WO2022053051A1 - Film adhésif d'encapsulation de résine ionique et procédé de préparation, structure stratifiée et module photovoltaïque - Google Patents

Film adhésif d'encapsulation de résine ionique et procédé de préparation, structure stratifiée et module photovoltaïque Download PDF

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Publication number
WO2022053051A1
WO2022053051A1 PCT/CN2021/118073 CN2021118073W WO2022053051A1 WO 2022053051 A1 WO2022053051 A1 WO 2022053051A1 CN 2021118073 W CN2021118073 W CN 2021118073W WO 2022053051 A1 WO2022053051 A1 WO 2022053051A1
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WIPO (PCT)
Prior art keywords
ionic resin
adhesive film
film according
carboxylic acid
resin encapsulation
Prior art date
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PCT/CN2021/118073
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English (en)
Chinese (zh)
Inventor
李民
Original Assignee
上海海优威新材料股份有限公司
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Priority claimed from CN202010956133.1A external-priority patent/CN114163932A/zh
Priority claimed from CN202010956377.XA external-priority patent/CN114163936A/zh
Priority claimed from CN202010955685.0A external-priority patent/CN114163935A/zh
Application filed by 上海海优威新材料股份有限公司 filed Critical 上海海优威新材料股份有限公司
Publication of WO2022053051A1 publication Critical patent/WO2022053051A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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 application relates to the technical field of adhesive films, in particular to an ionic resin encapsulation adhesive film, a preparation method thereof, a laminated structure, and a photovoltaic module.
  • Photovoltaic ethylene-vinyl acetate copolymer (EVA) film is a thermosetting adhesive film, which is placed in the middle of photovoltaic modules or laminated glass. Due to the advantages of photovoltaic EVA in adhesion, durability, optical properties, etc., it is more and more widely used in current components and various optical products. Although photovoltaic EVA accounts for a small part of the overall cost of the module, it is closely related to the reliability of the module and requires high technical requirements. Therefore, considering the cost control, process route, etc., optimizing the formulation of photovoltaic EVA to make it have anti-potential induced decay (PID) performance has become one of the most realistic and feasible methods.
  • PID anti-potential induced decay
  • the purpose of the present application is to provide an ionic resin encapsulation film and its preparation method, laminate structure, photovoltaic module, the ionic resin encapsulation film can improve the anti-PID performance while ensuring high light transmittance, and It has excellent adhesion to glass, which ensures the safety of its use in laminated glass.
  • the embodiment of the present application proposes an ionic resin encapsulation adhesive film, which includes at least two layers of adhesive films, one of which is an adhesive film layer on the side close to the power generation surface of the battery, and the other layer is an ionization functional layer.
  • the functional layer contains ionic resin, wherein the ionic resin contains 50-99% of matrix resin, 0.01-40% of unsaturated carboxylate metal salt, and 0.01-5% of initiator, based on the total mass content of 100 parts; the adhesive film The transmittance is ⁇ 85%, and the haze is ⁇ 5%.
  • the matrix resin is an ethylene-vinyl acetate copolymer or an elastomer.
  • the ionic resin encapsulation adhesive film provided in the embodiments of the present application includes at least one ionization functional layer, which contains a sufficient amount of unsaturated carboxylic acid metal salt, so as to ensure that the adhesive film has improved anti-PID performance.
  • the unsaturated carboxylic acid metal salt can be sufficiently and uniformly dispersed in the ethylene-vinyl acetate copolymer matrix resin of the ionization functional layer, so that the multilayer encapsulation film can obtain High light transmittance and low haze.
  • the ionized functional layer of the ion-type resin encapsulation adhesive film of the present application also contains a certain amount of initiator.
  • a free radical reaction can be initiated by an initiator, thereby forming a network structure in the ethylene-vinyl acetate copolymer, which can generate high volume resistivity and improve the anti-PID performance of the module.
  • the network structure of ethylene-vinyl acetate copolymer can also limit the migration and diffusion of unsaturated carboxylate metal salts, preventing the unsaturated carboxylate metal salts from agglomerating to form particles with larger particle sizes, thereby deteriorating the light transmittance and fogging of the adhesive film.
