WO2021253612A1 - 胶膜及包含其的电子器件 - Google Patents

胶膜及包含其的电子器件 Download PDF

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Publication number
WO2021253612A1
WO2021253612A1 PCT/CN2020/109634 CN2020109634W WO2021253612A1 WO 2021253612 A1 WO2021253612 A1 WO 2021253612A1 CN 2020109634 W CN2020109634 W CN 2020109634W WO 2021253612 A1 WO2021253612 A1 WO 2021253612A1
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WIPO (PCT)
Prior art keywords
group
adhesive film
ethylene
layer
modified polyolefin
Prior art date
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PCT/CN2020/109634
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English (en)
French (fr)
Inventor
魏梦娟
唐国栋
侯宏兵
周光大
Original Assignee
杭州福斯特应用材料股份有限公司
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Publication date
Application filed by 杭州福斯特应用材料股份有限公司 filed Critical 杭州福斯特应用材料股份有限公司
Priority to EP20934879.6A priority Critical patent/EP3957694A4/en
Priority to US17/614,574 priority patent/US11905398B2/en
Priority to JP2021572665A priority patent/JP7375051B2/ja
Publication of WO2021253612A1 publication Critical patent/WO2021253612A1/zh

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • 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
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
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    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • 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
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    • C08J5/18—Manufacture of films or sheets
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C—CHEMISTRY; METALLURGY
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
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    • H—ELECTRICITY
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    • 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
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    • C09J2451/00—Presence of graft polymer

Definitions

  • the present invention relates to the field of photoelectric conversion devices, in particular, to a glue film and an electronic device containing the same.
  • Photoelectric conversion refers to the conversion of solar energy into electrical energy through the photovoltaic effect.
  • electronic devices photoelectric conversion devices
  • solar cells such as crystalline silicon batteries, amorphous silicon batteries, cadmium telluride batteries, copper indium gallium tin batteries, perovskite batteries
  • Liquid crystal panels Liquid crystal panels, electroluminescence devices, plasma display devices, sensors, etc.
  • the sealing material is then bonded to the upper and lower substrates to form a complete electronic device module.
  • crystalline silicon solar cell modules are usually laminated according to the front glass substrate, front sealing layer polymer, crystalline silicon battery, rear sealing layer polymer, rear glass substrate or polymer substrate, and then heated and heated by a vacuum laminator. After pressing, a complete solar module is formed.
  • Polymer sealing materials usually need to meet the following conditions: I) Adhesion. The polymer sealing material is chemically bonded to the electronic device and the substrate after being heated and melted, and it is generally expected that no delamination will occur between the sealing material and the electronic device and the substrate during long-term use. II) Softness. It has a low modulus of elasticity and protects electronic devices from damage caused by external impact; III) Transparency. For example, for solar cells, the sealing material needs to have high light transmittance, so as to maximize the use of sunlight and improve the efficiency of power generation. IV) Insulation. Generally, the polymer sealing material needs high volume resistivity to avoid large leakage current. V) Chemical stability.
  • the sealing material When solar modules are exposed to high temperature, high humidity, and ultraviolet radiation during long-term outdoor use, the sealing material should not be severely deteriorated, resulting in yellowing, decreased mechanical properties, and release of corrosive compounds. VI) Heat resistance. Solar modules are exposed to long-term high temperature outdoors, and the sealing material should not flow or creep. Therefore, the sealing material usually needs to be cross-linked.
  • the commonly used packaging materials for photoelectric conversion devices are ethylene-vinyl acetate and polyolefin.
  • Ethylene-vinyl acetate will produce acetic acid during the use of photovoltaic modules, causing corrosion of electronic devices or PID (potential potential induced attenuation) problems.
  • PID potential potential induced attenuation
  • the water vapor barrier and air tightness of polyolefin are better than ethylene-vinyl acetate copolymer, but the cost of polyolefin is higher, and the two can be used together. While taking into account the performance, the cost is reduced, but the adhesiveness of the film is significantly reduced when the two are used at the same time.
  • small molecular amide compounds are directly added during the polymerization process of the adhesive film.
  • bubbles are easily generated on the surface of the adhesive film during the lamination process, which affects the appearance of the assembly, reduces the crosslinking degree of the packaging material, and causes the packaging material to interact with each other.
  • the adhesive force of the module is reduced, and the power generation is further reduced, and it is difficult to reach the 25-year service life of the photovoltaic module.
  • the main purpose of the present invention is to provide an adhesive film and an electronic device containing it, so as to solve the technical problems of poor adhesion between the existing polyolefin film and the ethylene-vinyl acetate copolymer layer and PID.
  • an adhesive film includes: at least one modified polyolefin resin layer, and the resin forming the modified polyolefin resin layer includes 1-100% of the modified polyolefin resin layer.
  • Polyolefin resin the main chain of the modified polyolefin resin is ethylene- ⁇ olefin copolymer
  • the graft branch is selected from anhydride group, hydroxyl group, ester group, carbonyl group, amide group, pyridyl group, epoxy group, pyrrolidone
  • a compound formed by one or more vinyl monomers in the glycidyl group and the glycidyl group, the molecular weight of the grafted branch is 150 ⁇ 8000g/mol; and the adjacent layers are not ethylene-vinyl acetate copolymer layers at the same time .
  • the grafted branch is a compound containing an amide group with a molecular weight of 1000-5000 g/mol; in the modified polyolefin resin, the grafted branch has a grafting rate of 0.5-15%.
  • the grafted branch is formed by a compound formed from a vinyl monomer containing an amide group represented by the formula (I) and the main chain is formed by a radical grafting reaction,
  • R 1 is a substituent formed by H, group A, and at least one hydrogen atom in group A being substituted by a hydroxyl group or epoxy group, or a substituent formed by replacing at least one methylene group in group A by a carbonyl group
  • the group A is a straight chain alkyl group, a branched chain alkyl group or a cycloalkyl group, and the first substituent has carbon atoms ⁇ 10, and R 2 is an alkenyl group with 2 to 20 carbon atoms.
  • R 2 is selected from vinyl, propenyl, butadienyl, butenyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, decaene Group, undecenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl.
  • the vinyl monomer containing an amide group is selected from the group consisting of acrylamide, methacrylamide, N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N- Tert-butyl acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl) acrylamide, N,N'-methylene bisacrylamide , Maleimide group, oleic acid amide group, 9-hexadecenamide group, N-(2-hydroxyethyl)-undec-10-enamide group, 9-tetradecenamide group, One or more of the group consisting of 9-dodecenamido, 9-decenamido, octenamido, heptenamido, hexenamido, pentenamido and butenamido kind.
  • the ethylene- ⁇ -olefin copolymer is a copolymer of ethylene and at least one ⁇ -olefin having a carbon number of ⁇ 10.
  • ⁇ -olefin having carbon atoms ⁇ 10 is selected from the group consisting of propylene, 1-butene, 1-hexene, 1-pentene, 1-octene and 4-methyl-1-pentene One or more.
  • the density of the ethylene- ⁇ olefin copolymer is 0.86 to 0.89 g/cm 3
  • the melt index of the ethylene- ⁇ olefin copolymer is 1 to 40 g/10 min.
  • the density of the ethylene- ⁇ olefin copolymer is 0.87 to 0.88 g/cm 3
  • the melt index of the ethylene- ⁇ olefin copolymer is 3 to 30 g/10 min.
  • the aforementioned adhesive film further includes at least one ethylene-vinyl acetate copolymer layer, and adjacent layers are not ethylene-vinyl acetate copolymer layers at the same time.
  • the ratio of the thickness of the adjacent modified polyolefin resin layer to the ethylene-vinyl acetate copolymer layer is 1: (1 to 3).
  • the raw materials for forming the modified polyolefin resin layer and the ethylene-vinyl acetate copolymer layer also include crosslinking agents, crosslinking aids, antioxidants, ultraviolet absorbers, light stabilizers, tackifiers, and corrosion inhibitors. , One or more of the pigments.
  • Another aspect of the present application provides an electronic device, including an encapsulating adhesive film, and the encapsulating adhesive film includes the above-mentioned adhesive film.
  • the modified group in the graft branch is easy to graft with the ethylene- ⁇ olefin copolymer, and the above several groups contain heteroatoms, so the above polar groups are introduced, especially the strong polarity
  • the amide group is conducive to the formation of intermolecular hydrogen bonds, improves the crosslinking degree and crosslink density of the modified POE layer in the packaging material, improves the water vapor barrier and ion barrier properties of the modified POE film layer, and improves the glue The anti-PID performance of the membrane.
  • the surface resistance of EVA or other polar materials in the surface layer is low, and the ability to collect the charges on the back of the battery is higher.
