylene / ⁇ -olefin copolymer A having an MFR (conforming to JIS K7210, measured at a temperature of 190 ° C. and a load of 2.16 kg, the same applies hereinafter) of 2 to 5 g / 10 min does not increase.
  • a molecular chain linking step to obtain an ethylene / ⁇ -olefin copolymer A ′ having a viscosity of 550 to 5000 kPa ⁇ s; By mixing the ethylene / ⁇ -olefin copolymer A ′ with the ethylene / ⁇ -olefin copolymer B having an MFR of 20 to 50 g / 10 min, the elongational viscosity at 80 ° C.
  • a mixing step of obtaining a composition for producing a solar cell encapsulant having a storage elastic modulus at °C (measured in accordance with JIS K7244 under the conditions of a strain of 10% and a frequency of 1 Hz; the same shall apply hereinafter);
  • a molding step of obtaining the solar cell sealing material by molding the composition for manufacturing the solar cell sealing material into a sheet shape; It is achieved by the manufacturing method of the sealing material for solar cells containing.
  • the two ethylene / ⁇ -olefin copolymers having the predetermined MFR are used, and the ethylene / ⁇ -olefin copolymer A having the lower MFR is subjected to a molecular chain linking reaction.
  • the elongation viscosity can be significantly increased without excessively increasing the elasticity of the solar cell encapsulant manufacturing composition, resulting in sheet breakage or sagging during the production of the solar cell encapsulant.
  • the processability is improved, and the appearance of the produced solar cell encapsulant is also improved.
  • the preferable aspect of the manufacturing method of the sealing material for solar cells of this invention is as follows.
  • the molecular chain linking step is performed by adding an organic peroxide to the ethylene / ⁇ -olefin copolymer A and then heating to decompose the organic peroxide.
  • the heating is performed by heating during mixing of the ethylene / ⁇ -olefin copolymer A and the organic peroxide.
  • the molecular chain linking step is performed by irradiating the ethylene / ⁇ -olefin copolymer A with ionizing radiation.
  • the transparency of the produced solar cell encapsulant is also good.
  • the molding step is performed by calendar molding.
  • the above object is to provide an ethylene / ⁇ -olefin copolymer A ′ having an elongation viscosity at 80 ° C. in a molten state of 550 to 5000 kPa and an MFR of 0.1 to 3.5 g / 10 min, and an MFR of 20 to A sealing for solar cells comprising a resin mixture with an ethylene / ⁇ -olefin copolymer B of 50 g / 10 min, an elongational viscosity at 80 ° C. of 100 kPa ⁇ s or more and a storage elastic modulus at 80 ° C. of 40 kPa or less It is also achieved by a composition for manufacturing a material.
  • the preferable aspect of the sealing material for solar cells of this invention is as follows. (1)
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer B is 0.01 to 50 kPa ⁇ s.
  • the content of the ethylene / ⁇ -olefin copolymer A ′ is 10 to 75 parts by mass based on 100 parts by mass of the total amount of the ethylene / ⁇ -olefin copolymer A ′ and B,
  • the content of ⁇ -olefin copolymer B is 25 to 90 parts by mass.
  • the present invention is a solar cell module comprising a solar cell and a surface side protective member, a solar cell element and a back side protective member, wherein the composition for producing a solar cell encapsulant is formed into a sheet shape,
  • a solar cell module in which a solar cell element is sealed with the solar cell sealing material of the present invention.
  • the composition for producing a solar cell encapsulant according to the present invention has good processability, and the produced solar cell encapsulant has an excellent appearance. Therefore, it is possible to stably and efficiently manufacture a solar cell sealing material having excellent appearance.
  • the method for producing a solar cell encapsulant of the present invention is also referred to as an ethylene / ⁇ -olefin copolymer A (hereinafter simply referred to as “copolymer A”) having an MFR of 2 to 5 g / min. )
  • copolymer A having an MFR of 2 to 5 g / min.
  • copolymer B having an MFR of 20 to 50 g / 10 min.
  • the molecular chain linking step of the ethylene / ⁇ -olefin copolymer A can be performed using an organic peroxide or ionizing radiation.
  • an organic peroxide is added to the ethylene / ⁇ -olefin copolymer A, and the organic peroxide is decomposed by heating to generate radicals.
  • -It is carried out by connecting the molecular chains of the olefin copolymer A together.