  • the ionic resin encapsulation film provided in this application, if the particle size of the unsaturated carboxylic acid metal salt is too large and the distribution is uneven, the film will have low light transmittance and high haze, and only the particle size will be small to a certain extent. , in order to achieve high transmittance and low haze.
  • the unsaturated carboxylic acid metal salt in the adhesive film of the present application has good compatibility with ethylene-vinyl acetate copolymer or elastomer.
  • the network structure formed in the vinyl acetate copolymer or elastomer can produce high volume resistivity and improve the anti-PID performance of the component.
  • the cationic metal of the unsaturated carboxylic acid metal salt may include, but is not limited to, one or more of magnesium, zinc, copper, lithium, sodium, and potassium.
  • the carboxylic acid group of the unsaturated carboxylic acid metal salt may be a carboxylic acid containing an ethylenic bond and/or an alkyne bond, including but not limited to a methacrylic acid group, an acrylic acid group, a crotonic acid group group, one or more of itaconic acid group, cinnamic acid group, butyndioic acid group and maleic acid group.
  • At least a part of the unsaturated carboxylate metal salt is bonded with the base resin by a secondary bond force.
  • the initiator is an initiator that can generate free radicals by photo-initiation or thermal initiation.
  • the volume resistivity of the ionic resin encapsulation adhesive film is ⁇ 1.0*10 14 ⁇ cm.
  • the ionic resin encapsulant film may further include at least one ethylene-vinyl acetate layer.
  • the elastomers include rubber elastomers and polyolefin elastomers, and the rubber elastomers include but are not limited to natural rubber (NR), ethylene propylene diene monomer (EPDM), hydrogenated styrene butyl One or more of diene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) kind.
  • NR natural rubber
  • EPDM ethylene propylene diene monomer
  • SEBS diene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • the ionic resin encapsulation film is used as an encapsulation film of a solar cell.
  • the ionic resin encapsulation film is used as the intermediate film of the laminated glass.
  • the present application also relates to a laminate structure comprising at least one outer layer, and at least one ionic resin encapsulant film.
  • the laminated structure is in the form of a photovoltaic module, safety glass or insulating glass.
  • the present application also relates to a photovoltaic module, comprising at least one outer layer, a battery sheet, and the ionic resin encapsulating film as described in the first aspect of the present application.
  • the outer layer is photovoltaic glass and/or a backsheet.
  • the present application also relates to a preparation method of an ionic resin encapsulation film, the preparation method is to add metal oxides or hydroxides, unsaturated carboxylic acids, initiators, other Additives and matrix resin, cast or calendered into film.
  • the metal oxide or hydroxide reacts with the unsaturated carboxylic acid in-situ in the matrix resin to generate the unsaturated carboxylic acid metal salt.
  • the particle size of the unsaturated carboxylic acid metal salt is very small, and it is uniformly distributed in the matrix resin.
  • the adhesive film prepared by this method has low light transmittance and high haze.
  • the metal salt of unsaturated carboxylate generated in situ by this method has good compatibility with ethylene-vinyl acetate copolymer or elastomer.
  • a network structure is formed in vinyl acetate copolymer or elastomer, which can produce high volume resistivity and improve the anti-PID performance of components.
  • the network structure of the ethylene-vinyl acetate copolymer or elastomer can also limit the migration and diffusion of unsaturated carboxylic acid metal salts, preventing unsaturated carboxylic acid metal salts from agglomerating to form particles with larger particle sizes, thereby deteriorating the light transmission of the adhesive film. rate and haze.
  • the content of the matrix resin is 50-99%, the content of the metal oxide or hydroxide is 0.01-40%, and the content of the unsaturated carboxylic acid is 0.01-40%.
  • the content is 0.01-40%, the content of the initiator is 0.01-5%, and the content of other auxiliary agents is 0.01-5%, based on 100 parts of the total mass content.