  • the collected charges can be absorbed by the modified POE layer to further improve Anti-PID performance of co-extrusion film.
  • the modified group in the grafted branch can improve the polarity of the modified POE layer, and has good compatibility with the ethylene-vinyl acetate copolymer, and the above-mentioned polar group can be used in the lamination process. It has good thermal stability, so the introduction of the above-mentioned polar groups can improve the bonding performance of the modified POE layer and the EVA layer, and avoid the appearance of the lamination interface during lamination.
  • the existing polyolefin film and the ethylene-vinyl acetate copolymer layer (EVA layer) have poor bonding performance, and at the same time there is a problem of PID.
  • the present application provides an adhesive film, the adhesive film includes: at least one modified polyolefin resin layer (modified POE layer), the resin forming the modified polyolefin resin layer includes 1-100%
  • the modified polyolefin resin, wherein the main chain in the modified polyolefin resin is an ethylene- ⁇ olefin copolymer, and the grafted branches contain acid anhydride groups, hydroxyl groups, ester groups, carbonyl groups, amide groups, pyridyl groups, and epoxy groups.
  • the above-mentioned groups are easy to graft with ethylene- ⁇ -olefin copolymers, and all of the above-mentioned groups contain heteroatoms. Therefore, the introduction of the above-mentioned polar groups is conducive to the formation of intermolecular hydrogen bonds and improves the polymerization of the packaging material.
  • the degree of crosslinking and crosslinking density of the olefin layer can destroy the regularity of the polyolefin layer segments, inhibit the crystallization of the segments, reduce the size of the crystal nucleus, and make the crystal grain size smaller than the wavelength of visible light, thereby improving the light transmittance of the adhesive film.
  • the above several groups can improve the polarity of the modified POE layer, because the above polar groups have better thermal stability during the lamination process, and have better compatibility with the ethylene-vinyl acetate copolymer Therefore, the introduction of the above-mentioned polar groups can improve the bonding performance of the modified POE layer and the EVA layer.
  • the surface resistance of EVA or other polar materials in the co-extruded film formed is low, and the ability to collect the charges on the back of the battery is higher. The collected charges can be absorbed by the modified POE layer, so the co-extrusion film has excellent properties. Anti-PID performance.
  • the grafted branch is an amide group-containing compound with a molecular weight of 1000-5000 g/mol.
  • the grafting rate of the grafted branch is 0.5-15%.
  • the grafting rate of the above-mentioned large molecular weight polar group includes but is not limited to the above range, and limiting it to the above range is beneficial to further improve the compatibility of the large molecular weight polar group with the ethylene-vinyl acetate copolymer. So as to further improve the bonding performance of the modified POE layer and the EVA layer.
  • the amide group-containing compound with a molecular weight of 1000 ⁇ 5000g/mol has good thermal stability during the lamination process, so it will not form bubbles during the lamination process, so it is used as a graft branch to form a modified POE When layering, it can avoid affecting the appearance of the component, and will not affect the bonding force of the packaging material and the component due to the generation of air bubbles.
  • the above-mentioned amide-modified POE has better absorption capacity for additives, so compared to other polar group-modified POE materials, the amide-modified POE has better overall performance.
  • the amide group is formed by removing a hydrogen atom connected to a carbon atom from the organic compound represented by formula (I),
  • R 1 is H, group A, a substituent formed by the substitution of at least one hydrogen atom in the aforementioned group A with a hydroxyl group or an epoxy group, or a substituent formed by the substitution of at least one methylene group in the aforementioned group A with a carbonyl group
  • the group A is a straight chain alkyl group, a branched chain alkyl group or a cycloalkyl group, and the number of carbon atoms of the group A is ⁇ 10
  • R 2 is an alkenyl group with 2 to 20 carbon atoms.
  • the organic compound represented by formula (I) removes a hydrogen atom connected to a carbon atom to form an amide group which has a polymerizable group and an alkenyl group with carbon atoms of 2-20, which can cause the modified POE layer to undergo cross-linking polymerization during the lamination process Therefore, the degree of cross-linking of the modified POE layer can be increased, and the combination of the modified POE layer and the EVA layer can be tighter, and the degree of viscosity can be higher.
  • R 2 includes, but is not limited to, vinyl, propenyl, butadienyl, butenyl, pentenyl, pentadienyl, hexenyl, and hexadienyl. Alkenyl, heptenyl, octenyl, decaenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, or octadecenyl.
  • the vinyl monomer containing an amide group is acrylamide, methacrylamide, N-methacrylamide, N-ethylacrylamide, N-isopropyl propylene Amido, N-tert-butylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-(2-hydroxypropyl)acrylamide, N,N'-methylene Bisacrylamide group, maleimide group, oleic acid amide, 9-hexadecenamide group, N-(2-hydroxyethyl)-undec-10-enamide group, 9-tetradecenyl Carbenamide, 9-dodecenamide, 9-decenamide, octenamide, heptenamide, hexenamide, pentenamide, or crotonamide.
  • ethylene- ⁇ olefin copolymer has better water vapor barrier properties, higher insulation properties and higher light transmittance. Therefore, the selection of it as a thermoplastic polymer resin is beneficial to further improve the water vapor barrier of the film. Performance, insulation and light transmittance.
  • the ⁇ -olefin forming the ethylene- ⁇ -olefin copolymer is a copolymer of ethylene and at least one ⁇ -olefin having less than 10 carbon atoms.
  • the alpha olefin forming the ethylene-alpha olefin copolymer is selected from the group consisting of propylene, 1-butene, 1-hexene, 1-pentene, 1-octene and 4-methyl-1-pentene One or more of. More preferably, it is 1-butene and/or 1-octene.
  • the density of the ethylene- ⁇ olefin copolymer is 0.86 to 0.89 g/cm 3 , preferably 0.87 to 0.88 g/cm 3 . If the density of the copolymer is too high, it may affect the light transmittance of the film; if the density is too low, it may make the thermoplastic polymer resin sticky and affect the processing performance.
  • the melt index of the ethylene- ⁇ olefin copolymer and ethylene homopolymer is 1-40 g/10 min, preferably 3-30 g/10 min, more preferably 5-25 g/10 min.
  • melt index of the thermoplastic polymer resin is too low, it will be difficult to form the film, and it will also reduce the wettability with glass and other substrates, thereby reducing the adhesion; if the melt index is too high, the packaging film will be in the production process It is easy to adhere to the film or embossing roller.
  • the polymer has high fluidity after melting, which causes the phenomenon of edge overflow. Limiting the melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer within the above range is beneficial to improve the moldability of the adhesive film, the adhesion to the substrate, and the aesthetics of the adhesive film product.
  • the ratio of the thickness of the adjacent modified POE layer to the EVA layer is 1: (1 to 3).
  • the raw materials for forming the modified polyolefin resin layer and the ethylene-vinyl acetate copolymer layer also include a crosslinking agent, a crosslinking aid, an antioxidant, One or more of the group consisting of ultraviolet absorbers, light stabilizers, tackifiers, anti-corrosion agents, and pigments.
  • the raw materials for forming the modified polyolefin resin layer and the ethylene-vinyl acetate copolymer layer further include 0.01 to 3 parts by weight Parts of crosslinking agent, 0.01-10 parts by weight of auxiliary crosslinking agent, 0-0.4 parts by weight of ultraviolet light absorber, 0-0.5 parts by weight of antioxidant, 0-1.0 parts by weight of light stabilizer, 0- 3.0 parts by weight of tackifier.
  • the crosslinking agent is a molecule with multiple ethylenically unsaturated groups, which can promote the crosslinking of the polymer to achieve a higher degree of crosslinking.
  • the cross-linking agent in the above composition can be selected from the types commonly used in the art.
  • the cross-linking agent includes but not limited to tert-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-(di-tert Butylperoxy)hexane, tert-butylperoxycarbonate-2-ethylhexyl ester, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1, 1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy) Oxygen) cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-amyl peroxide 2-ethylhexyl carbonate, 2,5-dimethyl 2,5-dimethyl 2,5 -Dimethyl 2,5-bis(benzoylperoxy)
  • the co-crosslinking agent includes but is not limited to triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethyl Oxidized glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane Tetramethacrylate, propoxylated pentaerythritol tetraacryl
  • Antioxidants are used to improve the stability of the polymer extrusion process and the long-term use process, and delay the degradation due to the action of hot oxygen.
  • the antioxidant is a hindered phenol compound and/or a phosphite compound. Compared with other antioxidants, the above-mentioned antioxidants have better stability and antioxidant properties.