  • the amount of the organic peroxide added is preferably 0.05 to 0.125 parts by mass, more preferably 0.08 to 0.12 parts by mass with respect to 100 parts by mass of the ethylene / ⁇ -olefin copolymer A.
  • the organic peroxide that can be used can be the same as the organic peroxide described later that is used for cross-linking during modularization when manufacturing the solar cell module.
  • the molecular chain linking reaction is preferably performed by heating when an organic peroxide is added to the ethylene / ⁇ -olefin copolymer A and mixed.
  • the heating temperature at this time may be higher than the temperature at which the organic peroxide is decomposed, but is, for example, 160 to 200 ° C.
  • the molecular chain linking reaction may be performed by irradiating the ethylene / ⁇ -olefin copolymer A with ionizing radiation. Irradiation with ionizing radiation is performed so that the 80 ° C. extensional viscosity is in the range described below within a range where the gel fraction of the copolymer A does not increase.
  • ionizing radiation electron beams, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays and the like can be used, and among them, ⁇ rays are preferable.
  • the irradiation intensity of the ionizing radiation may be set so that the 80 ° C. extensional viscosity of the ethylene / ⁇ -olefin copolymer A falls within the following range, for example, 5 to 15 kGy.
  • the shape of the ethylene / ⁇ -olefin copolymer at the time of irradiation is not particularly limited, and may be a pellet or the like.
  • the transparency (light transmittance and haze) of the solar cell encapsulant to be produced is better than that by the organic peroxide.
  • the gel fraction does not increase.
  • the phrase “the gel fraction does not increase” means that the gel fraction is 0% before and after the molecular chain linking reaction.
  • the 80 ° C. extensional viscosity of the ethylene / ⁇ -olefin copolymer A ′ after the molecular chain linking reaction is 550 to 5000 kPa ⁇ s. When the 80 ° C.
  • extensional viscosity is less than 550 kPa ⁇ s, when mixed with the ethylene / ⁇ -olefin copolymer B, the elongation viscosity at 80 ° C. of the composition for producing a sealing material for solar cells does not increase, and the workability decreases. . If it is greater than 5000 kPa ⁇ s, gels (grains) are always generated even when mixed, and the appearance of the solar cell encapsulant as a product is degraded.
  • the molecular chain linking reaction is preferably carried out so as to be in the range of 550 to 3000 kPa ⁇ s, more preferably 800 to 2700 kPa ⁇ s.
  • reaction product After completion of the molecular chain linking reaction, the reaction product is cooled, pelletized as appropriate, and may be subjected to the next mixing step, or may be directly mixed with the ethylene / ⁇ -olefin copolymer B in the next mixing step. May be.
  • the mixing step the ethylene / ⁇ -olefin copolymer A ′ having undergone the molecular chain linking reaction is converted into an ethylene / ⁇ -olefin copolymer B having an MFR of 20 to 50 g / 10 min, and additives described later as necessary.
  • Mixing can be performed by a normal method such as a roll mill.
  • the temperature at the time of mixing may be at least the melting point of the ethylene / ⁇ -olefin copolymers A ′ and B, and is, for example, 60 to 100 ° C.
  • This composition for producing a sealing material for a solar cell has an elongational viscosity at 80 ° C. (viscosity when the Henky strain is 1.0 under the condition of a strain rate of 0.05 / s. The same applies hereinafter).
  • S or more preferably 100 to 2000 kPa ⁇ s, more preferably 100 to 1000 kPa ⁇ s, still more preferably 100 to 500 kPa ⁇ s, and storage elastic modulus at 80 ° C. (strain amount 10% in accordance with JIS K7244) , Measured at a frequency of 1 Hz.
  • the mixing ratio of the ethylene / ⁇ -olefin copolymers A ′ and B is sufficient if the 80 ° C. storage elastic modulus and 80 ° C. elongation viscosity of the composition for producing a solar cell encapsulant are within the above ranges. -It can be appropriately changed according to the 80 ° C elongation viscosity of the olefin copolymer A '.
  • the ethylene / ⁇ -olefin copolymer A ′ and B have a total mass of 100 parts by mass, and the ethylene / ⁇ -olefin copolymer A ′ content is 10 to 75 parts by mass.
  • the content of the olefin copolymer B is preferably 25 to 90 parts by mass.
  • the content of the ethylene / ⁇ -olefin copolymer A ′ is 20 to 50 parts by mass with respect to 100 parts by mass of the total mass of the ethylene / ⁇ -olefin copolymers A ′ and B,
  • the content of ⁇ -olefin copolymer B is preferably 50 to 80 parts by mass.