  • the matrix resin is an ethylene-vinyl acetate copolymer or an elastomer;
  • the elastomer includes a rubber elastomer and a polyolefin elastomer, and the rubber elastomer includes but is not limited to natural rubber (NR), EPDM, hydrogenated styrene butadiene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene
  • NR natural rubber
  • SEBS hydrogenated styrene butadiene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS olefin-styrene block copolymers
  • the metal oxides or hydroxides include, but are not limited to, one or more of oxides or hydroxides of magnesium, zinc, copper, lithium, sodium, and potassium.
  • the unsaturated carboxylic acid is a carboxylic acid containing ethylenic and acetylenic bonds, including but not limited to methacrylic acid, acrylic acid, crotonic acid, itaconic acid, cinnamic acid, butynedi One or more of acid and maleic acid, etc.
  • the initiator is an initiator that can generate free radicals by photo-initiation or thermal initiation.
  • the other auxiliary agents are one or more of auxiliary crosslinking agents, antioxidants, and silane coupling agents.
  • the embodiments of the present application provide an ionic resin encapsulation adhesive film, which includes at least one ionized functional layer, the ionized functional layer includes an ionic resin, and the ionic resin includes 50-99% of a matrix resin, unsaturated Carboxylic acid metal salt 0.01-40%, initiator 0.01-5%, based on the total mass content of 100 parts; the matrix resin includes ethylene-vinyl acetate copolymer or elastomer; the light transmittance of the adhesive film ⁇ 85%, haze ⁇ 5%.
  • the ionic resin encapsulating adhesive film of the present application can be used in photovoltaic modules. Since in the ionic resin encapsulating adhesive film of the present application, the ionizing functional layer contains a predetermined amount of unsaturated metal carboxylate, when the component is laminated and used, a free radical reaction can be initiated by an initiator, thereby forming a network in the matrix resin The structure traps metal ions and thus can provide improved anti-PID performance for photovoltaic modules. In addition, the ionic resin encapsulating film of the present application maintains excellent optical properties, that is, light transmittance ⁇ 85% and haze ⁇ 5%.
  • the particulate metal ion scavenger is often directly mixed into the matrix resin raw material for film formation. Due to the high melting point of such metal ion scavengers, they cannot be uniformly dispersed in the matrix resin, and can only exist in the form of particles with large particle sizes, which adversely affects the light transmittance and haze of the produced film. Therefore, prior to the present application, if the prior art encapsulation film contains a sufficient content of metal ion scavenger, it is necessary to sacrifice optical properties as the expense, and it is impossible to obtain a light transmittance ⁇ 85% and a haze ⁇ 5%.
  • the corresponding unsaturated carboxylic acid and the unsaturated carboxylic acid metal salt that can react with the unsaturated carboxylic acid to form the unsaturated carboxylic acid metal salt can be added to the matrix resin raw material for film formation.
  • Metal ion basic compounds such as metal hydroxides, metal oxides.
  • the unsaturated carboxylic acid and the metal ion-containing basic compound react under the conditions of melt blending with the matrix resin to form the unsaturated carboxylic acid metal salt.
  • the in-situ generated metal salt of unsaturated carboxylate can be uniformly dispersed in the matrix resin.
  • the average particle size of the unsaturated carboxylic acid metal salt may be ⁇ 900 nm, or ⁇ 120 nm, or ⁇ 110 nm, ⁇ 50 nm, ⁇ 20 nm, or ⁇ 10 nm, or even ⁇ 1 nm.
  • the content of the unsaturated carboxylic acid metal salt in the encapsulating film may be, based on 100 parts by mass of the ionized functional layer base resin, ⁇ 35%, ⁇ 30%, ⁇ 25%, ⁇ 20%, ⁇ 15%, or ⁇ 10%. In some embodiments, the content of the unsaturated carboxylic acid metal salt in the encapsulating film may be, based on 100 parts by mass of the ionized functional layer base resin, ⁇ 0.05%, ⁇ 0.1%, ⁇ 0.5%, ⁇ 1%, or ⁇ 5%.
  • the unsaturated carboxylate metal salt can be very uniformly dispersed in the matrix resin of the ionized functional layer, so even if the content of the unsaturated carboxylate metal salt is low, the anti-PID performance of the photovoltaic module can be effectively improved.