  • hindered phenol compounds include but are not limited to 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylene-bis-(4-methyl-6-tert-butyl Phenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-butylene-bis-(3-methyl-6-tert-butylphenol) ), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyl Phenyl) propionate), 7-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate, tetra-(methylene-3- (3',5'-di-tert-butyl
  • Ultraviolet absorber refers to a substance that can absorb most of the ultraviolet energy and convert it into heat, thereby protecting certain electronic devices from being damaged by ultraviolet rays.
  • the above-mentioned ultraviolet light absorbers include but are not limited to benzophenones and/or benzotriazoles. More preferably, the ultraviolet light absorbers include but are not limited to 2-hydroxy-4 -N-octyloxybenzophenone, 2,2-tetramethylenebis(3,1-benzoxazin-4-one), 2-(2'-hydroxy-5-methylphenyl)benzene One or more of the group consisting of triazole and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
  • Light stabilizers are used to improve the stability of the packaging film under long-term ultraviolet radiation.
  • the light stabilizer is a hindered amine compound.
  • light stabilizers include but are not limited to bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2) ,2,6,6-Tetramethyl-4-piperidinyl) sebacate, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine and ⁇ -ene Graft copolymer obtained by polymerization of similar monomers, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecanoic acid Alkyl ester, Sebacic acid bis-2,2,6,6-tetramethylpiperidinol and tris(1,2,2,6,6-pentamethyl-4-piperidinyl) pho
  • the adhesion promoter includes but is not limited to ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(2,3-cyclic (Oxypropyloxy) propyltrimethoxysilane, vinyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethylsilane , One or more of the group consisting of 3-aminopropyltrimethylsilane.
  • the above-mentioned adhesive film further includes at least one ethylene-vinyl acetate copolymer layer (EVA layer), and adjacent layers are not ethylene-vinyl acetate copolymer layers at the same time.
  • EVA layer ethylene-vinyl acetate copolymer layer
  • Ethylene- ⁇ olefin copolymer has excellent water vapor barrier properties, higher insulation properties, higher light transmittance, and low cost. Therefore, the modified POE layer and EVA layer with the above-mentioned main chain and grafted branches are selected to form When the adhesive film is used, the layers have good bonding performance, there is no lamination interface, and the adhesive film also has the advantages of excellent water vapor barrier performance, good insulation performance, high light transmission and low cost.
  • anti-corrosion agent can improve the corrosion resistance of the film.
  • the anti-corrosion agent refers to a substance that can absorb free acid in the film, including but not limited to metal oxides, metal hydroxides, and metal carbonates.
  • Corrosion inhibitors include, but are not limited to, magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, magnesium carbonate, calcium carbonate, zinc carbonate, One or more of the group consisting of barium carbonate and hydrotalcite.
  • the pigment includes, but is not limited to, one or more of the following materials mixed in any proportion: calcium carbonate, barium sulfate, talc, titanium dioxide, zinc oxide, carbon black, graphite Alkene, graphene oxide, copper chrome black, magnesium hydroxide, aluminum hydroxide, aluminum oxide, magnesium oxide, boron nitride, silicon carbide, ammonium phosphate, ammonium polyphosphate, pentaerythritol, dipentaerythritol, polypentaerythritol ester, polyphosphate melamine One or more of the group consisting of borates.
  • Another aspect of the present invention also provides a preferred method for preparing an adhesive film, which includes mixing the materials forming the modified POE layer and the EVA layer separately, and then adding them to different extruders; extruding the modified POE layer
  • the extruded materials of the material and EVA layer are respectively melted and plasticized and injected into the same die, merged in the T die to form a melt stream, and undergoes processes such as melt extrusion, casting to film, cooling, slitting, and winding.
  • an electronic device including an encapsulating adhesive film, and the encapsulating adhesive film includes the above-mentioned adhesive film provided in the present application.
  • the adhesive film prepared by the preparation method provided in this application has good bonding performance between the layers, there is no lamination interface, and the adhesive film also has excellent water vapor barrier performance and high insulation performance, Anti-PID performance, and high light transmittance. Therefore, using the above-mentioned adhesive film as an encapsulating adhesive film is beneficial to the power generation of electronic devices and increases their service life.
  • Modified polyolefin layer In parts by weight, 99 parts of ethylene-hexene copolymer, 1 part of ethylene-hexene copolymer grafted with polyacrylamide (the molecular weight of the grafted branch is 150g/mol, the grafting rate is 10wt% , The density is 0.875g/cm 3 , the melt index is 25g/10min), 0.5 parts of crosslinking agent tert-butylperoxy isopropyl carbonate and 0.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate are added.
  • Ethylene-vinyl acetate copolymer layer In parts by weight, take 100 parts of ethylene-vinyl acetate (VA content 28%, DuPont, USA), and add 0.5 parts of crosslinking agent tert-butylperoxycarbonate-2-ethyl Hexyl ester, 0.5 parts of co-crosslinking agent trimethylolpropane triacrylate.
  • the double-layer composite photovoltaic encapsulation film EVA-POE is prepared by the processes of extraction, casting, film formation, cooling, slitting, and winding, which is marked as E1.
  • the thickness of the modified polyolefin layer of the encapsulation film calculated by the distributor is 0.2mm.
  • the thickness of the ethylene-vinyl acetate copolymer layer is 0.3 mm.
  • Modified polyolefin layer In parts by weight, take 90 parts of ethylene-octene copolymer and 10 parts of ethylene-octene copolymer grafted with 9-hexadecenamide group (grafted branched chain molecular weight 5000g/ mol, the grafting rate is 0.5wt%, the density is 0.862g/cm 3 , the melt index is 15g/10min), 1.5 parts of crosslinking agent 1,1-bis(tert-butylperoxy)-3,3,5- Trimethylcyclohexane, 3 parts of co-crosslinking agent ethoxylated trimethylolpropane triacrylate.
  • Ethylene-vinyl acetate copolymer layer In parts by weight, take 100 parts of ethylene-vinyl acetate (VA content 24%, DuPont, USA), and add 1 part of crosslinking agent tert-butylperoxycarbonate-2-ethyl Hexyl ester, 2 parts of co-crosslinking agent tris(2-hydroxyethyl)isocyanurate triacrylate.
  • the extruded material of the modified polyolefin layer and the extruded material of the ethylene-vinyl acetate copolymer layer are respectively melted and plasticized and then injected into the same die, merged in the T die to form a melt stream, and undergoes melt extrusion.
  • the three-layer composite photovoltaic encapsulation film EVA-POE-EVA with the outer layer of EVA and the middle layer of POE is prepared by the processes of extraction, casting, film forming, cooling, slitting and winding, etc.
  • the thickness of the modified polyolefin layer is 0.2 mm, and the thickness of the ethylene-vinyl acetate copolymer layer is 0.15 mm.
  • Modified polyolefin layer In parts by weight, take 100 parts of ethylene-butene copolymer grafted with poly-N-methylolacrylamide (the molecular weight of the grafted branch is 1000g/mol, the grafting rate is 5wt%, and the density is 0.870 g/cm 3 , the melt index is 20g/10min), add 2 parts of crosslinking agent 1,1-bis(tert-amylperoxy)cyclohexane, 0.02 parts of auxiliary crosslinking agent trimethylolpropane triacrylate, 1.0 part of co-crosslinking agent ethoxylated glycerol triacrylate 0.8 part of tackifier vinyl triperoxide tert-butyl silane, 0.8 part of light stabilizer sebacic acid bis-2,2,6,6-tetramethylpiperidine alcohol.
  • Ethylene-vinyl acetate copolymer layer In parts by weight, take 100 parts of ethylene-vinyl acetate (VA content 28%, DuPont, USA), and add 2 parts of crosslinking agent tert-butylperoxycarbonate-2-ethyl Hexyl ester, 1 part of co-crosslinking agent diethylene glycol dimethacrylate, 0.8 part of light stabilizer tris(1,2,2,6,6-pentamethyl-4-piperidinyl) phosphite.
  • the double-layer composite photovoltaic encapsulation film EVA-POE is prepared by the processes of extraction, casting, film formation, cooling, slitting, and winding, which is marked as E3.
  • the thickness of the modified polyolefin layer of the encapsulation film calculated by the distributor is 0.2mm.
  • the thickness of the ethylene-vinyl acetate copolymer layer is 0.25 mm.
  • the modified polyolefin layer is ethylene-butene copolymer grafted with polyN,N'-methylenebisacrylamide (the molecular weight of the grafted branch is 2000g/mol, and the grafting rate is 1.5wt% , The density is 0.880g/cm 3 , the melt index is 18g/10min).
  • Example 3 The difference from Example 3 is that the modified polyolefin layer is ethylene-butene copolymer grafted with poly N-(2-hydroxyethyl)-undec-10-enamide group (grafted branched chain molecular weight 8000g/ mol, graft ratio 1.0wt%, a density of 0.873g / cm 3, a melt index of 3g / 10min).