  • the content of the ethylene / ⁇ -olefin copolymer A ′ is 20 to 40 parts by mass with respect to 100 parts by mass of the total mass of the ethylene / ⁇ -olefin copolymers A ′ and B
  • the content of ⁇ -olefin copolymer B is preferably 60 to 80 parts by mass.
  • the solar cell encapsulant manufacturing composition is formed into a sheet shape to obtain a solar cell encapsulant.
  • the molding method is not particularly limited, and it can be produced by a method of obtaining a sheet by molding by ordinary extrusion molding, calendar molding (calendering) or the like.
  • the thickness of the solar cell encapsulant is not particularly limited, but is 0.05 to 2 mm, preferably 0.3 to 0.8 mm, and more preferably 0.4 to 0.7 mm.
  • the method for producing the solar cell sealing material of the present invention is performed.
  • the two ethylene / ⁇ -olefin copolymers A and B having the predetermined MFR are used, and the ethylene / ⁇ -olefin copolymer A having the lower MFR is subjected to a molecular linking reaction. .
  • the elongation viscosity can be significantly increased without excessively increasing the elasticity of the solar cell encapsulant manufacturing composition, resulting in sheet breakage or sagging during the production of the solar cell encapsulant.
  • the processability is improved, and the appearance of the produced solar cell encapsulant is also improved.
  • the MFR of the ethylene / ⁇ -olefin copolymer A (before the molecular chain linking reaction) is 2 to 5 g / 10 min. If the MFR is less than 2 g / 10 min, the fluidity is too low to be mixed well and the appearance deteriorates. On the other hand, if the MFR is larger than 5 g / 10 min, the crosslinking effect is not so much. It is preferably 2 to 4 g / 10 min. On the other hand, the MFR of the ethylene / ⁇ -olefin copolymer B is 20 to 50 g / 10 min.
  • the MFR is less than 20 g / 10 min, the appearance is not improved. Moreover, when MFR is larger than 50 g / 10 min, it becomes difficult to mix. It is preferably 25 to 40 g / 10 min, more preferably 27 to 35 g / 10 min.
  • the MFR of the ethylene / ⁇ -olefin copolymer A ′ (after the molecular chain linking reaction) is lower than that of the copolymer A, for example, 0.1 to 3.5 g / 10 min, preferably 0.5 to 2.5 g. / 10 min.
  • the difference in density between the ethylene / ⁇ -olefin copolymers A and A ′ and B is preferably less than 0.01 g / cm 3 . Further, the difference in melting point between the ethylene / ⁇ -olefin copolymers A and A ′ and B is preferably less than 10 ° C. Thereby, the composition for solar cell sealing film manufacture which is further excellent in external appearance property and workability can be obtained.
  • the density of the ethylene / ⁇ -olefin copolymers A and A ′ and B is preferably 0.86 to 0.90 g / cm 3 , and 0.875 to 0.885 g / cm 3 . It is particularly preferred.
  • the density of ethylene- ⁇ -olefins A and B is a value determined according to JIS K 7112.
  • the melting points of the ethylene / ⁇ -olefin copolymers A and A ′ and B are preferably 50 to 80 ° C., and more preferably 50 to 70 ° C.
  • the melting points of the ethylene / ⁇ -olefin copolymers A and B are melting peak temperatures in a DSC curve obtained by heat flux differential scanning calorimetry according to JIS K7121.
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer A in the molten state before the molecular chain linking reaction is generally 50 to 200 kPa ⁇ s.
  • the elongation viscosity at 80 ° C. in the molten state of the ethylene / ⁇ -olefin copolymer A ′ after the molecular chain linking reaction is 550 to 5000 kPa ⁇ s as described above.
  • the elongation viscosity at 80 ° C. of the copolymer A ′ is preferably 2.5 to 100 times that of the copolymer A.
  • the height viscosity of copolymer B at 80 ° C. is preferably 0.01 to 50 kPa ⁇ s, more preferably 0.01 to 10 kPa.
  • the difference in refractive index between the ethylene / ⁇ -olefin copolymer A ′ and B is preferably 0.001 or less from the viewpoint of improving the transparency of the solar cell encapsulant.