  • the unsaturated carboxylate metal salt is added in an in-situ manner, so even if the content of the unsaturated carboxylate metal salt is high, the encapsulant film can maintain satisfactory optical properties.
  • the cationic metal of the unsaturated metal carboxylate is selected from one or more of magnesium, zinc, copper, lithium, sodium, potassium.
  • the cationic metal of the unsaturated carboxylic acid metal salt is selected from one or more of magnesium, zinc, and copper.
  • the carboxylic acid group of the metal unsaturated carboxylate is a carboxylic acid group containing an ethylenic and/or acetylenic bond.
  • the carboxylic acid group is selected from the group consisting of a methacrylic acid group, an acrylic acid group, a crotonic acid group, an itaconic acid group, a cinnamic acid group, a butynedioic acid group and a maleic acid group. one or more.
  • the metal salt of an unsaturated carboxylate is magnesium acrylate, zinc methacrylate.
  • the ionizing functional layer further contains an initiator.
  • the initiator is selected from initiators that can photo- or thermally generate free radicals. Examples of the initiator include organic peroxides, alkylphenone-based initiators, azo compounds, and the like.
  • the initiator can generate free radicals to initiate a free radical reaction, so that the ethylene-vinyl acetate copolymer matrix resin forms a network structure, which can generate high volume resistivity and improve the resistance of the module. PID performance.
  • the volume resistivity of the encapsulant film according to the present application is ⁇ 1.0*10 14 ⁇ cm.
  • the volume resistivity of the encapsulating film according to the present application is ⁇ 1.0*10 15 ⁇ cm, or even ⁇ 1.0*10 16 ⁇ cm.
  • such a network structure can also limit the migration and diffusion of unsaturated carboxylate metal salts, and prevent unsaturated carboxylate metal salts from agglomerating to form larger particles during the use of the encapsulating film, thereby deteriorating the light transmittance and haze. Therefore, the encapsulating adhesive film of the present application has improved durability when used in photovoltaic modules, and can maintain good optical performance even after a long period of use.
  • At least a portion of the unsaturated carboxylate metal salt is subvalently bonded to the matrix resin.
  • Such secondary bonding can be generated by the reaction of the unsaturated groups of the unsaturated carboxylic acid groups with the matrix resin initiated by the initiator.
  • the peel strength of the encapsulating film of the present application and glass is ⁇ 170N/cm, ⁇ 175N/cm, or ⁇ 176N/cm, or even ⁇ 180N/cm.
  • the ionic resin encapsulant film may further include at least one layer of ethylene-vinyl acetate.
  • the ethylene-vinyl acetate layer is arranged close to the power generation surface of the cell. In this way, the ethylene-vinyl acetate layer can be used as a barrier layer between the ionized functional layer and the battery sheet, to block the reaction product during the lamination and use of the segregated functional layer, thereby protecting the battery sheet.
  • Embodiments of the present application further provide a laminated structure comprising at least one outer layer and any one of the above-mentioned ionic resin encapsulating adhesive films.
  • the laminated structure is in the form of photovoltaic modules, safety glass or insulating glass.
  • the embodiments of the present application further provide a photovoltaic module, comprising at least one outer layer, a battery sheet, and any one of the above-mentioned ionic resin encapsulation adhesive films according to the present application.
  • the outer layers of the photovoltaic assembly are photovoltaic glass and/or a backsheet.
  • the photovoltaic modules according to the present application can obtain improved anti-PID performance.
  • the photovoltaic module of the present application after 192 hours of aging under the conditions of a temperature of 85° C., a humidity of 85%, and a pressure of 1500V, the photovoltaic module of the present application has a power attenuation of ⁇ 5%, or ⁇ 3%, or even ⁇ 2.5%.
  • the embodiment of the present application also provides a method for preparing an ionic resin encapsulation film, the preparation method is to add metal oxides or hydroxides, unsaturated carboxylic acids, initiators, and other auxiliary agents to the film-making equipment And matrix resin, casting or calendering into film.
  • the content of matrix resin is 50-99%, the content of metal oxide or hydroxide is 0.01-40%, the content of unsaturated carboxylic acid is 0.01-40%, the initiator The content is 0.01-5%, and the content of other auxiliary agents is 0.01-5%, based on the total mass content of 100 parts.
