WO2022021770A1 - 一种多功能封装胶膜及其制备方法 - Google Patents

一种多功能封装胶膜及其制备方法 Download PDF

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WO2022021770A1
WO2022021770A1 PCT/CN2020/139131 CN2020139131W WO2022021770A1 WO 2022021770 A1 WO2022021770 A1 WO 2022021770A1 CN 2020139131 W CN2020139131 W CN 2020139131W WO 2022021770 A1 WO2022021770 A1 WO 2022021770A1
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group
adhesive film
layer
optionally
multifunctional
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PCT/CN2020/139131
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English (en)
French (fr)
Inventor
王磊
韩晓航
郑亚
闫烁
陈洪野
吴小平
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苏州赛伍应用技术股份有限公司
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Publication of WO2022021770A1 publication Critical patent/WO2022021770A1/zh

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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
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • H01L31/049—Protective back sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or 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
    • C09J2429/00—Presence of polyvinyl alcohol
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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 application belongs to the technical field of packaging adhesive films, and relates to a multifunctional packaging adhesive film and a preparation method thereof.
  • the encapsulation material plays a role in bonding and protection in the module. More and more cells are used in photovoltaic modules. The performance of various cells is different, and the demand for packaging films is also different; for example, P-type cells require high resistance Films with PID performance; heterojunction cells with round ribbons need non-slippery films; CIGS cells are afraid of heat and require low temperature lamination, etc. The requirements for the packaging film are getting higher and higher, and it is difficult for a single-layer film or a single material to meet the packaging requirements. There is an increasing demand for adhesive films with multilayer structures and adhesive films prepared by blending various materials.
  • ethylene-vinyl acetate copolymer EVA
  • ethylene- ⁇ -olefin copolymer POE
  • EMMA ethylene-methyl methacrylate copolymer
  • EMA ethyl acetate - Methacrylate copolymer
  • EAA ethylene-acrylic acid copolymer
  • PVB polyvinyl butyral
  • POE also has certain shortcomings. With the MBB multi-busbar technology, the surface friction coefficient of POE is small and the polarity is low, which may easily lead to cell slippage. Because of the small polarity of POE, the additives are easy to precipitate and lead to storage. Shorter period, POE crosslinking speed is slower than ethylene-vinyl acetate copolymer (EVA), which affects production efficiency. At the same time, the price of POE is much higher than that of EVA, which puts pressure on the cost of photovoltaic power generation. The peeling force of the conventional POE film is small, and its peeling force is weak in the ability to resist moisture and heat aging. Conventional packaging material EVA film can increase the reliability of components to a certain extent, but for high-efficiency new batteries and components in conventional packaging, the reliability problem cannot be ignored, and more stringent requirements are placed on packaging materials.
  • the encapsulation material comprises the following components: A) 66-99.5 wt % ethylene copolymer, B) 0.5-0.6 wt % organic peroxide, C ) 0.1-3% by weight of alkoxysilane oligomer, and D) optional 0-30% by weight of other auxiliary agents; wherein the sum of the weight percentages of each component is 100%; and the alkoxy group
  • the silane oligomers are alkoxysilane homopolymers, copolymers or mixtures thereof, the average molecular weight of which is 300-2000 g/mol.
  • the encapsulation film of the invention has significantly improved volume resistivity and long-term adhesion to glass and backplane, but its anti-PID performance needs to be further improved.
  • the addition of the alkoxysilane oligomers of this invention may reduce the crosslinking speed.
  • the material of the matrix (except the auxiliary) used in each layer of adhesive films is a single material. In the actual production process of its products, the yield rate is low, and the scraps cannot be recycled.
  • the purpose of the present application is to provide a multifunctional encapsulation adhesive film and a preparation method thereof, and the prepared multifunctional encapsulation adhesive film has excellent peeling force attenuation resistance and anti-PID performance.
  • a multifunctional encapsulation adhesive film based on 100% of the total mass of the multifunctional encapsulation adhesive film, the multifunctional encapsulation adhesive film comprises 90-99% of a polymer and 1-10% of an auxiliary, the The adjuvant contains silane oligomers.
  • the multifunctional encapsulation film of the present application can make the multifunctional encapsulation film have excellent resistance to peeling force attenuation and anti-PID performance, and the silane oligomer The addition of the compound did not reduce the crosslinking speed.
  • the multi-functionality of the multifunctional encapsulation film means that the encapsulation film has peel strength, moisture and heat aging resistance, anti-PID performance, can shorten the lamination time, can be light-cured (reduce energy consumption), and has a laminated appearance. good.
  • the silane oligomer is an oligomer of one silane, an oligomer of two silanes, or an oligomer of three silanes.
  • the chemical formula of the oligomer of a silane is as formula 1, and formula 1 is:
  • R 1 is any of alkane group, alkene group, chlorohydrocarbyl group, aminohydrocarbyl group, epoxy hydrocarbyl group, methacryloyloxyalkyl group, sulfur-containing hydrocarbyl group, ester group, hydroxyl group, isocyanate group, urea group or quaternary aminohydrocarbyl group
  • the alkene group can be optionally a vinyl group
  • X is any one of an alkoxy group, an acetoxy group, a tert-butyl peroxide, a hydroxyl group, a halogen group or a halogenated alkane group
  • the alkoxy group can be optionally an ethoxy group, Methoxy, 2-methoxyethoxy, methyldiethoxy or methyldimethoxy
  • X is alkoxy, acetoxy, tert-butyl peroxide
  • X' is one less than X Oxygen atom
  • R 1 and R 2 are independently selected from alkane, alkene, chlorohydrocarbyl, aminohydrocarbyl, epoxy hydrocarbyl, methacryloyloxyalkyl, sulfur-containing hydrocarbyl, ester, hydroxyl, isocyanate, urea or Any one of the quaternary amino hydrocarbon groups, and the alkene group can be optionally a vinyl group;
  • X and Y are independently selected from any one of alkoxy, acetoxy, tert-butyl peroxide, hydroxy, halo or haloalkane , alkoxy can be ethoxy, methoxy, 2-methoxyethoxy, methyldiethoxy or methyldimethoxy; when Y is alkoxy, acetoxy, peroxide When tert-butyl, Y' is one less oxygen atom than Y; when Y is hydroxyl, halo or haloalkane, Y' is hydrogen;
  • n is any integer from 1 to 10, for example, m is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; n is any integer from 1 to 10, for example n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • R 1 , R 2 , R 3 are independently selected from alkane group, alkene group, chlorohydrocarbyl group, aminohydrocarbyl group, epoxy hydrocarbyl group, methacryloyloxyalkyl group, sulfur-containing hydrocarbyl group, ester group, hydroxyl group, isocyanate group, Any one of urea group or quaternary amino hydrocarbon group, alkene group can be optionally vinyl group;
  • X, Y, Z are independently selected from alkoxy group, acetoxy group, tert-butyl peroxide, hydroxyl group, halogen group or halogenated alkane group Any one of the alkoxy groups can be ethoxy, methoxy, 2-methoxyethoxy, methyldiethoxy or methyldimethoxy; when Z is alkoxy, acetyl When oxy, tert-butyl peroxide, Z' is one oxygen atom less than Z; when Z is hydroxyl, halo or
  • the auxiliary includes the following components:
  • the mass percentage of the main crosslinking agent is 0.2-1.1wt%, for example, the mass percentage of the main crosslinking agent is 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt% , 0.9 wt %, 1 wt % or 1.1 wt %, etc.