  • poly N-(2-hydroxyethyl)-undec-10-enamide group grafted branched chain molecular weight 8000g/ mol, graft ratio 1.0wt%, a density of 0.873g / cm 3, a melt index of 3g / 10min.
  • the modified polyolefin layer is ethylene-butene copolymer grafted with poly-N-ethylacrylamide (the molecular weight of the grafted branch is 500g/mol, the grafting rate is 15wt%, and the density is 0.862g /cm 3 , the melt index is 15g/10min).
  • the modified polyolefin layer is ethylene-butene copolymer grafted polyhydrolyzed polymaleic anhydride (the molecular weight of the grafted branch is 2300g/mol, the grafting rate is 1.5wt%, and the density is 0.875g/ cm 3 , the melt index is 20g/10min).
  • the modified polyolefin layer is ethylene-butene copolymer grafted polyhydrolyzed poly(4-vinylpyridine) (branched molecular weight 300g/mol, grafting rate 10wt%, density 0.865g /cm 3 , the melt index is 25g/10min.).
  • the modified polyolefin layer is ethylene-butene copolymer grafted polyhydrolyzed poly(N-vinyl-2-pyrrolidone) (branched molecular weight 330g/mol, grafting rate 5wt%, density It is 0.870g/cm 3 and the melt index is 24g/10min).
  • the modified polyolefin layer is ethylene-butene copolymer grafted polyhydrolyzed polyglycidyl cage polysilsesquioxane (branched molecular weight 1300g/mol, grafting rate 2.5wt% , The density is 0.873g/cm 3 , the melt index is 19g/10min).
  • the modified polyolefin layer is an ethylene-butene copolymer grafted poly N-methylol acrylamide (branched molecular weight 1000g/mol, grafting rate 0.1wt%, density 0.869g/ cm 3 , the melt index is 19g/10min).
  • the modified polyolefin layer is ethylene-butene copolymer grafted poly N-methylol acrylamide (branched molecular weight 1000g/mol, grafting rate 18wt%, density 0.870g/cm 3 , the melt index is 21g/10min).
  • the grafted branch is an ethylene-butene copolymer containing both epoxy and amide groups (the molecular weight of the branch is 1000g/mol, the grafting rate is 15wt%, and the density is 0.875g/cm 3 , (The melt index is 21g/10min)
  • the grafted branch is ethylene-hexene copolymer grafted with polyacrylamide, the molecular weight of the grafted branch is 1000g/mol, the grafting rate is 5wt%, the density is 0.875g/cm 3 , and the melt index It is 15g/10min.
  • Example 3 The difference from Example 3 is: the molecular weight of the grafted branch is 200 g/mol, the grafting rate is 15%, the density is 0.875 g/cm 3 , and the melt index is 15 g/10 min.
  • the molecular weight of the grafted branch is 5000 g/mol
  • the grafting rate is 0.5%
  • the density is 0.875 g/cm 3
  • the melt index is 10 g/10 min.
  • Modified polyolefin layer single-layer film In parts by weight, take 100 parts of ethylene-butene copolymer grafted with poly-N-methylolacrylamide (grafted branched chain molecular weight 1000g /mol, the grafting rate is 5wt%, the density is 0.870g/cm3, the melt index is 20g/10min), 2 parts of crosslinking agent 1,1-bis(tert-amylperoxy)cyclohexane are added, and 0.02 parts are used to assist cross-linking Linking agent trimethylolpropane triacrylate, 1.0 part of co-crosslinking agent ethoxylated glycerol triacrylate 0.8 part of tackifier vinyl triperoxide tert-butyl silane, 0.8 part of light stabilizer sebacic acid bis-2, 2,6,6-Tetramethylpiperidinol.
  • the mixture is uniformly mixed, and the above-mentioned mixture is pre-mixed, melt-extrusion, film-forming, cooling, slitting, and winding, etc., to prepare the single-layer modified polyolefin layer adhesive film packaging material.
  • Example 17 The difference from Example 17 is that the modified polyolefin layer is ethylene-butene copolymer grafted with polyN,N'-methylenebisacrylamide (the molecular weight of the grafted branch is 2000g/mol, and the grafting rate is 1.5wt% , The density is 0.880g/cm 3 , the melt index is 18g/10min).
  • the modified polyolefin layer is ethylene-butene copolymer grafted with poly N-(2-hydroxyethyl)-undec-10-enamide group (grafted branched chain molecular weight 8000g/ mol, graft ratio 1.0wt%, a density of 0.873g / cm 3, a melt index of 3g / 10min).
  • the modified polyolefin layer is an ethylene-butene copolymer grafted polyhydrolyzed polymaleic anhydride (the molecular weight of the grafted branch is 2300g/mol, the grafting rate is 1.5wt%, and the density is 0.875g/ cm 3 , the melt index is 20g/10min).
  • Polyolefin film In parts by weight, take 100 parts of ethylene-hexene copolymer (density 0.870g/cm 3 , melt index 25g/10min), add 3 parts acrylamide, 0.5 parts crosslinking agent tert-butyl Based on isopropyl peroxycarbonate, 0.5 parts of auxiliary crosslinking agent trimethylolpropane trimethacrylate.
  • the modified polyolefin layer is ethylene-hexene copolymer grafted with acrylamide (branched molecular weight 71g/mol, grafting rate 10wt%)
  • the modified polyolefin layer is ethylene-hexene copolymer grafted polyacrylamide (branched molecular weight 10000g/mol, grafting rate 10wt%)
  • Examples 1 to 20 and Comparative Examples 1 to 3 were tested for adhesion and degree of crosslinking, and the lamination characteristics of the components were compared.
  • the glass/adhesive film (two layers)/flexible backplane of 300mm ⁇ 150mm was stacked in sequence and placed in a vacuum laminator, followed by a lamination process at 150°C for 18 minutes to produce a laminate.
  • Test using xylene heating extraction method The ratio of the mass that has not been dissolved in xylene to the initial mass is the degree of crosslinking. Take the arithmetic average of three samples and express it as a percentage.
  • the specification of the module is 60 pieces ( 6 ⁇ 10) The format of the cell.
  • 100 modules were made for appearance evaluation. The evaluation criteria are based on the occurrence of bubbles, impurities, and delamination between the glue film and the cell or glass, as follows:
  • the double-sided battery was selected and tested in accordance with IECTS 2804-1:2015.
  • the test conditions were tightened to 85°C, 85% RH, and a constant negative 1500V DC voltage was applied. After 192h, the power attenuation before and after the PID test of the photovoltaic module was measured.