  • the ethylene / ⁇ -olefin copolymers A and B are composed mainly of structural units derived from ethylene and further have an ⁇ -olefin having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene. , Ethylene- ⁇ -olefin copolymer having one or more structural units derived from 4-methylpentene-1, 4-methyl-hexene-1, 4,4-dimethyl-pentene-1, etc. (terpolymer) Etc.).
  • the ethylene / ⁇ -olefin copolymer examples include an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer, an ethylene-4-methyl-pentene-1 copolymer, an ethylene / butene / hexene copolymer. Center polymers, ethylene / propylene / octene terpolymers, ethylene / butene / octene terpolymers, and the like.
  • the content of ⁇ -olefin in the ethylene / ⁇ -olefin copolymer is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 15 to 30% by mass. If the ⁇ -olefin content is small, the solar cell encapsulant may not have sufficient flexibility and impact resistance, and if it is too much, the heat resistance may be low.
  • the ethylene / ⁇ -olefin copolymers A and B may be those polymerized using a Ziegler-Natta catalyst or a metallocene catalyst, and in particular, linear ethylene / ⁇ -olefin copolymers. Can be preferably used.
  • the molecular weight distribution Mw / Mn is preferably 2.0 to 3.5.
  • the ethylene / ⁇ -olefin copolymers A and B may be random copolymers or block copolymers, and are preferably random copolymers.
  • the ethylene / ⁇ -olefin copolymers A and B may be crystalline or amorphous, and preferably amorphous.
  • the composition for producing a sealing material for solar cells of the present invention preferably contains a crosslinking agent to form a crosslinked structure of the ethylene / ⁇ -olefin copolymers A and B.
  • a crosslinking agent an organic peroxide or a photopolymerization initiator is preferably used.
  • an organic peroxide because a sealing material with improved temperature dependency of adhesive strength, moisture resistance, and penetration resistance can be obtained.
  • Any organic peroxide may be used as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals.
  • the organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing temperature, the heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.
  • organic peroxide examples include, from the viewpoint of processing temperature and storage stability of the resin, for example, benzoyl peroxide curing agent, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 3, 5, 5- Trimethylhexanoyl peroxide, di-n-octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, tert-hexylpa Oxy-2-ethylhexano
  • benzoyl peroxide-based curing agent any can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate radicals, and those having a decomposition temperature of 50 hours or higher with a half-life of 10 hours are preferable, It can be appropriately selected in consideration of preparation conditions, film formation temperature, curing (bonding) temperature, heat resistance of the adherend, and storage stability.
  • Usable benzoyl peroxide curing agents include, for example, benzoyl peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, p-chlorobenzoyl peroxide, m-toluoyl peroxide, 2, Examples include 4-dichlorobenzoyl peroxide and t-butyl peroxybenzoate.
  • the benzoyl peroxide curing agent may be used alone or in combination of two or more.
  • organic peroxide 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane or tert-butylperoxy-2-ethylhexyl monocarbonate is particularly preferable.
  • crosslinked favorably and has the outstanding transparency is obtained.
  • the content of the organic peroxide used in the composition for producing a sealing material for solar cells is preferably 0.1 to 5 with respect to 100 parts by mass of the total amount of the ethylene / ⁇ -olefin copolymers A and B. It is preferable that the amount is part by mass, more preferably 0.2 to 3 parts by mass. If the content of the organic peroxide is small, the crosslinking speed may be lowered during the crosslinking and curing, and if the content is large, the compatibility with the copolymer may be deteriorated.
  • photopolymerization initiator any known photopolymerization initiator can be used, but a photopolymerization initiator having good storage stability after blending is desirable.
  • photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- (4- (methylthio) phenyl).
  • Acetophenones such as -2-morpholinopropane-1, benzoins such as benzyldimethylketal, benzophenones such as benzophenone, 4-phenylbenzophenone and hydroxybenzophenone, thioxanthones such as isopropylthioxanthone and 2-4-diethylthioxanthone, As other special ones, methylphenylglyoxylate can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone.
  • photopolymerization initiators may contain one or more known photopolymerization accelerators such as benzoic acid-based or tertiary amine-based compounds such as 4-dimethylaminobenzoic acid, if necessary. Can be mixed and used. Moreover, it can be used individually by 1 type of only a photoinitiator, or 2 or more types of mixture.
  • the content of the photopolymerization initiator is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the total amount of the ethylene / ⁇ -olefin copolymers A and B.
  • the composition for manufacturing a sealing material for solar cells of the present invention further contains a crosslinking aid.