  • the main crosslinking agent is 2-ethylhexyl tert-butyl peroxide (TBEC), 2-ethylhexyl tert-amyl peroxide (TAEC), 2,5-dimethyl-2,5-bis (tert-butyl peroxide) hexane or tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl 2-ethylhexanoate peroxy, tert-pentyl peroxide 2-ethylhexanoate Esters, dicumyl peroxide, benzoyl peroxide, 1,4-di-tert-butyl cumyl peroxybenzene, tert-butyl peroxybenzoate, tert-amyl peroxide (TAP), peroxybenzoate Any one or a mixture of at least two of tert-butyl oxyisopropyl carbonate (TBIC) and 1,1-bis(ter
  • the mass percentage of the crosslinking accelerator is 0.2-2wt%, for example, the mass percentage of the crosslinking accelerator is 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt% or 2wt% etc.
  • the crosslinking accelerator is any one of triallyl isocyanurate auxiliary crosslinking agent, triacrylate cyanurate auxiliary crosslinking agent or acrylate auxiliary crosslinking agent or A mixture of at least two.
  • the mass percentage of the photoinitiator is 0-3wt%, for example, the mass percentage of the photoinitiator is 0, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, etc.
  • the photoinitiator is benzoin and its derivative photoinitiator, benzil and its derivative photoinitiator, acetophenone derivative photoinitiator, ⁇ -hydroxy ketone derivative Photoinitiator, ⁇ -amino ketone derivative photoinitiator, acylphosphorus oxide photoinitiator, sulfur-containing photoinitiator, benzophenone and its derivatives photoinitiator, thioxanthone and Its derivative photoinitiator, anthraquinone and its derivative photoinitiator, aryldiazonium salt photoinitiator, diaryliodonium salt photoinitiator, triarylsulfonium salt photoinitiator, aryl Any one or a
  • the mass percentage of the silane coupling agent is 0.05-1wt%, for example, the mass percentage of the silane coupling agent is 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt% etc.
  • the silane coupling agent is vinyl silane coupling agent, chlorohydrocarbyl silane coupling agent, aminohydrocarbyl silane coupling agent, epoxy hydrocarbyl silane coupling agent, methacryloyloxyalkane Any one or a mixture of at least two of the radical-based silane coupling agent, the sulfur-containing hydrocarbon-based silane coupling agent, the pseudo-halogen-based silane coupling agent or the quaternary amino hydrocarbon-based silane coupling agent.
  • the mass percentage of silane oligomer is 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt% or 4wt% etc.
  • the silane oligomer may be an oligomer of one silane, an oligomer of two silanes, or an oligomer of three silanes. The structure is as described above.
  • the mass percentage of the ion trapping agent is 0-3wt%, for example, the mass percentage of the ion trapping agent is 0, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, etc.
  • the ion scavenger is a xanthate ion scavenger, a dithiocarbamate derivative, an insoluble inorganic compound exhibiting cation exchange properties in the presence of water, or a cation exchange with ion exchange function Any one or a mixture of at least two of the resin and or anion exchange resin.
  • the insoluble inorganic compound is a divalent metal oxide, a trivalent metal oxide, a tetravalent metal oxide, a pentavalent metal oxide, a hexavalent metal oxide, a heptavalent metal oxide or a metal phosphate salt. Any one or a mixture of at least two.
  • the selected ion exchange resin is a styrene-based ion-exchange resin and/or an acrylic-based ion-exchange resin;
  • the insoluble inorganic compound is more optionally silica, zirconium phosphate and/or titanium phosphate.
  • the mass percentage of the antioxidant is 0.05-0.5wt%, for example, the mass percentage of the antioxidant is 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% or 0.5wt%.
  • the antioxidant is any of hindered phenol antioxidants, aromatic amine antioxidants, phosphite antioxidants, thioether antioxidants or metal deactivator antioxidants. one or a mixture of at least two.
  • the mass percentage of the light stabilizer is 0.05-0.5 wt %, for example, the mass percentage of the light stabilizer is 0.05 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt % or 0.5 wt %.
  • the light stabilizer is any one of a light shielding agent-based light stabilizer, a quencher-based light stabilizer, a radical scavenger-based light stabilizer, or a hydroperoxidative decomposer-based light stabilizer or A mixture of at least two.
  • the mass percentage of the ultraviolet light absorbing agent is 0-0.5 wt %, for example, the mass percentage of the ultraviolet light absorbing agent is 0, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt % or 0.5 wt %.
  • the UV absorber is a benzophenone UV absorber, a benzotriazole UV absorber, a salicylate UV absorber, a substituted acrylonitrile UV absorber or a triazine. Any one or a mixture of at least two of the UV-like absorbers.
  • the multifunctional encapsulation adhesive film is a single-layer encapsulation adhesive film, and the single-layer encapsulation adhesive film contains 90-99% of a polymer and 1-10% of an auxiliary agent, and the polymer is ethylene- Vinyl acetate copolymer, ethylene- ⁇ -olefin copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethyl-methacrylate copolymer, ethylene- Any one or a mixture of at least two of butyl acrylate copolymer, polyvinyl butyral, ionomer or polyurethane.