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Abstract

本发明提供了一种胶膜及包含其的电子器件。该胶膜包括至少一个改性聚烯烃树脂层，形成改性聚烯烃树脂层的树脂包括1～100％的改性聚烯烃树脂，改性聚烯烃树脂中的主链为乙烯-α烯烃共聚物，接枝支链选自包含酸酐基、羟基、酯基、羰基、酰胺基、吡啶基、环氧基、吡咯烷酮基和缩水甘油基中的一种或多种的乙烯基单体所形成的化合物，接枝支链的分子量为150～8000g/mol。选用具有上述主链和接枝支链的改性POE层制得的胶膜具有优异的抗PID性能；改性POE层与EVA层形成共挤胶膜时，各层之间具有较好的粘结性能，不存在层压界面，且共挤胶膜还具有优异的水汽阻隔性能，较高的绝缘性能和较高的透光性。

Description

胶膜及包含其的电子器件 技术领域
本发明涉及光电转化器件领域，具体而言，涉及一种胶膜及包含其的电子器件。
背景技术
光电转化是指通过光伏效应将太阳能转化为电能。常用的能够实现上述光电转化过程的电子器件(光电转化器件)包括但不限于太阳能电池(如晶硅电池、非晶硅电池、碲化镉电池、铜铟镓锡电池、钙钛矿电池)、液晶面板、场致发光器件、等离子显示器件、传感器等，通常经过一层或多层聚合物材料的密封，该密封材料再和上下两个基板相粘接从而形成一个完整电子器件模块。例如晶硅太阳能电池组件，通常是按照前层玻璃基板、前密封层聚合物、晶硅电池、后密封层聚合物、后层玻璃基板或聚合物基板层叠好后，通过真空层压机加热加压后形成一个完整的太阳能组件。
聚合物密封材料通常需要满足以下条件：Ⅰ)粘接性。聚合物密封材料在受热融化后通过化学作用和电子器件以及基板进行粘接，并通常期望在长期的使用过程中，密封材料和电子器件以及和基板之间不会发生分层。Ⅱ)柔软性。具有较低的弹性模量，保护电子器件以免受到外力冲击而损坏；Ⅲ)透明性。例如太阳能电池，需要密封材料具有高的透光率，从而最大化的利用太阳光，提高发电效率。Ⅳ)绝缘性。通常该聚合物密封材需要较高的体积电阻率，从而避免产生较大漏电流。Ⅴ)化学稳定性。太阳能组件在长期户外使用时所经受高温、高湿气、紫外光辐射等，密封材料不应该发生严重的劣化，从而造成黄变，机械性能下降，释放腐蚀性化合物等。Ⅵ)耐热性。太阳能组件在户外经受长期高温作用，密封材料不应该发生流动或蠕变，因此密封材料通常需要进行交联处理。
目前，常用的光电转化器件的封装材料为乙烯-乙酸乙烯酯和聚烯烃，乙烯-乙酸乙烯酯在光伏组件使用过程中会产生醋酸，引起电子器件腐蚀或PID(潜在电势诱导衰减)的问题。聚烯烃水汽阻隔性和气密性都优于乙烯-醋酸乙烯酯共聚物，但聚烯烃成本较高，可以将二者一起使用。在兼顾性能的同时降低成本，但二者同时使用时胶膜的粘结性显著降低。现有文献中有在胶膜聚合过程中直接加入小分子酰胺类化合物，但在层压过程中容易在胶膜表面产生气泡，影响组件的外观，降低封装材料的交联度，导致封装材料与组件的粘结力降低，进一步降低发电功率，难以达到光伏组件25年的使用寿命。
因此，有必要提供一种新的电子器件用封装材料，以提高改性聚烯烃胶膜，或改性聚烯烃胶膜与乙烯-醋酸乙烯酯共聚物共挤胶膜的粘结性和抗PID性能。
发明内容
本发明的主要目的在于提供一种胶膜及包含其的电子器件，以解决现有的聚烯烃膜与乙烯-醋酸乙烯酯共聚物层之间的粘结性能较差和PID的技术问题。
为了实现上述目的，根据本发明的一个方面，提供了一种胶膜，该胶膜包括：至少一个改性聚烯烃树脂层，形成该改性聚烯烃树脂层的树脂包括1～100％的改性聚烯烃树脂，改性聚烯烃树脂中的主链为乙烯-α烯烃共聚物，接枝支链选自包含酸酐基、羟基、酯基、羰基、酰胺基、吡啶基、环氧基、吡咯烷酮基和缩水甘油基中的一种或多种的乙烯基单体所形成的化合物，接枝支链的分子量为150～8000g/mol；且相邻层不同时为乙烯-醋酸乙烯酯共聚物层。
进一步地，接枝支链为分子量为1000～5000g/mol的含酰胺基的化合物；改性聚烯烃树脂中，接枝支链的接枝率为0.5～15％。
进一步地，接枝支链由式(Ⅰ)所示包含酰胺基的乙烯基单体形成的化合物与主链通过自由基接枝反应形成，
Figure PCTCN2020109634-appb-000001
其中，R 1为H、基团A、基团A中至少一个氢原子被羟基或环氧基取代形成的取代基，或基团A中至少一个亚甲基被羰基取代形成的取代基，基团A为直链烷基、支链烷基或环烷基，且第一取代基的碳原子数≤10，R 2为碳原子数为2～20的烯基。
进一步地，R 2选自乙烯基、丙烯基、丁二烯基、丁烯基、戊烯基、戊二烯基、己烯基、己二烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。
进一步地，包含酰胺基的乙烯基单体选自丙烯酰胺基、甲基丙烯酰胺基、N-甲基丙烯酰胺基、N-乙基丙烯酰胺基、N-异丙基丙烯酰胺基、N-叔丁基丙烯酰胺基、N-羟甲基丙烯酰胺基、N-羟乙基丙烯酰胺基、N-(2-羟基丙基)丙烯酰胺基、N,N’-亚甲基双丙烯酰胺基、马来酰亚胺基、油酸酰胺、9-十六碳烯酰胺基、N-(2-羟基乙基)-十一碳-10-烯酰胺基、9-十四碳烯酰胺基、9-十二碳烯酰胺基、9-十碳烯酰胺基、辛烯酰胺基、庚烯酰胺基、己烯酰胺基、戊烯酰胺基和丁烯酰胺基组成的组中的一种或多种。
进一步地，乙烯-α烯烃共聚物为乙烯与至少一种碳原子数≤10的α-烯烃的共聚物。
进一步地，碳原子数≤10的α-烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种。
进一步地，乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3，乙烯-α烯烃共聚物的熔融指数为1～40g/10min。
进一步地，乙烯-α烯烃共聚物的密度为0.87～0.88g/cm 3，乙烯-α烯烃共聚物的熔融指数为3～30g/10min。
进一步地，上述胶膜还包括至少一个乙烯-醋酸乙烯酯共聚物层，相邻层不同时为乙烯-醋酸乙烯酯共聚物层。
进一步地，相邻的改性聚烯烃树脂层与乙烯-醋酸乙烯酯共聚物层的厚度之比为1:(1～3)。
进一步地，形成改性聚烯烃树脂层和乙烯-醋酸乙烯酯共聚物层的原料还包括交联剂、助交联剂、抗氧剂、紫外线吸收剂、光稳定剂、增粘剂、抗腐蚀剂、颜料中的一种或多种。
本申请的另一方面提供了一种电子器件，包括封装胶膜，该封装胶膜包括上述胶膜。
应用本发明的技术方案，具有以下优异的技术效果：
(1)接枝支链中的改性基团容易与乙烯-α烯烃共聚物进行接枝，且上述几种基团中均含有杂原子，因而引入上述极性基团，尤其是强极性的酰胺基团，有利于形成分子间氢键，提高封装材料中改性POE层的交联度和交联密度，提高了改性POE胶膜层的水汽阻隔性和离子阻隔性，提高了胶膜的抗PID性能。
(2)上述胶膜形成的共挤胶膜中，表面层的EVA或其他极性材料表面电阻低，收集电池片背面电荷能力更高，收集好的电荷可以被改性POE层吸附，进一步提高共挤胶膜的抗PID性能。
(3)接枝支链中的改性基团能够提高改性POE层的极性，且与乙烯-醋酸乙烯酯共聚物具有较好的相容性，并且上述极性基团在层压过程中具有较好的热稳定性，因而上述极性基团的引入能够提高改性POE层与EVA层粘结性能，避免层压时出现层压界面。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的聚烯烃膜与乙烯-醋酸乙烯酯共聚物层(EVA层)之间的粘结性能较差，同时存在PID的问题。为了解决上述技术问题，本申请提供了一种胶膜，该胶膜包括：至少一个改性聚烯烃树脂层(改性POE层)，形成该改性聚烯烃树脂层的树脂包括1～100％的改性聚烯烃树脂，其中，改性聚烯烃树脂中的主链为乙烯-α烯烃共聚物，接枝支链为包含酸酐基、羟基、酯基、羰基、酰胺基、吡啶基、环氧基、吡咯烷酮基和缩水甘油基中的一种或多种的乙烯基单体所形成的化合物，接枝支链的分子量为150～8000g/mol。
上述几种基团容易与乙烯-α烯烃共聚物进行接枝，且上述几种基团中均含有杂原子，因而引入上述极性基团有利于形成分子间氢键，并提高封装材料中聚烯烃层的交联度和交联密度。交联反应的发生可以破坏聚烯烃层链段的规整性，抑制链段结晶，减小晶核尺寸，使晶 粒粒径小于可见光波长，从而能够提高胶膜的透光率。同时上述几种基团能够提高改性POE层的极性，由于上述极性基团在层压过程中具有较好的热稳定性，且与乙烯-醋酸乙烯酯共聚物具有较好的相容性，因而上述极性基团的引入能够提高改性POE层与EVA层等的粘结性能。其形成的共挤胶膜中表面层的EVA或其他极性材料表面电阻低，收集电池片背面电荷能力更高，收集好的电荷可以被改性POE层吸附，因而共挤胶膜具有优异的抗PID性能。
为了进一步提高改性POE层的极性，同时进一步提高其与EVA层之间的粘结性能，优选地，接枝支链为分子量为1000～5000g/mol的含酰胺基的化合物。
