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WO2020011105A1 - 一种低流动性封装胶膜 - Google Patents

一种低流动性封装胶膜 Download PDF

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Publication number
WO2020011105A1
WO2020011105A1 PCT/CN2019/094773 CN2019094773W WO2020011105A1 WO 2020011105 A1 WO2020011105 A1 WO 2020011105A1 CN 2019094773 W CN2019094773 W CN 2019094773W WO 2020011105 A1 WO2020011105 A1 WO 2020011105A1
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WIPO (PCT)
Prior art keywords
parts
tert
low
bis
adhesive film
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Application number
PCT/CN2019/094773
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English (en)
French (fr)
Inventor
彭瑞群
穆丹华
侯宏兵
熊曦
周光大
林建华
桑燕
Original Assignee
杭州福斯特应用材料股份有限公司
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Publication of WO2020011105A1 publication Critical patent/WO2020011105A1/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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • C09J123/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J123/0869—Acids or derivatives thereof
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—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 C09J159/00 - C09J187/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • 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
    • 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 invention relates to a photovoltaic material, in particular to a low-fluidity encapsulation film for photovoltaic packaging.
  • crystalline silicon photovoltaic modules have continued to advance in terms of improving module power.
  • the thickness of photovoltaic ribbons has gradually increased from 0.12mm to 0.23 or 0.25mm.
  • Some high-power photovoltaic modules have also introduced reflective tapes, which has led to photovoltaic
  • the module requires that the thickness of the front-layer packaging film be gradually increased.
  • the melting index of conventional packaging film is mostly 20-40g / 10min.
  • crystalline silicon single-glass components have also begun to be laminated; some manufacturers of components with lower automation have increased artificially.
  • Positioning tape solves this problem.
  • the patent CN201711310617.3 with the increasing automation of photovoltaic module manufacturers, due to the constraints of production line layout, most module manufacturers cannot artificially increase the positioning tape.
  • the purpose of the present invention is to provide a low-flow packaging film; the packaging film is cleverly designed, and the low-flow design of the packaging film is used to increase the displacement of the battery sheet. Resistance, combined with the optimization of the lamination process of the module (appropriately shorten the vacuum time and reduce the lamination pressure), can effectively avoid the phenomenon of cell sheet lamination; when the adhesive film is used on the back of the cell sheet, it can also solve the problem of containing pigment The phenomenon of poor anti-corrosion performance of the sealing film.
  • a low-flow encapsulation adhesive film including the following components by weight:
  • the base material is made of ethylene-vinyl acetate copolymer (EVA), metallocene-catalyzed polyethylene, ethylene butene copolymer, ethylene octene copolymer, ethylene pentene copolymer, ethylene methyl acrylate copolymer, ethylene methyl
  • EVA ethylene-vinyl acetate copolymer
  • metallocene-catalyzed polyethylene ethylene butene copolymer
  • ethylene octene copolymer ethylene pentene copolymer
  • ethylene methyl acrylate copolymer ethylene methyl
  • One or more of the methyl acrylate copolymers are mixed and mixed according to any proportion, and the melting index is 0.2-9g / 10min, and the ML value of the low-flow encapsulation film is 0.1-0.75dN ⁇ m.
  • the peroxide-based cross-linking agent is composed of one or more of the following materials mixed at any ratio: tert-butyl isopropylperoxycarbonate, 2,5-dimethyl-2,5 -Bis (tert-butylperoxy) hexane, 1,1, -di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxycarbonate-2-ethyl Hexyl ester, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl ring Hexane, 1,1-bis (tert-pentylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-pentylperoxy) cyclohexane, 1,1-bis (Tert-butylperoxy) cyclo
  • the co-crosslinking agent is composed of one or more of the following materials mixed in any proportion: triallyl isocyanurate, triallyl cyanurate, and trimethylolpropane Triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
  • the hindered amine light stabilizer is composed of one or more of the following materials mixed in an arbitrary ratio: 3,5-di-tert-butyl-4-hydroxy-benzoic acid cetyl ester, tris (1,2,2,6,6-pentamethyl-4-piperidinyl) phosphite, sebacic acid bis-2,2,6,6-tetramethylpiperidinol ester, bis-1- Decaneoxy-2,2,6,6-tetramethylpiperidine-4-ol sebacate, succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine Polymers of pyridyl alcohol, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine, morpholine-2,4,6-tri Polymer of chloro-1,3,5-triazine.
  • the ultraviolet light absorber is composed of one or more of the following materials mixed in any proportion: 2-hydroxy-4-n-octyloxybenzophenone, 2,2-tetramethylenebis (3,1-benzoxazin-4-one), 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2,2'-dihydroxy-4,4'-dimethyl Oxybenzophenone.