  • the multifunctional packaging film is a multi-layer packaging film
  • the multi-layer packaging film includes at least two layers of packaging film
  • each layer of the packaging film contains 90-99% polymer and 1-10% of auxiliary agent
  • the polymer is ethylene-vinyl acetate copolymer, ethylene- ⁇ -olefin copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer Any one or a mixture of at least two of ester copolymer, ethyl-methacrylate copolymer, ethylene-butyl acrylate copolymer, polyvinyl butyral, ionic polymer or polyurethane.
  • the multi-layer encapsulation adhesive film includes an upper surface layer and a lower surface layer that are sequentially arranged from top to bottom.
  • the cross-linking degree of the multi-layer encapsulation adhesive film is greater than or equal to 70%.
  • the visible light transmittance of the multilayer encapsulation adhesive film is greater than or equal to 85%.
  • the number of layers of the multilayer encapsulation adhesive film is 2 to 5 layers, for example, the number of layers of the multilayer encapsulation adhesive film is 2 layers, 3 layers, 4 layers or 5 layers.
  • the second purpose of the present application is to provide a method for preparing a multifunctional encapsulation film according to one of the purposes. Compound molding is performed to obtain the multifunctional encapsulation film.
  • the single-layer encapsulation film can be prepared by extrusion casting, extrusion calendering, denim calendering, planetary extruder calendering and other methods.
  • the multifunctional encapsulation adhesive film of the present application can be made into light curing or light/heat hybrid curing according to the selection of auxiliary agents, so that the adhesive film can realize tool-less lamination, reduce production costs (reduce energy consumption, shorten time), and improve production efficient.
  • the multifunctional encapsulation adhesive film is a multi-layer encapsulation adhesive film
  • the preparation method of the co-extrusion molding of the multilayer encapsulation adhesive film includes the following steps: mixing the raw materials of each layer according to the proportions, and in the setting The respective extruders with a predetermined temperature are extruded separately, distributed through a distributor, shaped by a die head, and embossed by a roller to obtain the multi-layer encapsulation film.
  • the preparation method of the lamination molding of the multi-layer encapsulation film includes the following steps: mixing the raw materials of each layer according to the proportion, first extruding the middle layer in an extruder, the surface of the middle layer is smooth, and the rest Each layer is sequentially coated on the upper and lower surfaces of the intermediate layer, and the rollers are embossed to obtain the multi-layer encapsulation film.
  • the preparation method of the composite molding of the multi-layer encapsulation adhesive film includes the following steps of composite molding, including the following steps: mixing the raw materials of each layer according to the proportion, and extruding each layer separately in an extruder to a predetermined size.
  • the thickness of the single-layer film, each layer of film is laminated at one time according to the set structure, and lamination and roll embossing are performed on the compound roll to obtain the multi-layer encapsulation film.
  • the multifunctional encapsulation film of this application has excellent resistance to peeling force attenuation and anti-PID performance, wherein, the peeling force between DH3000h and glass is ⁇ 70N/cm, the peeling force attenuation is small, and the front power attenuation of photovoltaic modules after PID192h is 0.8-2.1 %, the rear power attenuation is 1.3-2.8%.
  • the photo-curing cross-linking molding or the heat/light dual-curing cross-linking molding reduces the production energy consumption and shortens the lamination time.
  • the lamination process can realize lamination without tooling, or lamination without auxiliary equipment for lamination, which improves the lamination efficiency of the component factory, has the feasibility of production operation, and can recycle leftovers, which greatly improves the production yield.
  • the multifunctional encapsulation adhesive film of this embodiment is a single-layer encapsulation adhesive film. Based on the total mass of the multifunctional encapsulation adhesive film being 100%, the multifunctional encapsulation adhesive film includes the following components:
  • the preparation method of the multifunctional encapsulation film of this embodiment is as follows: after mixing the polymer and the auxiliary agent according to the above ratio, the extrusion calendering at a set temperature (screw sampling 60-85°C, die area 100°C) Equipment machine extrusion, three-roller embossing and shaping, to prepare a single-layer encapsulation film.
  • the multifunctional packaging adhesive film of this embodiment is a multi-layer packaging adhesive film, specifically a three-layer structure, the upper/middle/lower thickness is 1:1:1, and the upper layer and the lower layer are made of the same material.
  • the multifunctional packaging adhesive film of this embodiment is a multi-layer packaging adhesive film, specifically a three-layer structure, the upper/middle/lower thickness is 1:2:1, and the upper layer and the lower layer are made of the same material.
  • the formula of the upper layer and lower layer film is as follows:
  • the middle layer formula is as follows:
  • the multifunctional encapsulation adhesive film of this embodiment is a single-layer structure encapsulation adhesive film. Based on the total mass of the multifunctional encapsulation adhesive film being 100%, the multifunctional encapsulation adhesive film includes the following components:
  • silane oligomer is a structural formula of silane oligomer
  • the multifunctional packaging adhesive film of this embodiment is a single-layered packaging adhesive film, but has the characteristics of light/heat hybrid curing. Based on the total mass of the multifunctional packaging adhesive film being 100%, the multifunctional packaging adhesive film includes the following groups: Minute:
  • the multifunctional encapsulation adhesive film of this embodiment is a multi-layer encapsulation adhesive film, specifically a three-layer structure, the upper/middle/lower thickness is 1:1:1, the upper, middle and lower layers are all made of EVA resin, and the upper layer and the lower layer are the same formula, the middle layer is another formula.
  • the formula of the upper layer and lower layer film is as follows:
  • the formula of the middle layer is as follows:
  • the multifunctional encapsulation film of this embodiment is a multi-layer encapsulation film, specifically a three-layer structure, the upper/middle/lower thickness is 1:3:1, the upper, middle and lower are POE resin, the upper layer and the lower layer are the same formula, The middle layer is another recipe.
  • the formula of the upper layer and lower layer film is as follows:
  • the middle layer formula is as follows:
  • the multifunctional encapsulation adhesive film of this embodiment is a multi-layer encapsulation adhesive film, specifically a two-layer structure, the upper/lower thickness is 1:1, the upper and lower layers are both EVA resin, and the formula of the upper and lower layers of the adhesive film is as follows:
  • Example 2 The difference between this comparative example and Example 2 is that silane oligomers are not contained, and the reduced mass percentage of silane oligomers is added to other additives on average to ensure that the total amount of additives remains unchanged.