  • the particulate metal ion scavenger is often directly mixed into the matrix resin raw material for film formation. Due to the high melting point of such metal ion scavengers, they cannot be uniformly dispersed in the matrix resin, and can only exist in the form of particles with large particle sizes, which adversely affects the light transmittance and haze of the produced film. Therefore, prior to the present application, if the prior art encapsulation film contains a sufficient content of metal ion scavenger, it is necessary to sacrifice optical performance as the expense, and cannot obtain light transmittance ⁇ 85% and haze ⁇ 5%.
  • the corresponding unsaturated carboxylic acid and the unsaturated carboxylic acid metal salt that can react with the unsaturated carboxylic acid to form the unsaturated carboxylic acid metal salt can be added to the matrix resin raw material for film formation.
  • Metal ion basic compounds such as metal hydroxides, metal oxides.
  • the unsaturated carboxylic acid and the metal ion-containing basic compound react under the conditions of melt blending with the matrix resin to form the unsaturated carboxylic acid metal salt.
  • the in-situ generated metal salt of unsaturated carboxylate can be uniformly dispersed in the matrix resin.
  • the average particle size of the unsaturated carboxylic acid metal salt may be ⁇ 900 nm, or ⁇ 130 nm, or ⁇ 25 nm, or even ⁇ 2 nm.
  • the metal oxide or hydroxide is selected from one or more of the oxides or hydroxides of the metals magnesium, zinc, copper, lithium, sodium, potassium;
  • the unsaturated carboxylic acid is selected from one or more of methacrylic acid, acrylic acid, crotonic acid, itaconic acid, cinnamic acid, butynedioic acid, maleic acid, and the like.
  • the initiator is selected from initiators that can photo- or thermally generate free radicals.
  • examples of the initiator include organic peroxides, alkylphenone-based initiators, azo compounds, and the like.
  • the initiator can generate free radicals to initiate a free radical reaction, so that the matrix resin forms a network structure, which can generate high volume resistivity and improve the anti-PID performance of the module.
  • the volume resistivity of the encapsulant film according to the present application is ⁇ 1.0*10 14 ⁇ cm.
  • the volume resistivity of the encapsulating film according to the present application is ⁇ 1.0*10 15 ⁇ cm, or even ⁇ 1.0*10 16 ⁇ cm.
  • such a network structure can also limit the migration and diffusion of unsaturated carboxylate metal salts, and prevent unsaturated carboxylate metal salts from agglomerating to form larger particles during the use of the encapsulating film, thereby deteriorating the light transmittance and haze.
  • outer layer is defined as ethylene-vinyl acetate layer
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3.5% ⁇ -aminopropyltriethoxysilane
  • Antioxidant 1% 2,6-di-tert-butyl-4-methylphenol
  • the formula of the ionized functional layer, that is, the interlayer film, is as follows:
  • Ethylene-vinyl acetate copolymer 86%
  • Unsaturated carboxylic acid 6% methacrylic acid
  • Metal oxide 0.5% zinc oxide
  • Initiator 0.5% tert-butyl peroxybenzoate
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3.5% ⁇ -aminopropyltriethoxysilane
  • Antioxidant 0.5% 2,6-di-tert-butyl-4-methylphenol
  • the materials are weighed, and after the weighing is completed, they are respectively added to the hoppers of three plastic extruders for extrusion. film.
  • the three-layer adhesive film obtained by co-extrusion is denoted as S1-1.
  • ethylene-vinyl acetate layer is as follows: (This formula is defined as ordinary ethylene-vinyl acetate film D1-1)
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3.5% ⁇ -aminopropyltriethoxysilane
  • Ethylene-vinyl acetate copolymer 50%;
  • Unsaturated carboxylic acid 30% acrylic acid
  • Metal oxide 10% magnesium oxide
  • Co-crosslinking agent 2.8% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 3% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 1.2% 2,6-di-tert-butyl-4-methylphenol
  • the materials are weighed. After the weighing is completed, the materials are added to the hoppers of two plastic extruders for extrusion.