  • the tackifier is composed of one or more of the following materials mixed in any proportion: ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane , ⁇ - (2,3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -shrink Glyceryl ether oxypropyltrimethylsilane, 3-aminopropyltrimethylsilane.
  • the pigment is composed of calcium carbonate, barium sulfate, talc, titanium dioxide, zinc oxide, carbon black, graphene, graphene oxide, copper chrome black, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and silica fume.
  • the species or species are composed in any ratio.
  • the encapsulating film can further reduce the fluidity of the lamination process by thermal pre-crosslinking, and the pre-crosslinking degree of the encapsulating film is 0-75%.
  • the low-fluidity encapsulating adhesive film is prepared by the following method: 100 parts by weight of a base material having a melt index of 0.2-9g / 10min, and 0.1-5 parts of a peroxide-based crosslinking agent. , 0.1-5 parts of cross-linking aid, 0.1-3 parts of tackifier, 0-5 parts of hindered amine light stabilizer, 0-2 parts of ultraviolet light absorber, 0-40 parts of pigment are mixed uniformly; add to the extruder
  • the film is extruded through a T-shaped flat die, and thermal pre-crosslinking is performed before or after rewinding.
  • the crosslink method is selected from infrared heating, drying tunnel heating, die heating, and microwave heating.
  • the ML value is obtained. 0.1 to 0.75 dN ⁇ m, with a degree of crosslinking of 0 to 75%.
  • the ML value is preferably 0.15-0.7 dN ⁇ m.
  • the beneficial effects of the present invention are mainly reflected in the following:
  • the packaging adhesive film prepared by using the low-fluidity system formula in the present invention effectively increases the resistance of battery cell displacement, and optimizes the lamination process of the module, thereby greatly reducing the occurrence of battery cells. Probability of lamination phenomenon, to prevent material fluidity at high temperature from contaminating the battery cell, and better heat resistance.
  • the thermal pre-crosslinking method is used to significantly reduce the residue of the acidic material of the encapsulating film, and relatively less corrosion of the module's welding tape, bus bar and battery chip can maintain the high power generation performance of the photovoltaic module for a longer time.
  • the encapsulating film obtained through the above embodiment is applied to the encapsulation of a solar cell module and evaluated by the following test methods.
  • the evaluation results are shown in Table 1:
  • Photovoltaic modules are made of tempered glass (0.32mm), F406P (as front-layer encapsulating film), crystalline silicon cells, and back-layer encapsulation.