  • Example 2 The difference between this comparative example and Example 2 is that the auxiliaries do not contain silane oligomers and ion scavengers, and the reduced mass percentages of silane oligomers and ion scavengers are added to other auxiliaries on average to ensure that the auxiliaries The total remains unchanged.
  • the multifunctional encapsulation adhesive films prepared in Examples 1-8 and Comparative Examples 1-3 were prepared into modules and tested for peel force performance and anti-PID performance. Table 1 shows the test results.
  • the structure of the module is glass/film/P-type cell/film/glass, and the upper and lower layers of film are made of the same film of the same gram weight, and are laminated in a laminator at 145°C for 5+15min. Among them, Example 5 can be cured by photothermal mixing.
  • test standard of peeling force performance is carried out with reference to GB/T 29848-2013, and the test standard of anti-PID performance is carried out with reference to standard IEC62804.
  • Example 1 after the photovoltaic module is subjected to PID192h, the front power is attenuated by 0.8%, and the rear power is attenuated by 1.3%.
  • the anti-PID performance of the module of the present application is greatly improved, and the resistance to peeling force attenuation is also greatly improved.
  • This application illustrates the detailed process equipment and process flow of the present application through the above-mentioned embodiments, but the application is not limited to the above-mentioned detailed process equipment and process flow, which does not mean that the application must rely on the above-mentioned detailed process equipment and process flow to implement. .

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Abstract

一种多功能封装胶膜及其制备方法，按质量百分比计包含90-99%的聚合物和1-10%的助剂，所述助剂包含硅烷低聚物。所制得的多功能封装胶膜具有优异的耐剥离力衰减性能和抗PID性能，可满足对不同功能的封装胶膜的需求。

Description

一种多功能封装胶膜及其制备方法 技术领域
本申请属于封装胶膜技术领域，涉及一种多功能封装胶膜及其制备方法。
背景技术
封装材料在组件中起到粘接保护等作用，光伏组件所用电池片越来越多，各种电池片的性能不一样，对封装胶膜的需求也不一样；比如P型电池片需要高抗PID性能的胶膜；配圆焊带的异质结电池片需要表面不滑的胶膜，CIGS的电池片怕热，需要低温层压等。对封装胶膜的要求越来越高，单层胶膜或者单种材料难以满足封装要求。对多层结构的胶膜以及各种材料共混所制备的胶膜需求越来越多。随着要求使用年限的增加，对封装胶膜的剥离力衰减要求越来越大，需要湿热老化后封装胶膜剥离力维持一个很高的值。现有技术为了提高封装胶膜的剥离力，在加入硅烷偶联剂作为第一硅烷的基础上会引入其他的硅烷化合物作为第二硅烷，但是很多第二硅烷的加入可能会降低交联速度。
目前，可做封装胶膜的材料有很多，比如乙烯-醋酸乙烯酯共聚物(EVA)、乙烯-α-烯烃共聚物(POE)、乙烯-甲基丙烯酸甲酯共聚物(EMMA)、乙基-甲基丙烯酸酯共聚物(EMA)、乙烯-丙烯酸共聚物(EAA)、聚乙烯醇缩丁醛(PVB)、离子聚合物等材料，各种材料的性能不一样；POE具有高阻水功能、抗PID功能；EVA具有高透光率高交联速度等优点；PVB内聚力大，适合BIPV建筑等功能。但是，POE也有一定的不足，随着MBB多主栅技术，POE表面摩擦系数小，极性低，造成容易导致电池片并片滑移，因为POE极性小，造成助剂容易析出，导致储存期短，POE交联速度较乙烯-醋酸乙烯酯共聚物(EVA)慢，影响生产效率。同时POE价格远高于EVA，给光伏发电成本造成压力。常规 POE胶膜的剥离力较小，其剥离力耐湿热老化后的能力较弱。常规封装材料EVA胶膜能够在一定程度上增加组件的可靠性，但对于常规封装的高效新型电池及组件，可靠性问题不容忽视，对封装材料提出了更严苛的要求。
CN110079244A一种太阳能电池封装材料及由它形成的胶膜，所述封装材料包含以下组分：A)66-99.5重量％的乙烯共聚物，B)0.5-0.6重量％的有机过氧化物，C)0.1-3重量％的烷氧基硅烷低聚物，以及D)任选的0-30重量％的其他助剂；其中各组分重量百分比的加和为100％；以及所述烷氧基硅烷低聚物为烷氧基硅烷均聚物、共聚物或其混合物，其平均分子量为300-2000g/mol。该发明的封装胶膜有显著提高的体积电阻率，对玻璃、背板具有长久的粘结力，但是其抗PID性能有待进一步提高。但是，该发明的烷氧基硅烷低聚物加入可能会降低交联速度。