  • the crosslinking aid can improve the gel fraction of the ethylene / ⁇ -olefin copolymers A and B and improve the adhesion and weather resistance of the solar cell encapsulant.
  • the content of the crosslinking aid is usually 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, particularly preferably 100 parts by mass of the total amount of the ethylene / ⁇ -olefin copolymers A and B. Is used at 0.5 to 2.5 parts by mass. Thereby, the sealing material which the hardness after bridge
  • crosslinking aid compound having a radical polymerizable group as a functional group
  • examples of the crosslinking aid include trifunctional crosslinking aids such as triallyl cyanurate and triallyl isocyanurate, and (meth) acrylic esters (eg, NK ester) ) Monofunctional or bifunctional crosslinking aids.
  • trifunctional crosslinking aids such as triallyl cyanurate and triallyl isocyanurate, and (meth) acrylic esters (eg, NK ester) ) Monofunctional or bifunctional crosslinking aids.
  • triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable.
  • the composition for producing a sealing material for solar cell of the present invention may further contain an adhesion improver.
  • an adhesion improver a silane coupling agent can be used. Thereby, it can be set as the sealing material for solar cells which has the further outstanding adhesive force.
  • the silane coupling agent include ⁇ -chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and ⁇ -glycidoxypropyl.
  • the content of the silane coupling agent in the composition for producing a solar cell sealing material of the present invention is 5 parts by mass or less, preferably 100 parts by mass of the total amount of ethylene / ⁇ -olefin copolymers A and B, preferably The amount is preferably 0.1 to 2 parts by mass.
  • composition for producing a sealing material for solar cells of the present invention improves or adjusts various physical properties of a film (optical properties such as mechanical strength and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially a machine.
  • Various additives such as a plasticizer, an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound may be further included as necessary for improving the mechanical strength.
  • the structure of the solar cell module of the present invention is not particularly limited as long as it includes a structure manufactured by sealing a solar cell element using the solar cell sealing material of the present invention.
  • a solar cell element single crystal or polycrystalline silicon cell or the like
  • Examples include a sealed structure.
  • front side the side of the solar cell element irradiated with light
  • back side the side opposite to the light receiving surface of the solar cell element
  • the front surface side transparent protective member 11 the front surface side sealing material 13A, the solar cell element 14, the back surface side sealing material 13B.
  • the back surface side protection member 12 is laminated
  • a laminated body in which each member is laminated is heated by a vacuum laminator at a temperature of 135 to 180 ° C., further 140 to 180 ° C., a degassing time of 0.1 to 5 minutes, and a press pressure of 0.1 to 1.
  • Heat pressing may be performed at 5 kg / cm 2 and a press time of 5 to 15 minutes.
  • the front surface side sealing material 13A and the back surface side sealing material 13B are sealed.
  • the solar cell element 14 can be sealed by integrating the front surface side transparent protective member 11, the back surface side transparent member 12, and the solar cell element 14 via the material 13B.
  • the solar cell elements 14 are electrically connected to each other by connection tabs 15.
  • the solar cell encapsulant of the present invention is not limited to a solar cell module using a single crystal or polycrystalline silicon crystal solar cell as shown in FIG. It can also be used as a sealing material for thin film solar cell modules such as solar cells and copper indium selenide (CIS) solar cells.
  • the solar cell of the present invention is formed on a thin film solar cell element layer formed by a chemical vapor deposition method or the like on the surface of a surface side transparent protective member such as a glass substrate, a polyimide substrate, or a fluororesin transparent substrate.
  • a structure that is bonded and integrated For example, a structure that is bonded and integrated.
  • a photovoltaic cell and a thin film solar cell element are named generically, and are called a solar cell element.
  • the surface side transparent protective member 11 is usually a glass substrate such as silicate glass.
  • the thickness of the glass substrate is generally from 0.1 to 10 mm, and preferably from 0.3 to 5 mm.
  • the glass substrate may generally be chemically or thermally strengthened.
  • the back side protective member 12 is preferably a plastic film such as polyethylene terephthalate (PET) or polyamide. Further, a film obtained by laminating a fluorinated polyethylene film, particularly a fluorinated polyethylene film / Al / fluorinated polyethylene film in this order in consideration of heat resistance and wet heat resistance may be used. Further, a glass plate may be used.