  • EVA Ethylene-vinyl acetate copolymer
  • the glue films of all the six examples have no lamination phenomenon, and the shrinkage of the glue films are ⁇ 3%. This ensures that the glue film is applied to photovoltaic modules without the risk of lack of glue due to shrinkage, and all maintain the sealing glue.
  • the film has good corrosion resistance (both power attenuation after HAST aging is ⁇ 5%); while C1 and C2 without thermal pre-crosslinking treatment will have lamination phenomenon, and C3 without thermal pre-crosslinking treatment will have partial shrinkage. High and lack of rubber, C4 using radiation cross-linking will have a significant decline in corrosion resistance (power attenuation after HAST aging has been> 5%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Photovoltaic Devices (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

本发明公开了一种低流动性封装胶膜，它由100重量份熔融指数为0.2-9g/10min的基体材料、0.1-5重量份的过氧化物类交联剂、0.1-5重量份助交联剂、0.1-3重量份增粘剂、0-5重量份受阻胺类光稳定剂、0-2重量份紫外光吸收剂、0-40重量份颜料混合均匀，加入挤出机，通过T形平板模具挤出成膜制得。所述胶膜能够降低光伏组件在层压过程中电池片移位的风险，并防止组件后层含颜料的封装胶膜在高温层压时因流动性好而覆盖到电池片正面；由于采用热预交联的方式，较辐射交联方式，所述胶膜的酸性物质含量显著减少，对组件的焊带、汇流条和电池片的腐蚀相对较少，能更长时间维持光伏组件的高发电性能。

Description

一种低流动性封装胶膜 技术领域
本发明涉及一种光伏材料，尤其涉及一种用于光伏封装的低流动性封装胶膜。
背景技术
近年来，晶硅光伏组件在提高组件功率方面持续前行，其中光伏焊带的厚度逐渐增加，从0.12mm已增至0.23或0.25mm；部分高功率光伏组件同时引入反光贴条，进而导致光伏组件要求前层封装胶膜的厚度逐渐增厚。
目前常规封装胶膜熔融指数大多为20-40g/10min，随着前层封装胶膜的增厚，晶硅单玻组件也开始出现并片现象；部分自动化程度较低的组件制造商通过人为增加定位胶带解决该问题，如专利CN201711310617.3，随着光伏组件制造商自动化程度越来越高，由于产线布局的限制，大多数组件制造商无法人为增加定位胶带。另外，由于组件制造商的层压机及层压工艺的差异，“增加定位胶带防止并片”的方案应用中发现，即使增加定位胶带，组件并片现象仍有较大机率发生，表明该方案并不具有普适性。
另一方面，由于分布式光伏组件的推广应用，光伏组件外观差异性需求日渐显现；封装胶膜体系引入颜料后，为了防止有色胶膜的上溢，优化组件外观目前主要采用将无纺布或玻璃纤维作为隔离层，使用共挤结构，如专利CN201720533068.5和CN201720643870.X，但工艺比较复杂，且使用过程中容易出现胶膜与背板粘结性问题。也有采用辐射交联的方式，降低封装胶膜的流动性，如专利CN201410061051.5，但由于辐射交联过程中，伴有封装胶膜的分解反应，产生的酸性物质会残留在封装胶膜内部，导致光伏组件焊带、汇流条及电池的加速腐蚀，缩短光伏组件高发电性能的运行时间。
鉴于上述状况，目前亟需一种新型的封装胶膜，满足组件对防并片的要求，同时保持封装胶膜抗腐蚀性能良好。
发明内容
为了克服上述现有封装胶膜技术中的缺陷，本发明目的是提供一种低流动性封装胶膜；该封装胶膜设计巧妙，利用封装胶膜的低流动性设计，增加电池片移位的阻力，并结合组件的层压工艺优化(适当缩短抽真空时间，并降低层压压力)，可有效避免发生电池片并片现象；当胶膜用于与电池片背面时，还可以解决含颜料封装胶膜抗腐蚀性能不良的现象。
为了实现上述目的，本发明采用的技术方案是：一种低流动性封装胶膜，包括以下重量份的组份：
Figure PCTCN2019094773-appb-000001
所述基体材料由乙烯-醋酸乙烯酯共聚物(EVA)、茂金属催化聚乙烯、乙烯丁烯共聚物、乙烯辛烯共聚物、乙烯戊烯共聚物、乙烯丙烯酸甲酯共聚物、乙烯甲基丙烯酸甲酯共聚物中的一种或多种按照任意配比混合组成，且其熔融指数为0.2-9g/10min，所述低流动性封装胶膜的ML值为0.1-0.75dN·m。
进一步地，所述过氧化物类交联剂由以下物质中的一种或多种按照任意配比混合组成：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、1，1，-二(叔丁基过氧)-3，3，5-三甲基环己烷、叔丁基过氧化碳酸-2-乙基己酯、2，5-二甲基-2，5-二(叔丁基过氧化)己烷、1,1-双(叔丁基过氧基)-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(叔丁基过氧基)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-双(过氧化苯甲酰)-己烷、过氧化(2-乙基己基)碳酸叔戊酯、过氧化3,5,5三甲基己酸叔丁酯。
进一步地，所述助交联剂由以下物质中的一种或多种按照任意配比混合组成：三烯丙基异氰脲酸酯、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。