另外，现有技术的多层胶膜，各层胶膜所用的基体(除助剂外的)材料为单一材料。其产品在实际生产过程中，良率较低，边角料无法回收利用。
因此，很有必要开发一种具有优异的耐剥离力衰减性能和抗PID性能的多功能封装胶膜及其制备方法，以满足对不同功能的封装胶膜的需求。
发明内容
本申请的目的在于提供一种多功能封装胶膜及其制备方法，制得的多功能封装胶膜具有优异的耐剥离力衰减性能和抗PID性能。
本申请的目的之一在于提供一种多功能封装胶膜，为达此目的，本申请采用以下技术方案：
一种多功能封装胶膜，按所述多功能封装胶膜的总质量为100％计，所述多功能封装胶膜包含90-99％的聚合物和1-10％的助剂，所述助剂包含硅烷低聚 物。
本申请的多功能封装胶膜，助剂中添加的硅烷低聚物，与其他助剂协同作用，可使多功能封装胶膜具有优异的耐剥离力衰减性能和抗PID性能，并且硅烷低聚物的加入没有降低交联速度。
需要说明的是，所述多功能封装胶膜的多功能是指封装胶膜具有剥离力耐湿热老化性能、抗PID性能，可以缩短层压时间、可以光固化(降低能耗)、层压外观好。
所述硅烷低聚物为一种硅烷的低聚物、两种硅烷的低聚物或三种硅烷的低聚物。
可选地，所述一种硅烷的低聚物的化学式如式1，式1为：
Figure PCTCN2020139131-appb-000001
其中，R 1为烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种，烯烃基可选为乙烯基；X为烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种，烷氧基可选为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基；当X为烷氧基、乙酰氧基、过氧化叔丁基时，X’比X少一氧原子；当X为羟基、卤基或卤代烷烃基时，X’为氢基；可选地，m为2-10中的任意一整数，例如m为2、3、4、5、6、7、8、9或10。可选地，两种硅烷的低聚物的化学式如式2，式2为：
Figure PCTCN2020139131-appb-000002
其中，R 1与R 2独立地选自烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、 甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种，烯烃基可选为乙烯基；X与Y独立地选自烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种，烷氧基可选为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基；当Y为烷氧基、乙酰氧基、过氧化叔丁基时，Y’比Y少一氧原子；当Y为羟基、卤基或卤代烷烃基时，Y’为氢基；
可选地，m为1-10中的任意一个整数，例如m为1、2、3、4、5、6、7、8、9或10；n为1-10中的任意一个整数，例如n为1、2、3、4、5、6、7、8、9或10。
可选地，三种硅烷的低聚物的化学式如式3，式3为：
Figure PCTCN2020139131-appb-000003
其中，R 1、R 2、R 3独立地选自烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种，烯烃基可选为乙烯基；X、Y、Z独立地选自烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种，烷氧基可选为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基；当Z为烷氧基、乙酰氧基、过氧化叔丁基时，Z’比Z少一氧原子；当Z为羟基、卤基或卤代烷烃基时，Z’为氢基；可选地，m为1-10中的任意一个整数，例如m为1、2、3、4、5、6、7、8、9或10；n为1-10中的任意一个整数，例如n为1、2、3、4、5、6、7、8、9或10；q为1-10中的任意一个整数，例如q为1、2、3、4、5、6、7、8、9或10。
按所述多功能封装胶膜总质量百分比为100％计，所述助剂包含如下组分：
Figure PCTCN2020139131-appb-000004
主交联剂的质量百分比为0.2-1.1wt％，例如主交联剂的质量百分比为0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％或1.1wt％等。所述主交联剂为过氧化2-乙基己基碳酸叔丁酯(TBEC)、过氧化2-乙基己基碳酸叔戊酯(TAEC)、2,5-二甲基-2,5-双(过氧化叔丁基)己烷或过氧化-3,5,5-三甲基己酸叔丁酯、过氧化2-乙基己酸叔丁酯、过氧化2-乙基己酸叔戊酯、过氧化二异丙苯、过氧化苯甲酰、1,4-双叔丁基过氧异丙基苯、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯(TAP)、过氧化异丙基碳酸叔丁酯(TBIC)、1,1-双(叔戊基过氧)环己烷中的任意一种或至少两种的混合物。
交联促进剂的质量百分比为0.2-2wt％，例如交联促进剂的质量百分比为0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％或2wt％等。可选地，所述交联促进剂为三烯丙基异氰脲酸酯助交联剂、 三聚氰酸三丙烯酯助交联剂或丙烯酸酯类助交联剂中的任意一种或至少两种的混合物。
光引发剂的质量百分比为0-3wt％，例如光引发剂的质量百分比为0、1wt％、1.5wt％、2wt％、2.5wt％或3wt％等。可选地，所述光引发剂为苯偶姻及其衍生物类光引发剂、苯偶酰及其衍生物类光引发剂、苯乙酮衍生物类光引发剂、α-羟基酮衍生物类光引发剂、α-胺基酮衍生物类光引发剂、酰基磷氧化物类光引发剂、含硫光引发剂、二苯甲酮及其衍生物类光引发剂、硫杂蒽酮及其衍生物类光引发剂、蒽醌及其衍生物类光引发剂、芳基重氮盐类光引发剂、二芳基碘鎓盐类光引发剂、三芳基硫鎓盐光引发剂、芳茂铁盐光引发剂、樟脑醌光引发剂或钛茂类光引发剂中的任意一种或至少两种的混合物。
硅烷偶联剂的质量百分比为0.05-1wt％，例如硅烷偶联剂的质量百分比为0.05wt％、0.06wt％、0.07wt％、0.08wt％、0.09wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％或1wt％等。可选地，所述硅烷偶联剂为乙烯基类硅烷偶联剂、氯烃基类硅烷偶联剂、氨烃基类硅烷偶联剂、环氧烃基类硅烷偶联剂、甲基丙烯酰氧烷基类硅烷偶联剂、含硫烃基类硅烷偶联剂、拟卤素类硅烷偶联剂或季氨烃基类硅烷偶联剂中的任意一种或至少两种的混合物。