在一种优选的实施例中，改性聚烯烃树脂中，接枝支链的接枝率为0.5～15％。上述大分子量的极性基团的接枝率包括但不限于上述范围，而将其限定在上述范围内有利于进一步提高大分子量极性基团与乙烯-醋酸乙烯酯共聚物的相容性，从而进一步提高改性POE层与EVA层的粘结性能。
分子量为1000～5000g/mol的含酰胺基的化合物在层压过程中具有较好的热稳定性，因而其不会在层压过程中形成气泡，因而采用其作为接枝支链形成改性POE层时，可以避免影响组件的外观，也不会因气泡的产生影响封装材料与组件的粘结力。同时上述酰胺基改性的POE对助剂具有较好的吸收能力，因而相比于其它极性基团改性的POE材料，酰胺基改性的POE具有更好的综合性能。在一种优选的实施例中，酰胺基由式(Ⅰ)所示有机物去掉一个与碳原子相连的氢原子形成，
Figure PCTCN2020109634-appb-000002
其中R 1为H、基团A、上述基团A中至少一个氢原子被羟基或环氧基取代形成的取代基，或上述基团A中至少一个亚甲基被羰基取代形成的取代基，基团A为直链烷基、支链烷基或环烷基，且基团A的碳原子数≤10，R 2为碳原子数为2～20的烯基。
式(Ⅰ)所示有机物去掉一个与碳原子相连的氢原子形成的酰胺基具有可聚合基团碳原子数为2～20的烯基，层压过程中能够使改性POE层发生交联聚合，从而能够提高改性POE层的交联度，并使其与EVA层结合的更加紧密，粘度程度也更高。为了进一步提高改性POE交联密度，更优选地，R 2包括但不限于乙烯基、丙烯基、丁二烯基、丁烯基、戊烯基、戊二烯基、己烯基、己二烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。
在一种优选的实施例中，包含酰胺基的乙烯基单体为丙烯酰胺基、甲基丙烯酰胺基、N-甲基丙烯酰胺基、N-乙基丙烯酰胺基、N-异丙基丙烯酰胺基、N-叔丁基丙烯酰胺基、N-羟甲基丙烯酰胺基、N-羟乙基丙烯酰胺基、N-(2-羟基丙基)丙烯酰胺基、N,N’-亚甲基双丙烯酰胺基、马来酰亚胺基、油酸酰胺、9-十六碳烯酰胺基、N-(2-羟基乙基)-十一碳-10-烯酰胺基、9- 十四碳烯酰胺基、9-十二碳烯酰胺基、9-十碳烯酰胺基、辛烯酰胺基、庚烯酰胺基、己烯酰胺基、戊烯酰胺基或丁烯酰胺基。
相比于其它聚合物，乙烯-α烯烃共聚物具有更优异的水汽阻隔性能，较高的绝缘性能和较高的透光性，因而选用其作为热塑性聚合树脂有利于进一步提高胶膜的水汽阻隔性能、绝缘性和透光率。在一种优选的实施例中，形成乙烯-α烯烃共聚物的α烯烃为乙烯与至少一种碳原子数小于10的α-烯烃的共聚物。更优选地，形成乙烯-α烯烃共聚物的α烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种。进一步优选为1-丁烯和/或1-辛烯。
在一种优选的实施例中，乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3，优选为0.87～0.88g/cm 3。若共聚物的密度过高，则有可能影响胶膜的透光率；若密度过低，则有可能使热塑性聚合树脂发粘，影响加工性能。在一种优选的实施例中，乙烯-α烯烃共聚物和乙烯均聚物的熔融指数为1～40g/10min，优选为3～30g/10min，更优选为5～25g/10min。若热塑性聚合树脂的熔融指数过低则会造成胶膜成型困难，也会造成和玻璃等基材的浸润性降低，从而使粘接力降低；若熔融指数过高，封装胶膜在生产过程中容易和胶膜或压花辊粘连，另外电子器件在压合过程中，聚合物因熔融后流动性高而产生边缘溢胶的现象。将乙烯-α烯烃共聚物和乙烯均聚物的熔融指数限定在上述范围，有利于提高胶膜的成型性、与基材的粘合力以及胶膜产品的美观性。
为了进一步提高胶膜的综合性能，优选地，相邻的改性POE层与EVA层的厚度之比为1:(1～3)。
为了提高胶膜的综合性能，在一种优选的实施例中，形成改性聚烯烃树脂层和乙烯-醋酸乙烯酯共聚物层的原料还包括交联剂、助交联剂、抗氧剂、紫外线吸收剂、光稳定剂、增粘剂、抗腐蚀剂、颜料组成的组中的一种或多种。进一步地，相对于100重量份的改性聚烯烃树脂材料或100重量份的光伏封装材料EVA树脂，形成改性聚烯烃树脂层和乙烯-醋酸乙烯酯共聚物层的原料还包括0.01～3重量份的交联剂，0.01～10重量份的助交联剂，0～0.4重量份的紫外光吸收剂，0～0.5重量份的抗氧剂，0～1.0重量份的光稳定剂，0～3.0重量份的增粘剂。
交联剂是具有多个烯属不饱和基团的分子，可以促进聚合物交联，达到更高的交联度。上述组合物中交联剂可以选用本领域常用的种类，优选地，交联剂包括但不限于叔丁基过氧化碳酸异丙酯、2,5-二甲基-2,5-(双叔丁过氧基)己烷、叔丁基过氧化碳酸-2-乙基己酯、1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)环己烷、1,1-双(叔丁基过氧)环己烷、2,2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基2,5-二甲基2,5-二甲基2,5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3,3,5三甲基己酸叔丁酯组成的组中的一种或多种。
在一种优选的实施例中，助交联剂包括但不限于三烯丙基异氰尿酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化甘油三丙烯酸酯、丙氧化甘油三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四甲基丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、2,4,6-三(2-丙烯基氧基)-1,3,5-三嗪、三环葵烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧化双酚A二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯和聚乙二醇二甲基丙烯酸酯组成的组中的一种或多种。
抗氧剂用来提高聚合物挤出加工过程，以及长期使用过程中的稳定性，延缓因为热氧的作用下而发生降解。在一种优选的实施例中，抗氧剂为受阻酚系化合物和/或亚磷酸酯系化合物。相比于其它抗氧剂，上述抗氧剂具有较好的稳定性和抗氧化性能。更优选地，受阻酚系化合物包括但不限于2,6-二-叔丁基-4-乙基苯酚、2,2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基-双-(4-乙基-6-叔丁基苯酚)、4,4’-亚丁基-双-(3-甲基-6-叔丁基苯酚)、十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯、季戊四醇-四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、7-十八烷基-3-(4’-羟基-3’,5’-二-叔丁基苯基)丙酸酯、四-[亚甲基-3-(3’,5’-二-叔丁基-4’-羟基苯基)丙酸酯]甲烷组成的组中的一种或多种；亚磷酸酯系化合物包括但不限于三(2,4-二-叔丁基苯基)亚磷酸酯、双[2,4-双(1,1-二甲基乙基)-6-甲基苯基]乙基酯亚磷酸、四(2,4-二-叔丁基苯基)[1,1-连苯基]-4,4’-二基双亚磷酸酯和双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯组成的组中的一种或多种。
紫外光吸收剂是指能够在吸收大部分的紫外线能量，转换成热量的物质，从而保护某些电子器件不被紫外线所破坏。在一种优选的实施例中，上述紫外光吸收剂包括但不限于二苯甲酮类和/或苯并三唑类物质，更优选地，紫外光吸收剂包括但不限于2-羟基-4-正辛氧基二苯甲酮、2,2-四亚甲基双(3,1-苯并噁嗪-4-酮)、2-(2’-羟基-5-甲基苯基)苯并三唑、2,2’-二羟基-4,4’-二甲氧基二苯甲酮组成的组中的一种或多种。
光稳定剂是用来提高封装胶膜在长期紫外线辐照下的稳定性。优选地，光稳定剂为受阻胺系化合物。在一种优选的实施例中，光稳定剂包括但不限于双(2,2,6,6-四甲基-4-哌啶基)葵二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)葵二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯组成的组中的一种或多种。
增粘剂加入可以提高胶膜的粘剂性能。在一种优选的实施例中，增粘剂包括但不限于γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲基硅烷、3-氨丙基三甲基硅烷组成的组中的一种或多种。