  • PET polyethylene terephthalate
  • a film obtained by laminating a fluorinated polyethylene film, particularly a fluorinated polyethylene film / Al / fluorinated polyethylene film in this order in consideration of heat resistance and wet heat resistance may be used. Further, a glass plate may be used.
  • the sealing material for solar cells of this invention has the characteristics in the sealing material used for the surface side and / or back surface side of a solar cell module (a thin film solar cell module is included). Therefore, members other than the sealing material such as the front surface side transparent protective member, the back surface side protective member, and the solar cell element may have the same configuration as that of a conventionally known solar cell module, and are not particularly limited.
  • molecular chain linking polymer (molecular chain linking step) (1) Preparation with organic peroxide (1-1) Molecular chain-linked polymer 1 to 3 Ethylene / ⁇ -olefin copolymer A (linear ethylene / ⁇ -olefin copolymer polymerized using metallocene catalyst, MFR: 3.5 g / 10 min, melting point: 60 ° C., density: 0.880 g / cm 3 (Kernel KS341T, manufactured by Nippon Polyethylene Co., Ltd.), random copolymer, amorphous) and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as an organic peroxide in the following amounts It mix
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer A before the molecular chain linking reaction was 110 kPa ⁇ s.
  • the elongational viscosities of the molecular chain linked polymers 1 to 3 at 80 ° C. were 1500 kPa ⁇ s, 2200 kPa ⁇ s, and 3000 kPa ⁇ s, respectively.
  • the MFRs of the molecular chain linked polymers 1 to 3 were 1 g / 10 min, 0.7 g / 10 min, and 0.5 g / 10 min, respectively.
  • Molecular chain linking polymer 8 The ethylene / ⁇ -olefin copolymer A is converted into an ethylene / ⁇ -olefin copolymer D (a linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst, MFR: 12 g / 10 min, melting point: Molecular chain-linked polymer 8 was obtained in the same manner as molecular chain-linked polymer 1, except that the temperature was changed to 60 ° C. and density: 0.88 g / cm 3 .
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer D before the molecular chain linking reaction was 6 kPa ⁇ s.
  • the elongational viscosity at 80 ° C. of the molecular chain linked polymer 8 was 500 kPa ⁇ s.
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer A before the molecular chain linking reaction was 110 kPa ⁇ s.
  • the elongational viscosities of the molecular chain linked polymers 4 to 6 at 80 ° C. were 1000 kPa ⁇ s, 2700 kPa ⁇ s, and 4500 kPa ⁇ s, respectively.
  • the MFRs of the molecular chain linked polymers 1 to 3 were 1.2 g / 10 min, 1 g / 10 min, and 0.9 g / 10 min, respectively.
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer C before the molecular chain linking reaction was 10 kPa ⁇ s.
  • the extensional viscosity at 80 ° C. of the molecular chain linked polymer 10 was 600 kPa ⁇ s.
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer D before the molecular chain linking reaction was 6 kPa ⁇ s.
  • the elongational viscosity at 80 ° C. of the molecular chain linked polymer 11 was 500 kPa ⁇ s.
  • the elongation viscosity at 80 ° C. of the ethylene / ⁇ -olefin copolymer E before the molecular chain linking reaction was 200 kPa ⁇ s.
  • the elongational viscosity at 80 ° C. of the molecular chain linked polymer 12 was 6000 kPa ⁇ s.
  • composition for producing solar cell encapsulant (mixing step) Each material was supplied to a roll mill with the composition shown in the following table, and kneaded at 80 ° C. to prepare a composition for producing a solar cell encapsulant.