硅烷低聚物0.1～4wt％，例如硅烷低聚物的质量百分比为0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％或4wt％等。所述硅烷低聚物可以是一种硅烷的低聚物，也可以是两种硅烷的低聚物，还可以是三种硅烷的低聚物。结构如上所述。
离子捕捉剂的质量百分比为0～3wt％，例如离子捕捉剂的质量百分比为0、0.05wt％、0.06wt％、0.07wt％、0.08wt％、0.09wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.5wt％、2wt％、2.5wt％或3wt％等。可选地，所述离子捕捉剂为黄原酸酯类离子捕捉剂、二硫代氨基甲酸盐类衍生物、在水存在下表现出阳离子交换特性的不溶性无机化合物或者具有离子交换功能的阳离子交换树脂和或阴离子交换树脂中的任意一种或至少两种的混合物。
可选地，所述不溶性无机化合物为二价金属氧化物、三价金属氧化物、四价金属氧化物、五价金属氧化物、六价金属氧化物、七价金属氧化物或磷酸金属盐中的任意一种或至少两种的混合物。
可选地，所选离子交换树脂为苯乙烯系离子交换树脂和/或丙烯酸系离子交换树脂；所述不溶性无机化合物更可选为二氧化硅、磷酸锆和/或磷酸钛。
抗氧剂的质量百分比为0.05～0.5wt％，例如抗氧剂的质量百分比为0.05wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％或0.5wt％等。可选地，所述抗氧剂为受阻酚类抗氧剂、芳香胺类抗氧剂、亚磷酸酯类抗氧剂、硫醚类抗氧剂或金属钝化剂类抗氧剂中的任意一种或至少两种的混合物。
光稳定剂的质量百分比为0.05～0.5wt％，例如光稳定剂的质量百分比为0.05wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％或0.5wt％等。可选地，所述光稳定剂为光屏蔽剂类光稳定剂、淬灭剂类光稳定剂、自由基捕获剂类光稳定剂或氢过氧化分解剂类光稳定剂中的任意一种或至少两种的混合物。
紫外光吸收剂的质量百分比为0～0.5wt％，例如紫外光吸收剂的质量百分比为0、0.1wt％、0.2wt％、0.3wt％、0.4wt％或0.5wt％等。可选地，所述紫外光吸 收剂为苯酮类紫外光吸收剂、苯并三唑类紫外光吸收剂、水杨酸酯类紫外光吸收剂、取代丙烯腈类紫外光吸收剂或三嗪类紫外光吸收剂中的任意一种或至少两种的混合物。
作为可选方案，所述多功能封装胶膜为单层封装胶膜，所述单层封装胶膜包含90-99％的聚合物和1-10％的助剂，所述聚合物为乙烯-醋酸乙烯酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙基-甲基丙烯酸酯共聚物、乙烯-丙烯酸丁酯共聚物、聚乙烯醇缩丁醛、离子聚合物或聚氨酯中的任意一种或至少两种的混合物。
作为可选方案，所述多功能封装胶膜为多层封装胶膜，所述多层封装胶膜包含至少两层封装胶膜，每一层所述封装胶膜包含90-99％的聚合物和1-10％的助剂，所述聚合物为乙烯-醋酸乙烯酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙基-甲基丙烯酸酯共聚物、乙烯-丙烯酸丁酯共聚物、聚乙烯醇缩丁醛、离子聚合物或聚氨酯中的任意一种或至少两种的混合物。
作为可选方案，所述多层封装胶膜包括由上至下依次设置的上表层和下表层。
所述多层封装胶膜的交联度≥70％。可选地，所述多层封装胶膜的可见光透光率≥85％。
可选地，所述多层封装胶膜的层数为2～5层，例如多层封装胶膜的层数为2层、3层、4层或5层。
本申请的目的之二在于提供一种目的之一所述的多功能封装胶膜的制备方法，所述制备方法包括如下步骤：按配比将聚合物和助剂混合，经共挤、淋膜 或复合成型，得到所述多功能封装胶膜。
单层封装胶膜可以选择挤出流延、挤出压延、密练压延、行星挤出机压延等方法制备得到。
本申请的多功能封装胶膜根据助剂的选择可以做成光固化或者光/热混合固化，这样胶膜可以实现无工装层压，降低了生产成本(降低能耗、缩短时间)，提高生产效率。
作为本申请的可选方案，所述多功能封装胶膜为多层封装胶膜，所述多层封装胶膜的共挤成型的制备方法包括如下步骤：按配比将各层原料混合，在设定好温度的各自挤出机分别挤出，经分配器分配，模头定型，辊筒压花，得到所述多层封装胶膜。
可选地，所述多层封装胶膜的淋膜成型的制备方法包括如下步骤：按配比将各层原料混合，先将中间层在挤出机挤出，中间层的表面为光面，其余各层按顺序依次在中间层的上下表面进行淋膜，辊筒压花，得到所述多层封装胶膜。
可选地，所述多层封装胶膜的复合成型的制备方法包括如下步骤复合成型，包括如下步骤：按配比将各层原料混合，将各层分别在挤出机中单独挤出成设定厚度的单层膜，各层膜按照设定结构一次层叠，在复合辊上进行复合及辊筒压花，得到所述多层封装胶膜。
与现有技术相比，本申请的有益效果为：
本申请的多功能封装胶膜，具有优异的耐剥离力衰减性能和抗PID性能，其中，DH3000h与玻璃的剥离力≥70N/cm，剥离力衰减小，PID192h后光伏组件正面功率衰减0.8-2.1％，背面功率衰减1.3-2.8％。
本申请的多功能封装胶膜的制备方法，光固化交联成型或者热/光双固化交 联成型降低了生产能耗缩短了层压时间，采用光固化层压工艺或者光/热混合固化层压工艺，可以实现无工装层压，或者无层压辅助设备层压，提高了组件厂层压效率，具有生产操作可行性，可以回收利用边角料，大幅度提高了生产的良率。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。
如无具体说明，本申请的各种原料均可市售购得，或根据本领域的常规方法制备得到。
实施例1
本实施例的多功能封装胶膜为单层封装胶膜，按多功能封装胶膜的总质量为100％计，多功能封装胶膜包含如下组分：
Figure PCTCN2020139131-appb-000005
其中，硅烷低聚物的结构式为：
Figure PCTCN2020139131-appb-000006
本实施例的多功能封装胶膜的制备方法如下：将聚合物和助剂按上述比例混合好后，经设定好温度(螺杆取样60-85℃、模头区域100℃)的挤出压延设备机挤出，经三辊压花定型，制备得到单层封装胶膜。
实施例2
本实施例的多功能封装胶膜为多层封装胶膜，具体为三层结构，上/中/下厚度为1:1:1，上层与下层为同一材料。
上层下层胶膜的配方如下：
Figure PCTCN2020139131-appb-000007
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000008
其中，中间层的配方如下：CH 2
Figure PCTCN2020139131-appb-000009
Figure PCTCN2020139131-appb-000010
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000011
实施例3