  • the temperature of the plastic extruders is 90 °C, and the required double-layer structure hot melt film.
  • the double-layer adhesive film obtained by co-extrusion is denoted as S1-2.
  • Both outer layers are formulated as follows (defined as an ethylene vinyl acetate layer)
  • Co-crosslinking agent 1.5% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 1.5% vinyltrimethoxysilane
  • Antioxidant 1% tetrakis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester;
  • the formula of the ionized functional layer, that is, the interlayer film, is as follows:
  • Ethylene-vinyl acetate copolymer 85%;
  • Unsaturated carboxylic acid 6% acrylic acid
  • Metal oxide 1% zinc oxide
  • Initiator 0.5% azobisisobutyronitrile
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3.5% ⁇ -aminopropyltriethoxysilane
  • Antioxidant 1% 2,6-di-tert-butyl-4-methylphenol
  • the materials are weighed, and after the weighing is completed, they are added to the hoppers of three plastic extruders for extrusion. film.
  • the three-layer adhesive film obtained by co-extrusion is denoted as S1-3.
  • ethylene-vinyl acetate layer is as follows: (this formula is defined as ordinary ethylene-vinyl acetate film D1-2)
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 4.5% ⁇ -aminopropyltriethoxysilane
  • Ethylene-vinyl acetate copolymer 50%;
  • Unsaturated carboxylate metal salt 20% acrylic acid
  • Metal oxide 20% zinc oxide
  • Co-crosslinking agent 2.8% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 3% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 1.2% 2,6-di-tert-butyl-4-methylphenol
  • the materials are weighed. After the weighing is completed, the materials are added to the hoppers of two plastic extruders for extrusion.
  • the temperature of the plastic extruders is 90 °C, and the required double-layer structure hot melt film.
  • the double-layer adhesive film obtained by co-extrusion is denoted as S1-4.
  • Example 1 Put the three-layer adhesive film prepared in Example 1 in the order of tempered glass (float glass)-S1-1-battery sheet-S1-1-tempered glass (float glass or backplane), and place the laminator.
  • the lamination temperature is 142°C
  • the lamination time is 18min
  • the obtained module structure is denoted as C1-1.
  • Example 2 Put the adhesive film prepared in Example 2 in the order of tempered glass (float glass)-S1-2-battery sheet-S1-2-tempered glass (float glass or backplane), and place them in a laminator for lamination.
  • the lamination temperature is 142°C
  • the lamination time is 18min
  • the obtained component structure is denoted as C1-3.
  • Example 1 Put the adhesive films prepared in Example 1 in the order of float glass (tempered glass)-S1-1-float glass (tempered glass), place them in a laminator for lamination, and the lamination process is 90-135°C , the lamination time is 70min, and the obtained module structure is denoted as C1-4.
  • Example 2 Put the adhesive films prepared in Example 2 in the order of float glass (tempered glass)-S1-2-float glass (tempered glass), and place them in a laminator for lamination.
  • the lamination process is 90-135°C.
  • the lamination time is 70min
  • the obtained module structure is denoted as C1-5.
  • the film formulation is as follows:
  • Ethylene-vinyl acetate copolymer 60%;
  • Unsaturated carboxylic acid 20% methacrylic acid
  • Metal oxide 14% zinc oxide
  • Initiator 1% tert-butyl peroxybenzoate
  • Co-crosslinking agent 1% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3% ⁇ -aminopropyltriethoxysilane
  • Antioxidant 1% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion. 1.
  • the film formulation is as follows:
  • Polyolefin elastomer 50%;
  • Unsaturated carboxylic acid 30% acrylic acid
  • Metal oxide 10% magnesium oxide
  • Co-crosslinking agent 2.8% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 3% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 1.2% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion. 2.
  • the film formulation is as follows:
  • EPDM rubber 85%;
  • Unsaturated carboxylic acid 6% acrylic acid
  • Metal oxide 1% zinc oxide
  • Initiator 0.5% azobisisobutyronitrile
  • Co-crosslinking agent 3.5% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 3% ⁇ -aminopropyltriethoxysilane
  • Antioxidant 1% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion. 3.