进一步地，所述受阻胺类光稳定剂由以下物质中的一种或多种按照任意配比混合组成：3，5-二叔丁基-4-羟基-苯甲酸十六烷基酯、三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯、癸二酸双-2，2，6，6-四甲基哌啶醇酯、双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯、丁二酸和4-羟基-2，2，6，6-四甲基-1-哌啶醇的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺、吗啉-2，4，6-三氯-1，3，5-三嗪的聚合物。
进一步地，所述紫外光吸收剂由以下物质中的一种或多种按照任意配比混合组成：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。
进一步地，所述增粘剂由以下物质中的一种或多种按照任意配比混合组成：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。
进一步地，所述颜料由碳酸钙、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、氢氧化钙、硅灰石、高岭土、蒙脱土、分子筛、立德粉、复合钛白、氧化钙、水滑石、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、苯并氮三唑、碳二亚胺、锌铁黄、钛镍黄、钛铬黄、钴蓝、钴钛绿、钛铬锌棕和硅铁红的一种或多种按照任意比例组成。
进一步地，所述封装胶膜可以通过热预交联的方式进一步降低层压过程的流动性，所述封装胶膜的预交联度为0-75％。
进一步地，所述低流动性封装胶膜通过以下方法制备得到：按重量份数计，将100份熔融指数为0.2-9g/10min的基体材料、0.1-5份的过氧化物类交联剂、0.1-5份助交联剂、0.1-3份增粘剂、0-5份受阻胺类光稳定剂、0-2份紫外光吸收剂、0-40份颜料混合均匀；加入挤出机，通过T形平板模具挤出成膜，在收卷前或收卷后进行热预交联，所述交联方式选自红外加热、烘道加热、模头加热、微波加热，得到ML值为0.1-0.75dN·m，交联度为0-75％的封装胶膜。
进一步地，所述ML值优选为0.15-0.7dN·m。
本发明的有益效果主要体现在：本发明利用低流动性的体系配方设计制得的封装胶膜，有效增加电池片移位的阻力，并结合组件的层压工艺优化，进而大幅降低发生电池片并片现象的机率，防止高温时材料流动性较强而污染电池片，耐热性较好。同时利用热预交联方式，显著减少封装胶膜酸性物质的残留，对组件的焊带、汇流条和电池片的腐蚀相对较少，能更长时间维持光伏组件的高发电性能。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此。
实施例1
Figure PCTCN2019094773-appb-000002
混合均匀；加入挤出机，通过T形平板模具挤出成膜，收卷制得ML值0.12dN·m，的低流动性封装胶膜E1。
实施例2
Figure PCTCN2019094773-appb-000003
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过红外加热装置，收卷制得ML 值0.75dN·m，预交联度为30％的低流动性封装胶膜E2。
实施例3
Figure PCTCN2019094773-appb-000004
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过烘道加热装置，收卷制得ML值0.1dN·m，预交联度为5％的低流动性封装胶膜E3。
实施例4
Figure PCTCN2019094773-appb-000005
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过微波加热装置，收卷制得ML值0.7dN·m，交联度为75％的低流动性封装胶膜E4。
实施例5
Figure PCTCN2019094773-appb-000006
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过模头加热装置，收卷制得ML值0.35dN·m，交联度为10％的低流动性封装胶膜E5。
实施例6
Figure PCTCN2019094773-appb-000007
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过微波加热装置，收卷制得ML值0.35dN·m，交联度为2％的低流动性封装胶膜E6。
对比例1
Figure PCTCN2019094773-appb-000008
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过模头加热装置，收卷制得ML值0.08dN·m封装胶膜C1。
对比例2
Figure PCTCN2019094773-appb-000009
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过模头加热装置，收卷制得ML值0.09dN·m封装胶膜C2。
对比例3
Figure PCTCN2019094773-appb-000010
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过模头加热装置，收卷制得ML值0.2dN·m封装胶膜C3。
对比例4
Figure PCTCN2019094773-appb-000011
混合均匀；加入挤出机，通过T形平板模具挤出成膜，通过电子束辐射交联，收卷制得ML值0.4dN·m，预交联度为55％的封装胶膜C4。
性能测试
通过上述实施例得到的封装胶膜应用于太阳能电池组件的封装，经下述测试方法进行评价，评价结果列于表1：
1、封装胶膜交联度
测试方法参考国家标准GB/T29848-2013《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》交联度的测定部分。
2、封装双玻组件外观评估
使用封装胶膜进行双玻组件封装试验，按玻璃/透明胶膜/电池片/防并片封装胶膜/玻璃的次序放入真空层压机内，在150℃，先抽真空后加压，共固化15分钟。观察双玻组件电池片串偏移距离和并片现象。