本实施例的多功能封装胶膜为多层封装胶膜，具体为三层结构，上/中/下厚度为1:2:1，上层与下层为同一材料。
其中，上层下层胶膜的配方如下：
Figure PCTCN2020139131-appb-000012
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000013
其中，中间层配方如下：
Figure PCTCN2020139131-appb-000014
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000015
实施例4
本实施例的多功能封装胶膜是单层结构的封装胶膜，按多功能封装胶膜的总质量为100％计，多功能封装胶膜包含如下组分：
Figure PCTCN2020139131-appb-000016
Figure PCTCN2020139131-appb-000017
其中，硅烷低聚物的结构式为
Figure PCTCN2020139131-appb-000018
实施例5
本实施例的多功能封装胶膜是单层结构的封装胶膜，但是具有光/热混合固化的特性，按多功能封装胶膜的总质量为100％计，多功能封装胶膜包含如下组分：
Figure PCTCN2020139131-appb-000019
Figure PCTCN2020139131-appb-000020
其中，硅烷低聚物的结构式为：
Figure PCTCN2020139131-appb-000021
实施例6
本实施例的多功能封装胶膜为多层封装胶膜，具体为三层结构，上/中/下厚度为1:1:1，上中下三层都为EVA树脂，上层与下层为同一配方，中间层为另一配方。
其中，上层下层胶膜的配方如下：
Figure PCTCN2020139131-appb-000022
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000023
其中，中间层的配方如下：
Figure PCTCN2020139131-appb-000024
实施例7
本实施例的多功能封装胶膜为多层封装胶膜，具体为三层结构，上/中/下厚度为1:3:1，上中下都为POE树脂，上层与下层为同一配方，中层为另外一个配方。
其中，上层下层胶膜的配方如下：
Figure PCTCN2020139131-appb-000025
Figure PCTCN2020139131-appb-000026
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000027
其中，中间层配方如下：
Figure PCTCN2020139131-appb-000028
实施例8
本实施例的多功能封装胶膜为多层封装胶膜，具体为两层结构，上/下厚度为1:1，上下两层都为EVA树脂，上层下层胶膜的配方如下：
Figure PCTCN2020139131-appb-000029
Figure PCTCN2020139131-appb-000030
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000031
其中，下层的配方如下：
Figure PCTCN2020139131-appb-000032
其中，硅烷低聚物的结构式如下：
Figure PCTCN2020139131-appb-000033
对比例1
本对比例与实施例2的区别之处在于，不含硅烷低聚物，减少的硅烷低聚物的质量百分比平均加至其他助剂以保证助剂总量不变。
对比例2
本对比例与实施例2的区别之处在于，硅烷低聚物替换为
Figure PCTCN2020139131-appb-000034
对比例3
本对比例与实施例2的区别之处在于，助剂中不含硅烷低聚物及离子捕捉剂，减少的硅烷低聚物及离子捕捉剂的质量百分比平均加至其他助剂以保证助剂总量不变。
将实施例1-8与对比例1-3制得的多功能封装胶膜制备成组件进行剥离力性能和抗PID性能测试，测试结果如表1所示。组件结构为玻璃/胶膜/P型电池片/胶膜/玻璃，上下层胶膜采用同等克重同种胶膜，在层压机中145℃、5+15min层压。其中实施例5可以采用光热混合固化。
其中，剥离力性能的测试标准参照GB/T 29848-2013进行，抗PID性能的测试标准参照标准IEC62804进行。
表1
Figure PCTCN2020139131-appb-000035
Figure PCTCN2020139131-appb-000036
以实施例1为例，光伏组件经PID192h后，正面功率衰减0.8％，背面功率衰减1.3％。
相对于对比例1未加硅烷低聚物的封装胶膜制成的组件，本申请的组件抗PID性能大幅度提升，且耐剥离力衰减性能也大幅度提升。
对比例2硅烷低聚物替换为其他不含本申请的重复单元的类型后，抗PID性能大幅度和耐剥离力衰减性能也明显降低。
对比例3，未添加硅烷低聚物及离子捕捉剂，抗PID性能大幅度和耐剥离力衰减性能同样也明显降低。
本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述 详细工艺设备和工艺流程才能实施。

Claims (12)

  1. 一种多功能封装胶膜，其中，按所述多功能封装胶膜的总质量百分比为100％计，所述多功能封装胶膜包含90-99％的聚合物和1-10％的助剂，所述助剂包含硅烷低聚物。
  2. 根据权利要求1所述的多功能封装胶膜，其中，所述硅烷低聚物为一种硅烷的低聚物、两种硅烷的低聚物或三种硅烷的低聚物。
  3. 根据权利要求2所述的多功能封装胶膜，其中，所述一种硅烷的低聚物的化学式如式1，式1为：
    Figure PCTCN2020139131-appb-100001
    其中，R 1为烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种；X为烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种；当X为烷氧基、乙酰氧基、过氧化叔丁基时，X’比X少一氧原子；当X为羟基、卤基或卤代烷烃基时，X’为氢基；m为2-10中的任意一整数。
  4. 根据权利要求3所述的多功能封装胶膜，其中，所述烯烃基为乙烯基；
    可选地，所述烷氧基为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基。
  5. 根据权利要求2所述的多功能封装胶膜，其中，所述两种硅烷的低聚物的化学式如式2，式2为：
    Figure PCTCN2020139131-appb-100002