  • the film formulation is as follows:
  • Hydrogenated styrene butadiene block copolymer 50%;
  • Unsaturated carboxylic acid 20% acrylic acid
  • Metal oxide 20% zinc oxide
  • Co-crosslinking agent 2.8% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 3.5% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 1.2% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion. 4.
  • Example 1 Put the adhesive film prepared in Example 1 in the order of tempered glass (float glass)-S1-battery sheet-S1-tempered glass (float glass or backplane), place it in a laminator for lamination, and the lamination temperature The temperature was 142° C., the lamination time was 18 min, and the obtained module structure was denoted as C2-1.
  • Example 2 Put the adhesive film prepared in Example 2 in the order of tempered glass (float glass)-S2-battery sheet-S2-tempered glass (float glass or backplane), place it in a laminator for lamination, and the lamination temperature The temperature was 142° C., the lamination time was 18 min, and the resulting module structure was denoted as C2-3.
  • the adhesive films prepared in Example 1 were placed in the order of float glass (tempered glass)-S1-float glass (tempered glass), placed in a laminator for lamination, and the lamination process was 90-135° C.
  • the pressing time was 70 min, and the obtained assembly structure was denoted as C2-4.
  • the adhesive films prepared in Example 2 were placed in the order of float glass (tempered glass)-S2-float glass (tempered glass), placed in a laminator for lamination, and the lamination process was 90-135° C.
  • the pressing time was 70 min, and the obtained assembly structure was denoted as C2-5.
  • ethylene-vinyl acetate adhesive film (denoted as D2-1), polyolefin elastomer adhesive film (denoted as D2-2), Ethylene-vinyl acetate film assembly structure (denoted as D2-3), polyolefin elastomer film assembly structure (denoted as D2-4).
  • Ethylene-vinyl acetate copolymer 50%;
  • Unsaturated carboxylic acid 40% acrylic acid
  • Oxides or hydroxides of metals 8% magnesium hydroxide
  • Initiator 0.5% 2-hydroxy-2-methyl-1-phenylacetone
  • Co-crosslinking agent 0.5% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 0.5% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 0.5% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and casting into a film.
  • the temperature of the plastic extruder is 90 ° C, and the extrusion time is 15 minutes. S3-1.
  • Rubber elastomer 50% EPDM rubber
  • Unsaturated carboxylic acid 6% cinnamic acid
  • Co-crosslinking agent 2.0% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 0.4% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 0.1% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and casting into a film.
  • the temperature of the plastic extruder is 70 ° C, and the extrusion time is 15 minutes.
  • the obtained film is recorded as S3-2.
  • Rubber elastomer 60% hydrogenated styrene butadiene block copolymer
  • Unsaturated carboxylic acid 20% acrylic acid
  • Oxides or hydroxides of metals 10% zinc oxide
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 1% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 1% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and calendering into a film.
  • the temperature of the plastic extruder is 110 ° C, and the extrusion time is 25 minutes. -3.
  • Polyolefin 99% ethylene-octene copolymer
  • Unsaturated carboxylic acid 0.01% methacrylic acid
  • Oxides or hydroxides of metals 0.01% zinc oxide
  • Initiator 0.01% 2-hydroxy-2-methyl-1-phenylacetone
  • Co-crosslinking agent 0.03% 2,4,6-tri(allyloxy)-s-triazine
  • Silane coupling agent 0.02% ⁇ -methacryloyloxypropyltrimethoxysilane
  • Antioxidant 0.02% 2,6-di-tert-butyl-4-methylphenol
  • the material is weighed. After the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and calendering.
  • the temperature of the plastic extruder is 140 ° C and the extrusion time is 15 minutes. -4.
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 3.5% ⁇ -aminopropyltriethoxysilane
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and casting into a film.
  • the temperature of the plastic extruder is 90 ° C, and the extrusion time is 15 minutes.
  • Ethylene-octene copolymer 81%
  • Co-crosslinking agent 3% 2,4,6-tris(allyloxy)s-triazine
  • Silane coupling agent 4.5% ⁇ -aminopropyltriethoxysilane
  • the material is weighed, and after the weighing is completed, it is added to the hopper of the plastic extruder for extrusion and casting into a film.