  • Base polymer 1 linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst (Kernel KS341T, manufactured by Nippon Polyethylene Co., Ltd., random copolymer, amorphous) MFR: 3.5g / 10min Melting point: 60 ° C Density: 0.880 g / cm 3 Elongation viscosity at 80 ° C: 110 kPa ⁇ s
  • Base polymer 2 Linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst (Kernel KJ640T, manufactured by Nippon Polyethylene Co., Ltd., random copolymer, amorphous) ethylene / ⁇ -olefin copolymer As B MFR: 30g / 10min Melting point: 58 ° C Density: 0.880 g / cm 3 Elongation viscosity at 80 ° C: 0.03 kPa ⁇ s
  • Base polymer 3 linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst MFR: 65 g / 10 min Melting point: 60 ° C Density: 0.88 g / cm 3 Elongation viscosity at 80 ° C: 0.01 kPa ⁇ s
  • Base polymer 4 linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst MFR: 20 g / 10 min Melting point: 60 ° C Density: 0.88 g / cm 3 Elongation viscosity at 80 ° C: 0.1 kPa ⁇ s
  • Base polymer 5 linear ethylene / ⁇ -olefin copolymer polymerized using a metallocene catalyst MFR: 50 g / 10 min Melting point: 60 ° C Density: 0.88 g / cm 3 Elongation viscosity at 80 ° C: 0.01 kPa ⁇ s

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Abstract

L'invention concerne un procédé de fabrication de matériau d'étanchéité de cellule solaire, par lequel un matériau d'étanchéité de cellule solaire présentant un excellent aspect de surface peut être fabriqué avec une excellente aptitude au traitement lors de la fabrication du matériau d'étanchéité de cellule solaire. Le procédé de fabrication de matériau d'étanchéité de cellule solaire est destiné à fabriquer un film d'étanchéité de cellule solaire, contenant un mélange de deux types de copolymères éthylène/alpha-oléfine A et B ayant des indices de fluidité (MFR) différents, et comprend les étapes suivantes : la liaison de chaînes moléculaires consistant à provoquer une réaction de liaison entre les molécules du copolymère éthylène/alpha-oléfine A, qui possède un MFR (mesuré dans des conditions où la température est de 190 °C et la charge est de 2,16 kg conformément à la norme JIS K7210, de même ci-après) de 2 à 5 g/10 min, dans une plage dans laquelle sa fraction de gel n'augmente pas, pour obtenir un copolymère éthylène/alpha-oléfine A' possédant une viscosité d'élongation (viscosité lorsqu'une déformation de Hencky est de 1,0 dans des conditions où la vitesse de déformation est de 0,05/s, de même ci-après) de 550 à 5000 kPa·s à 80 °C, à laquelle le copolymère est à l'état fondu ; le mélange du copolymère éthylène/alpha-oléfine A' avec le copolymère éthylène/alpha-oléfine B, qui possède un MFR de 20 à 50 g/10 min, pour obtenir une composition pour la fabrication d'un matériau d'étanchéité de cellule solaire, la composition ayant une viscosité d'élongation supérieure ou égale à 100 kPa·s à 80 °C et ayant un module élastique de stockage (mesuré dans des conditions où la quantité de déformation est de 10 % et la fréquence est de 1 Hz conformément à la norme JIS K7244, de même ci-après) inférieur ou égal à 40 kPa à 80 °C ; le moulage, en forme de feuille, de la composition pour la fabrication d'un matériau d'étanchéité de cellule solaire, afin d'obtenir un matériau d'étanchéité de cellule solaire.
PCT/JP2016/080103 2015-12-04 2016-10-11 Procédé de fabrication de matériau d'étanchéité de cellule solaire et composition pour la fabrication de matériau d'étanchéité de cellule solaire WO2017094354A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662047A (zh) * 2020-04-16 2021-04-16 株式会社Lg化学 包含乙烯/α-烯烃共聚物的密封材料膜用组合物及包含其的密封材料膜

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11322862A (ja) * 1998-05-22 1999-11-26 Asahi Chem Ind Co Ltd 大型ブロー用成形材料およびその大型ブロー成形品
WO2011007871A1 (fr) * 2009-07-17 2011-01-20 三菱樹脂株式会社 Matériau d'étanchéité de cellule solaire et module de cellule solaire produit à partir de celui-ci
JP2013159673A (ja) * 2012-02-03 2013-08-19 Mitsui Chemicals Inc 太陽電池封止材および太陽電池モジュール

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11322862A (ja) * 1998-05-22 1999-11-26 Asahi Chem Ind Co Ltd 大型ブロー用成形材料およびその大型ブロー成形品
WO2011007871A1 (fr) * 2009-07-17 2011-01-20 三菱樹脂株式会社 Matériau d'étanchéité de cellule solaire et module de cellule solaire produit à partir de celui-ci
JP2013159673A (ja) * 2012-02-03 2013-08-19 Mitsui Chemicals Inc 太陽電池封止材および太陽電池モジュール

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662047A (zh) * 2020-04-16 2021-04-16 株式会社Lg化学 包含乙烯/α-烯烃共聚物的密封材料膜用组合物及包含其的密封材料膜
CN112662047B (zh) * 2020-04-16 2024-02-06 株式会社Lg化学 包含乙烯/α-烯烃共聚物的密封材料膜用组合物及包含其的密封材料膜

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