    其中，R 1与R 2独立地选自烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种，烯烃基可选为乙烯基；X与Y独立地选自烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种，烷氧基可选为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基；当Y为烷氧基、乙酰氧基、过氧化叔丁基时，Y’比Y少一氧原子；当Y为羟基、卤基或卤代烷烃基时，Y’为氢基；可选地，m为1-10中的任意一个整数；n为1-10中的任意一个整数；
    可选地，所述三种硅烷的低聚物的化学式如式3，式3为：
    Figure PCTCN2020139131-appb-100003
    其中，R 1、R 2、R 3独立地选自烷烃基、烯烃基、氯烃基、氨烃基、环氧烃基、甲基丙烯酰氧烷基、含硫烃基、酯基、羟基、异氰酸酯基、脲基或季氨烃基中的任意一种，烯烃基可选为乙烯基；X、Y、Z独立地选自烷氧基、乙酰氧基、过氧化叔丁基、羟基、卤基或卤代烷烃基中的任意一种，烷氧基可选为乙氧基、甲氧基、2-甲氧乙氧基、甲基二乙氧基或甲基二甲氧基；当Z为烷氧基、乙酰氧基、过氧化叔丁基时，Z’比Z少一氧原子；当Z为羟基、卤基或卤代烷烃基时，Z’为氢基；可选地，m为1-10中的任意一个整数；n为1-10中的任意一个整数；q为1-10中的任意一个整数。
  6. 根据权利要求1-5之一所述的多功能封装胶膜，其中，按所述多功能封装胶膜总质量百分比为100％计，所述助剂包含如下组分：
    Figure PCTCN2020139131-appb-100004
    Figure PCTCN2020139131-appb-100005
  7. 根据权利要求1-6之一所述的多功能封装胶膜，其中，所述主交联剂为过氧化2-乙基己基碳酸叔丁酯、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基-2,5-双(过氧化叔丁基)己烷或过氧化-3,5,5-三甲基己酸叔丁酯中、过氧化2-乙基己酸叔丁酯、过氧化2-乙基己酸叔戊酯、过氧化二异丙苯、过氧化苯甲酰、1,4-双叔丁基过氧异丙基苯、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化异丙基碳酸叔丁酯、1,1-双(叔戊基过氧)环己烷的任意一种或至少两种的混合物；
    可选地，所述交联促进剂为三烯丙基异氰脲酸酯助交联剂、三聚氰酸三丙烯酯助交联剂或丙烯酸酯类助交联剂中的任意一种或至少两种的混合物；
    可选地，所述光引发剂为苯偶姻及其衍生物类光引发剂、苯偶酰及其衍生物类光引发剂、苯乙酮衍生物类光引发剂、α-羟基酮衍生物类光引发剂、α-胺基酮衍生物类光引发剂、酰基磷氧化物类光引发剂、含硫光引发剂、二苯甲酮及其衍生物类光引发剂、硫杂蒽酮及其衍生物类光引发剂、蒽醌及其衍生物类光引发剂、芳基重氮盐类光引发剂、二芳基碘鎓盐类光引发剂、三芳基硫鎓盐光 引发剂、芳茂铁盐光引发剂、樟脑醌光引发剂或钛茂类光引发剂中的任意一种或至少两种的混合物；
    可选地，所述硅烷偶联剂为乙烯基类硅烷偶联剂、氯烃基类硅烷偶联剂、氨烃基类硅烷偶联剂、环氧烃基类硅烷偶联剂、甲基丙烯酰氧烷基类硅烷偶联剂、含硫烃基类硅烷偶联剂、拟卤素类硅烷偶联剂或季氨烃基类硅烷偶联剂中的任意一种或至少两种的混合物；
    可选地，所述离子捕捉剂为黄原酸酯类离子捕捉剂、二硫代氨基甲酸盐类衍生物、在水存在下表现出阳离子交换特性的不溶性无机化合物或者具有离子交换功能的阳离子交换树脂和或阴离子交换树脂中的任意一种或至少两种的混合物；
    可选地，所述无机化合物为二价金属氧化物、三价金属氧化物、四价金属氧化物、五价金属氧化物、六价金属氧化物、七价金属氧化物或磷酸金属盐中的任意一种或至少两种的混合物；
    可选地，所选离子交换树脂为苯乙烯系离子交换树脂和/或丙烯酸系离子交换树脂；所述不溶性无机化合物更可选为二氧化硅、磷酸锆和/或磷酸钛；
    可选地，所述抗氧剂为受阻酚类抗氧剂、芳香胺类抗氧剂、亚磷酸酯类抗氧剂、硫醚类抗氧剂或金属钝化剂类抗氧剂中的任意一种或至少两种的混合物；
    可选地，所述光稳定剂为光屏蔽剂类光稳定剂、淬灭剂类光稳定剂、自由基捕获剂类光稳定剂或氢过氧化分解剂类光稳定剂中的任意一种或至少两种的混合物；
    可选地，所述紫外光吸收剂为苯酮类紫外光吸收剂、苯并三唑类紫外光吸收剂、水杨酸酯类紫外光吸收剂、取代丙烯腈类紫外光吸收剂或三嗪类紫外光 吸收剂中的任意一种或至少两种的混合物。
  8. 根据权利要求1-7之一所述的多功能封装胶膜，其中，所述多功能封装胶膜为单层封装胶膜，所述单层封装胶膜包含90-99％的聚合物和1-10％的助剂，所述聚合物为乙烯-醋酸乙烯酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙基-甲基丙烯酸酯共聚物、乙烯-丙烯酸丁酯共聚物、聚乙烯醇缩丁醛、离子聚合物或聚氨酯中的任意一种或至少两种的混合物。
  9. 根据权利要求1-8之一所述的多功能封装胶膜，其中，所述多功能封装胶膜为多层封装胶膜，所述多层封装胶膜包含至少两层封装胶膜，每一层所述封装胶膜包含90-99％的聚合物和1-10％的助剂，所述聚合物为乙烯-醋酸乙烯酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙基-甲基丙烯酸酯共聚物、乙烯-丙烯酸丁酯共聚物、聚乙烯醇缩丁醛、离子聚合物或聚氨酯中的任意一种或至少两种的混合物。
  10. 根据权利要求9所述的多功能封装胶膜，其中，所述多层封装胶膜包括由上至下依次设置的上表层和下表层；
    可选地，所述多层封装胶膜的交联度≥70％；
    可选地，所述多层封装胶膜的可见光透光率≥85％；
    可选地，所述多层封装胶膜的层数为2～5层。
  11. 一种如权利要求1-10之一所述的多功能封装胶膜的制备方法，其中，所述制备方法包括如下步骤：按配比将聚合物和助剂混合，经共挤、淋膜或复合成型，得到所述多功能封装胶膜。
  12. 根据权利要求11所述的制备方法，其中，所述多功能封装胶膜为单层封装胶膜，所述单层封装胶膜的制备方法包括如下步骤：按配比将各层原料混合，经挤出流延、挤出压延、密练压延或行星挤出机压延，制备得到所述单层封装胶膜；
    可选地，所述多功能封装胶膜为多层封装胶膜，所述多层封装胶膜的共挤成型的制备方法包括如下步骤：按配比将各层原料混合，在各自挤出机分别挤出，经分配器分配，模头定型，压花，得到所述多层封装胶膜；
    可选地，所述多层封装胶膜的淋膜成型的制备方法包括如下步骤：按配比将各层原料混合，先将中间层在挤出机挤出，中间层的表面为光面，其余各层按顺序依次在中间层的上下表面进行淋膜，压花，得到所述多层封装胶膜；
    可选地，所述多层封装胶膜的复合成型的制备方法包括如下步骤：按配比将各层原料混合，将各层分别在挤出机中单独挤出成单层膜，各层膜按照设定结构一次层叠，经复合及压花，得到所述多层封装胶膜。
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