  • the temperature of the plastic extruder is 90 ° C, and the extrusion time is 15 minutes.
  • the particle size, haze, light transmittance, volume resistivity and peel strength of the unsaturated carboxylic acid metal salts in the adhesive films of Examples 1 to 4 were tested.
  • the haze, light transmittance and anti-PID performance of the laminated structures 1 to 5 were tested.
  • the particle size, haze, light transmittance, volume resistivity and peel strength of the unsaturated carboxylic acid metal salt in the adhesive films of Examples 10-13 were tested.
  • the haze, light transmittance and anti-PID performance of the laminated structures 1 to 5 were tested.
  • the particle size, haze, light transmittance, volume resistivity and peel strength of the unsaturated carboxylic acid metal salts in the adhesive films of Examples 19-22 were tested.
  • the haze, light transmittance and anti-PID performance of the laminated structures 1 to 5 were tested.
  • the particle size was measured by the transmission electron microscope sectioning method, a small amount of the sample was uniformly dispersed in the ethanol solution, the sample was dropped on the surface of the copper mesh, and the sample on the copper mesh was dried. After the copper mesh is completely dried, put the copper mesh into the testing instrument, and observe the particle size of the unsaturated carboxylic acid metal salt at different magnifications.
  • the lamination process is 145°C
  • the lamination pressure is 70kPa
  • the volume resistivity is measured after cooling for 18 minutes. Tested according to GB/T 29848 standard.
  • module structures C1-1 ⁇ C1-5 Compared with ordinary ethylene-vinyl acetate module structure D1-4, module structures C1-1 ⁇ C1-5 have lower haze and higher light transmittance; module structures C1-1 ⁇ C1-5 are different from ordinary ethylene-vinyl acetate module structures
  • the film component structure D1-3 and the ordinary ethylene-vinyl acetate component structure D1-4 have significantly improved anti-PID performance.
  • Component structures C2-1 to C2-5 have lower haze and higher light transmittance compared to ordinary polyolefin elastomer component structure D2-4; component structures C2-1 to C2-5 are different from ordinary ethylene-vinyl acetate glue For the membrane module structure D2-3 and the common polyolefin elastomer module structure D2-4, the anti-PID performance is significantly improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)

Abstract

La présente invention concerne un film adhésif d'encapsulation de résine ionique et un procédé de préparation, une structure stratifiée et un module photovoltaïque. Le film adhésif d'encapsulation de résine ionique comprend une couche fonctionnelle ionisée, et la couche fonctionnelle ionisée comprend une résine ionique ; la résine ionique comprend de 50 à 99 % d'un copolymère ou élastomère éthylène-acétate de vinyle, de 0,01 à 40 % d'un sel de carboxylate métallique insaturé, et de 0,01 à 5 % d'un initiateur, sur la base de la teneur en masse totale de 100 parties. Le sel de carboxylate métallique insaturé et le copolymère ou élastomère éthylène-acétate de vinyle dans le film adhésif de la présente invention présentent une bonne compatibilité, et pendant l'utilisation du film adhésif, l'initiateur déclenche une réaction radicalaire, de manière à former une structure de réseau dans le copolymère ou élastomère éthylène-acétate de vinyle, ce qui permet de produire une résistivité volumique élevée, d'améliorer les performances anti-PID des modules, et de maintenir la bonne transmittance de la lumière du film adhésif.
PCT/CN2021/118073 2020-09-11 2021-09-13 Film adhésif d'encapsulation de résine ionique et procédé de préparation, structure stratifiée et module photovoltaïque WO2022053051A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN202010955685.0 2020-09-11
CN202010956133.1A CN114163932A (zh) 2020-09-11 2020-09-11 离子型树脂封装胶膜的制备方法
CN202010956377.XA CN114163936A (zh) 2020-09-11 2020-09-11 离子型树脂封装胶膜和层压结构
CN202010956377.X 2020-09-11
CN202010956133.1 2020-09-11
CN202010955685.0A CN114163935A (zh) 2020-09-11 2020-09-11 用于光伏组件的多层离子型树脂封装胶膜和组件结构

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