在一种优选的实施例中，上述胶膜还包括至少一个乙烯-醋酸乙烯酯共聚物层(EVA层)，且相邻层不同时为乙烯-醋酸乙烯酯共聚物层。
乙烯-α烯烃共聚物具有优异的水汽阻隔性能，较高的绝缘性能和较高的透光性，且成本低，因而选用具有上述主链和接枝支链的改性POE层与EVA层形成胶膜时，各层之间具有较好的粘结性能，不存在层压界面，且胶膜还具有水汽阻隔性能优异，绝缘性能好和透光性高及成本低等优点。
抗腐蚀剂的加入可以提高胶膜的耐腐蚀性。在一种优选的实施例中，抗腐蚀剂指可以吸收胶膜中游离酸的物质，包括但不限于金属氧化物、金属氢氧化物和金属碳酸化合物。抗腐蚀剂包括但不限于氢氧化镁、氢氧化钙、氢氧化锌、氢氧化钡、氢氧化铝、氧化镁、氧化钙、氧化锌、氧化钡、氧化铝、碳酸镁、碳酸钙、碳酸锌、碳酸钡、水滑石等组成的组中的一种或多种。
颜料的加入可以根据客户需求满足不同的应用场景。在一种优选的实施例中，颜料包括但不限于由以下物质中的一种或多种按照任意配比混合组成：碳酸钙、硫酸钡、滑石粉、钛白粉、氧化锌、炭黑、石墨烯、氧化石墨烯、铜铬黑、氢氧化镁、氢氧化铝、氧化铝、氧化镁、氮化硼、碳化硅、磷酸铵、聚磷酸铵、季戊四醇、双季戊四醇、多季戊四醇酯、聚磷酸三聚氰胺硼酸盐组成的组中的一种或多种。
本发明的另一方面还提供了一种优选的胶膜的制备方法，包括将形成改性POE层与EVA层的材料分别混匀后，加入不同的挤出机；改性POE层的挤出物料、EVA层的挤出物料分别熔融塑化后注入同一模头中，在T模头内合并形成一个熔体流，经过熔融挤出、流延成膜、冷却、分切和收卷等工序制备多层胶膜。
本申请的又一方面还提供了一种电子器件，包括封装胶膜，该封装胶膜包括本申请提供的上述胶膜。
由于采用本申请提供的制备方法制得的胶膜中，各层之间具有较好的粘结性能，不存在层压界面，且胶膜还具有优异的水汽阻隔性能，较高的绝缘性能，抗PID性能，和较高的透光性。因而将上述胶膜作为封装胶膜有利于大大电子器件的发电功率，并提高其使用寿命。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
改性聚烯烃层：以重量份计，取99份乙烯-己烯共聚物，1份的乙烯-己烯共聚物接枝聚丙烯酰胺(接枝支链分子量150g/mol，接枝率10wt％，密度为0.875g/cm 3，熔融指数为25g/10min)，加入0.5份交联剂叔丁基过氧化碳酸异丙酯，0.5份助交联剂三羟甲基丙烷三甲基丙烯酸酯。
乙烯-醋酸乙烯酯共聚物层：以重量份计，取100份的乙烯-乙酸乙烯酯(VA含量28％，美国杜邦)，加入0.5份交联剂叔丁基过氧化碳酸-2-乙基己酯，0.5份助交联剂三羟甲基丙烷三丙烯 酸酯。
将上述改性聚烯烃层与乙烯-醋酸乙烯酯共聚物层的树脂与助剂的组合物混匀后，加入不同的挤出机。所述改性聚烯烃层的挤出物料、乙烯-醋酸乙烯酯共聚物层的挤出物料分别熔融塑化后注入同一模头中，在T模头内合并形成一个熔体流，经过熔融挤出、流延成膜、冷却、分切和收卷等工序制备双层复合光伏封装胶膜EVA-POE，记为E1，通过分配器计算所得封装胶膜改性聚烯烃层厚度为0.2mm，乙烯-醋酸乙烯酯共聚物层厚度0.3mm。
实施例2
改性聚烯烃层：以重量份计，取90份的乙烯-辛烯共聚物，10份的乙烯-辛烯共聚物接枝聚9-十六碳烯酰胺基(接枝支链分子量5000g/mol，接枝率0.5wt％，密度为0.862g/cm 3，熔融指数为15g/10min)，加入1.5份交联剂1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷，3份助交联剂乙氧化三羟甲基丙烷三丙烯酸酯。
乙烯-醋酸乙烯酯共聚物层：以重量份计，取100份的乙烯-乙酸乙烯酯(VA含量24％，美国杜邦)，加入1份交联剂叔丁基过氧化碳酸-2-乙基己酯，2份助交联剂三(2-羟乙基)异氰脲酸三丙烯酸酯。
将上述改性聚烯烃层与乙烯-醋酸乙烯酯共聚物层的树脂与助剂的组合物混匀后，加入不同的挤出机。所述改性聚烯烃层的挤出物料、乙烯-醋酸乙烯酯共聚物层的挤出物料分别熔融塑化后注入同一模头中，在T模头内合并形成一个熔体流，经过熔融挤出、流延成膜、冷却、分切和收卷等工序制备外层EVA中间层为POE的三层复合光伏封装胶膜EVA-POE-EVA，记为E2，通过分配器计算所得封装胶膜改性聚烯烃层厚度为0.2mm，乙烯-醋酸乙烯酯共聚物层厚度0.15mm。
实施例3
改性聚烯烃层：以重量份计，取100份的乙烯-丁烯共聚物接枝聚N-羟甲基丙烯酰胺(接枝支链分子量1000g/mol，接枝率5wt％，密度为0.870g/cm 3，熔融指数为20g/10min)，加入2份交联剂1,1-双(叔戊基过氧)环己烷，0.02份助交联剂三羟甲基丙烷三丙烯酸酯，1.0份助交联剂乙氧化甘油三丙烯酸酯0.8份增粘剂乙烯基三过氧化叔丁基硅烷，0.8份光稳定剂葵二酸双-2,2,6,6-四甲基哌啶醇。
乙烯-醋酸乙烯酯共聚物层：以重量份计，取100份的乙烯-乙酸乙烯酯(VA含量28％，美国杜邦)，加入2份交联剂叔丁基过氧化碳酸-2-乙基己酯，1份助交联剂二乙二醇二甲基丙烯酸酯，0.8份光稳定剂三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯。
将上述改性聚烯烃层与乙烯-醋酸乙烯酯共聚物层的树脂与助剂的组合物混匀后，加入不同的挤出机。所述改性聚烯烃层的挤出物料、乙烯-醋酸乙烯酯共聚物层的挤出物料分别熔融塑化后注入同一模头中，在T模头内合并形成一个熔体流，经过熔融挤出、流延成膜、冷却、 分切和收卷等工序制备双层复合光伏封装胶膜EVA-POE，记为E3，通过分配器计算所得封装胶膜改性聚烯烃层厚度为0.2mm，乙烯-醋酸乙烯酯共聚物层厚度0.25mm。
实施例4
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N,N’-亚甲基双丙烯酰胺(接枝支链分子量2000g/mol，接枝率1.5wt％，密度为0.880g/cm 3，熔融指数为18g/10min)。
实施例5
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N-(2-羟基乙基)-十一碳-10-烯酰胺基(接枝支链分子量8000g/mol，接枝率1.0wt％，密度为0.873g/cm 3，熔融指数为3g/10min)。
实施例6
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N-乙基丙烯酰胺基(接枝支链分子量500g/mol，接枝率15wt％，密度为0.862g/cm 3，熔融指数为15g/10min)。
实施例7
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚水解聚马来酸酐(接枝支链分子量2300g/mol，接枝率1.5wt％，密度为0.875g/cm 3，熔融指数为20g/10min)。
实施例8
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚水解聚(4-乙烯基吡啶)(支链分子量300g/mol，接枝率10wt％，密度为0.865g/cm 3，熔融指数为25g/10min.)。
实施例9
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚水解聚(N-乙烯基-2-吡咯烷酮)(支链分子量330g/mol，接枝率5wt％，密度为0.870g/cm 3，熔融指数为24g/10min)。
实施例10
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚水解聚缩水甘油基笼型聚倍半硅氧烷(支链分子量1300g/mol，接枝率2.5wt％，密度为0.873g/cm 3，熔融指数为19g/10min)。
实施例11
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N-羟甲基丙烯酰胺(支链分子量1000g/mol，接枝率0.1wt％，密度为0.869g/cm 3，熔融指数为19g/10min)。
实施例12
与实施例3的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N-羟甲基丙烯酰胺(支链分子量1000g/mol，接枝率18wt％，密度为0.870g/cm 3，熔融指数为21g/10min)。
实施例13
与实施例3的区别为：接枝支链为同时含有环氧基和酰胺基的乙烯-丁烯共聚物(支链分子量1000g/mol，接枝率15wt％，密度为0.875g/cm 3，熔融指数为21g/10min)
实施例14