3、光伏组件的发电性能
将上述封装胶膜(E1-E5，C1-C4)均作为背层封装胶膜，光伏组件由钢化玻璃(0.32mm)，F406P(作为前层封装胶膜)，晶硅电池片，背层封装胶膜(E1-E5，C1-C4)和BEC301背板(作为背板材料)构成。通过真空层压机，在145℃下，抽真空5min，分别加压30s(61kPa)，30s(81kPa)，最后保压12min(101kPa)制得。测试光伏组件HAST(105℃，100％RH，1.3atm，192h)老化前后的功率。
4、封装胶膜收缩率
测试方法参考国家标准GB/T29848-2013《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》收缩率的测定部分。
表1：实施例与比较例制得的封装性能比较
Figure PCTCN2019094773-appb-000012
由上表1可见，6个实施例胶膜均无并片现象，同时胶膜收缩率均≤3％，保证胶膜应用到光伏组件中无因收缩而缺胶的风险，并均保持封装胶膜良好的抗腐蚀性能(HAST老化后功 率衰减均<5％)；而未经热预交联处理的C1和C2会存在并片现象，未经热预交联处理的C3会存在收缩率偏高而发生缺胶现象，采用辐射交联的C4会存在抗腐蚀性能显著下降现象(HAST老化后功率衰减已>5％)。
最后应该说明的是：以上实施例仅用以说明本发明而非限制本发明所描述的技术方案；因此，尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明，但是，本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换；而一切不脱离本发明精神和范围的技术方案及其改进，其均应覆盖在本发明的权利要求范围中。

Claims (10)

  1. 一种低流动性封装胶膜，其特征在于，包括以下重量份的组份：
    Figure PCTCN2019094773-appb-100001
    所述基体材料由乙烯-醋酸乙烯酯共聚物、茂金属催化聚乙烯、乙烯丁烯共聚物、乙烯辛烯共聚物、乙烯戊烯共聚物、乙烯丙烯酸甲酯共聚物、乙烯甲基丙烯酸甲酯共聚物中的一种或多种按照任意配比混合组成，且其熔融指数约为0.2-9g/10min，所述低流动性封装胶膜的ML值约为0.1-0.75dN·m。
  2. 根据权利要求1所述一种低流动性封装胶膜，其特征在于，所述过氧化物类交联剂由以下物质中的一种或多种按照任意配比混合组成：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、1，1，-二(叔丁基过氧)-3，3，5-三甲基环己烷、叔丁基过氧化碳酸-2-乙基己酯、2，5-二甲基-2，5-二(叔丁基过氧化)己烷、1,1-双(叔丁基过氧基)-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(叔丁基过氧基)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-双(过氧化苯甲酰)-己烷、过氧化(2-乙基己基)碳酸叔戊酯、过氧化3,5,5三甲基己酸叔丁酯。
  3. 根据权利要求1所述一种低流动性封装胶膜，其特征在于，所述助交联剂由以下物质中的一种或多种按照任意配比混合组成：三烯丙基异氰脲酸酯、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。
  4. 根据权利要求1所述一种低流动性封装胶膜，其特征在于，所述受阻胺类光稳定剂由以下物质中的一种或多种按照任意配比混合组成：3，5-二叔丁基-4-羟基-苯甲酸十六烷基酯、三(1，2，2，6，6-五甲基-4-哌啶基)亚磷酸酯、癸二酸双-2，2，6，6-四甲基哌啶醇酯、双-1-癸烷氧基-2，2，6，6-四甲基哌啶-4-醇癸二酸酯、丁二酸和4-羟基-2，2，6，6-四甲基-1-哌啶醇的聚合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)-1，6-己二胺、吗啉-2，4，6-三氯-1，3，5-三嗪的聚合物；所述紫外光吸收剂由以下物质中的一种或多种按照任意配比 混合组成：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。
  5. 根据权利要求1所述一种低流动性封装胶膜，其特征在于，所述增粘剂由以下物质中的一种或多种按照任意配比混合组成：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。
  6. 根据权利要求1所述一种低流动性封装胶膜，其特征在于，所述颜料由碳酸钙、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、氢氧化钙、硅灰石、高岭土、蒙脱土、分子筛、立德粉、复合钛白、氧化钙、水滑石、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、苯并氮三唑、碳二亚胺、锌铁黄、钛镍黄、钛铬黄、钴蓝、钴钛绿、钛铬锌棕和硅铁红的一种或多种按照任意比例混合组成。
  7. 根据权利要求1-6任一项所述一种低流动性封装胶膜，其特征在于，所述封装胶膜可以通过热预交联的方式进一步降低层压过程的流动性，所述封装胶膜的预交联度为0-75％。
  8. 根据权利要求7所述一种低流动性封装胶膜其特征在于，热交联的方式可以是红外加热、烘道加热、模头加热、微波加热。
  9. 根据权利要求1所述的一种低流动性封装胶膜，其特征在于，所述低流动性封装胶膜通过以下方法制备得到：按重量份数计，将100份熔融指数为0.2-9g/10min的基体材料、0.1-5份的过氧化物类交联剂、0.1-5份助交联剂、0.1-3份增粘剂、0-5份受阻胺类光稳定剂、0-2份紫外光吸收剂、0-40份颜料混合均匀；加入挤出机，通过T形平板模具挤出成膜，在收卷前或收卷后进行热预交联，所述交联方式选自红外加热、烘道加热、模头加热、微波加热，得到ML值为0.1-0.75dN·m，交联度为0-75％的封装胶膜。
  10. 根据权利要求1-8任意一项权利要求所述的一种低流动性封装胶膜，其特征在于，所述ML值优选为0.15-0.7dN·m。
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