与实施例3的区别为：接枝支链为乙烯-己烯共聚物接枝聚丙烯酰胺，接枝支链分子量1000g/mol，接枝率5wt％，密度为0.875g/cm 3，熔融指数为15g/10min。
实施例15
与实施例3的区别为：接枝支链分子量为200g/mol，接枝率为15％，密度为0.875g/cm 3，熔融指数为15g/10min。
实施例16
与实施例3的区别为：接枝支链分子量为5000g/mol，接枝率为0.5％，密度为0.875g/cm 3，熔融指数为10g/10min。
实施例17
与实施例3的区别为：改性聚烯烃层单层胶膜：以重量份计，取100份的乙烯-丁烯共聚物接枝聚N-羟甲基丙烯酰胺(接枝支链分子量1000g/mol，接枝率5wt％，密度为0.870g/cm3，熔融指数为20g/10min)，加入2份交联剂1,1-双(叔戊基过氧)环己烷，0.02份助交联剂三羟甲基丙烷三丙烯酸酯，1.0份助交联剂乙氧化甘油三丙烯酸酯0.8份增粘剂乙烯基三过氧化叔丁基硅烷，0.8份光稳定剂葵二酸双-2,2,6,6-四甲基哌啶醇。混合均匀，上述混合物经预混合、熔融挤出、流延成膜、冷却、分切和收卷等工序，制得所述单层改性聚烯烃层胶膜封装材料。
实施例18
与实施例17的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N,N’-亚甲基双丙烯酰胺(接枝支链分子量2000g/mol，接枝率1.5wt％，密度为0.880g/cm 3，熔融指数为18g/10min)。
实施例19
与实施例17的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚N-(2-羟基乙基)-十一碳-10-烯酰胺基(接枝支链分子量8000g/mol，接枝率1.0wt％，密度为0.873g/cm 3，熔融指数为3g/10min)。
实施例20
与实施例17的区别为：改性聚烯烃层为乙烯-丁烯共聚物接枝聚水解聚马来酸酐(接枝支链分子量2300g/mol，接枝率1.5wt％，密度为0.875g/cm 3，熔融指数为20g/10min)。
对比例1
聚烯烃胶膜：以重量份计，取100份的乙烯-己烯共聚物(密度为0.870g/cm 3，熔融指数为25g/10min)，加入3份丙烯酰胺，0.5份交联剂叔丁基过氧化碳酸异丙酯，0.5份助交联剂三羟甲基丙烷三甲基丙烯酸酯。
对比例2
与实施例1的区别为：改性聚烯烃层为乙烯-己烯共聚物接枝丙烯酰胺(支链分子量71g/mol，接枝率10wt％)
对比例3
与实施例1的区别为：改性聚烯烃层为乙烯-己烯共聚物接枝聚丙烯酰胺(支链分子量10000g/mol，接枝率10wt％)
性能测试：
将实施例1至20和对比例1至3作粘结力和交联度测试以及组件的层压特性对比。
测试项目及测试方法
1、粘结力
按照300mm×150mm的玻璃/胶膜(两层)/柔性背板依次叠好放入真空层压机中，按照150℃，18分钟的层压工艺进行层压，制作层压件。
在宽度方向上每隔5mm将柔性背板/胶膜切割成10mm±0.5mm的试样用于测试胶膜与玻璃之间的粘结力。按照GB/T 2790-1995的试验方法，以100mm/min±10mm/min的拉伸速度在拉力试验机上测试胶膜与玻璃之间的剥离力，取三个试验的算术平均值，精确到0.1N/cm。
2、交联度
采用二甲苯加热萃取的方法测试。未经二甲苯溶解的质量与初始质量的比指即为交联度。取三个样品的算术平均值，以百分数表示。
3、组件层压外观评价
按照玻璃/胶膜/电池片/胶膜/玻璃的层叠顺序层叠好，按照上述粘结力测试的层压工艺进行层压，制作成标准的双玻太阳能电池组件，组件的规格为60片(6×10)电池片的版型。按照不同的胶膜，各制作100块组件进行外观评价。评价的标准以出现气泡、杂质、胶膜与电池片或玻璃之间脱层为判定对象，具体如下：
○：无 △：轻微 ×：严重
4、组件PID老化测试
选择双面电池，依据IECTS 2804-1：2015进行测试，测试条件加严到85℃，85％RH，外加负1500V恒定直流电压，经192h后，测定光伏组件PID试验前后的功率衰减。
各项性能参数的测试结果如表1所示。
表1 各项性能测试结果
Figure PCTCN2020109634-appb-000003
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
比较实施例1至20及对比例1至3可知，本申请提供的共挤胶膜具有更高的交联度和更好粘结性能，更高的抗PID性能。
比较实施例3至20可知，将改性聚烯烃树脂层中的接枝基团种类、接枝率及支链的分子量限定在本申请优选的范围内有利于提高共挤胶膜的交联度、粘结性能和抗PID性能。
需要说明的是，本申请的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的术语在适当情况下可以互换，以便这里描述的本申请的实施方式例如能够以除了在这里描述的那些以外的顺序实施。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种胶膜，其特征在于，所述胶膜包括：
    至少一个改性聚烯烃树脂层，形成所述改性聚烯烃树脂层的树脂包括1～100％的改性聚烯烃树脂，改性聚烯烃树脂的主链为乙烯-α烯烃共聚物，接枝支链选自包含酸酐基、羟基、酯基、羰基、酰胺基、吡啶基、环氧基、吡咯烷酮基和缩水甘油基中的一种或多种的乙烯基单体所形成的化合物，所述接枝支链的分子量为150～8000g/mol。
  2. 根据权利要求1所述的胶膜，其特征在于，所述接枝支链为分子量为1000～5000g/mol的含酰胺基的化合物；所述改性聚烯烃树脂中，接枝支链的接枝率为0.5～15％。
  3. 根据权利要求2所述的胶膜，其特征在于，所述接枝支链由式(Ⅰ)所示包含酰胺基的乙烯基单体形成的化合物与主链通过自由基接枝反应形成，
    Figure PCTCN2020109634-appb-100001
    其中，所述R 1为H、基团A、所述基团A中至少一个氢原子被羟基或环氧基取代形成的取代基，或所述基团A中至少一个亚甲基被羰基取代形成的取代基，所述基团A为直链烷基、支链烷基或环烷基，且所述基团A的碳原子数≤10，所述R 2为碳原子数为2～20的烯基。
  4. 根据权利要求3所述的胶膜，其特征在于，所述R 2选自乙烯基、丙烯基、丁二烯基、丁烯基、戊烯基、戊二烯基、己烯基、己二烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。
  5. 根据权利要求4所述的胶膜，其特征在于，所述包含酰胺基的乙烯基单体选自丙烯酰胺基、甲基丙烯酰胺基、N-甲基丙烯酰胺基、N-乙基丙烯酰胺基、N-异丙基丙烯酰胺基、N-叔丁基丙烯酰胺基、N-羟甲基丙烯酰胺基、N-羟乙基丙烯酰胺基、N-(2-羟基丙基)丙烯酰胺基、N,N’-亚甲基双丙烯酰胺基、马来酰亚胺基、油酸酰胺、9-十六碳烯酰胺基、N-(2-羟基乙基)-十一碳-10-烯酰胺基、9-十四碳烯酰胺基、9-十二碳烯酰胺基、9-十碳烯酰胺基、辛烯酰胺基、庚烯酰胺基、己烯酰胺基、戊烯酰胺基和丁烯酰胺基组成的组中的一种或多种。
  6. 根据权利要求1所述的胶膜，其特征在于，所述乙烯-α烯烃共聚物为乙烯与至少一种碳原子数≤10的α-烯烃的共聚物。
  7. 根据权利要求6所述的胶膜，其特征在于，所述碳原子数≤10的α-烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种。
  8. 根据权利要求6所述的胶膜，其特征在于，所述乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3；所述乙烯-α烯烃共聚物的熔融指数为1～40g/10min。
  9. 根据权利要求8所述的胶膜，其特征在于，所述乙烯-α烯烃共聚物的密度为0.87～0.88g/cm 3，所述乙烯-α烯烃共聚物的熔融指数为3～30g/10min。
  10. 根据权利要求1至9中任一项所述的胶膜，其特征在于，所述胶膜还包括；至少一个乙烯-醋酸乙烯酯共聚物层，且相邻层不同时为所述乙烯-醋酸乙烯酯共聚物层。
  11. 根据权利要求10所述的胶膜，其特征在于，相邻的所述改性聚烯烃树脂层与所述乙烯-醋酸乙烯酯共聚物层的厚度之比为1:(1～3)。
  12. 根据权利要求11所述的胶膜，其特征在于，形成所述改性聚烯烃树脂层和所述乙烯-醋酸乙烯酯共聚物层的原料还包括交联剂、助交联剂、抗氧剂、紫外线吸收剂、光稳定剂、增粘剂、抗腐蚀剂、颜料中的一种或多种。
  13. 一种电子器件，包括封装胶膜，其特征在于，所述封装胶膜包括权利要求1至12中任一项所述的胶膜。
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