CN113528046A - High-adhesion high-weather-resistance coating type solar cell backboard and preparation method thereof - Google Patents
High-adhesion high-weather-resistance coating type solar cell backboard and preparation method thereof Download PDFInfo
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- CN113528046A CN113528046A CN202110733469.6A CN202110733469A CN113528046A CN 113528046 A CN113528046 A CN 113528046A CN 202110733469 A CN202110733469 A CN 202110733469A CN 113528046 A CN113528046 A CN 113528046A
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
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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
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- 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
Abstract
The invention belongs to the technical field of solar cell back plates, and particularly relates to a high-adhesion high-weather-resistance coating type solar cell back plate and a preparation method thereof. Wherein the solar cell back sheet comprises: the composite material comprises a base resin layer, and a super weather-proof fluororesin polymer alloy layer and a high-adhesion fluoropolymer layer which are respectively attached to the two surfaces of the base resin layer. According to the high-adhesion high-weather-resistance coating type solar back plate, the modified acrylic resin is added into the high-adhesion fluorine-containing polymer layer, and the side chain of the modified acrylic resin contains the alkoxysilane group, so that the weather resistance and the acid resistance of the high-adhesion fluorine-containing polymer layer can be improved, the adhesion force between the solar cell back plate and a photovoltaic adhesive film is further improved, the high-adhesion high-weather-resistance coating type solar back plate has high weather resistance, and the solar cell back plate can be used for a long time.
Description
Technical Field
The invention belongs to the technical field of solar cell back plates, and particularly relates to a high-adhesion high-weather-resistance coating type solar cell back plate and a preparation method thereof.
Background
In recent years, efficient module technology has been highly desired in a cost-down roadmap of the photovoltaic industry chain. Revolutionary high-efficiency technologies such as half-piece, double-glass, multi-main-grid, lamination, splicing and the like are endless, and particularly, the splicing technology grown in 2019 greatly changes the interconnection materials and the cell spacing of photovoltaic modules on the basis of the MBB technology, and various discussion wave tides are brought up in the industry.
Through set up diffuse reflection structure like white EVA glued membrane, white high back of the body glass etc. in photovoltaic module battery interval, make shine the light secondary reflection of battery interval department on the battery piece, make full use of clearance light, promote subassembly power. However, the conventional EVA adhesive film is transparent, and in order to increase the reflectivity, a certain amount of high-reflection whitening filler such as titanium dioxide is generally added, but the addition of titanium dioxide can reduce the bond energy between the silane coupling agent and the glass or the back plate, and when the titanium dioxide is added to a certain amount, the formation of chemical bonds between the silane coupling agent and the glass or the back plate can be hindered, so that the peeling strength between the back plate or the glass and the EVA adhesive film is reduced, the delamination phenomenon between the back plate and the glass or the back plate can occur, and the service life of the assembly is directly influenced.
The solar cell backboard mainly has the advantages that the solar cell backboard is bonded with the EVA adhesive film, the overall mechanical strength of the solar cell panel is improved, and in addition, water vapor can be prevented from permeating into the sealing layer to affect the service life of the cell. The adhesive force between the back plate and the EVA adhesive film directly influences the service life of the assembly. In order to improve the adhesion performance of the back plate, a great number of improvements to the back plate have been proposed in the prior art. For example, the invention patent with publication number CN101177514A discloses a solar cell back sheet, which comprises a base material and a fluoropolymer layer, wherein the fluoropolymer layer comprises the following components in parts by weight: 25-45 parts of fluorine-containing resin; 1.5-3 parts of modified resin; 0.5-3 parts of polymer filler; 0.1-1 part of inorganic filler; 50-70 parts of a solvent. Most of the fluoropolymer layers in the scheme are made of fluorine materials, and although the fluorine materials can improve the weather resistance of the backboard, due to the characteristics of the fluorine materials, the use of a large amount of fluorine materials can cause the surface energy to be high and the surface to be hydrophobic, so that the bonding performance is poor.
Disclosure of Invention
The invention provides a high-adhesion high-weather-resistance coating type solar cell backboard and a preparation method thereof.
In order to solve the above technical problem, the present invention provides a solar cell back sheet, including: the composite material comprises a base resin layer, and a super weather-proof fluororesin polymer alloy layer and a high-adhesion fluoropolymer layer which are respectively attached to the two surfaces of the base resin layer.
In a second aspect, the present invention also provides a method for preparing a solar cell back sheet, including the following steps: mixing the raw materials of the high-adhesion fluorine-containing polymer layer, grinding and dispersing to obtain a high-adhesion fluorine-containing polymer coating liquid; mixing the raw materials of the super weather-proof fluororesin polymer alloy layer, extruding and granulating, and preparing the super weather-proof fluororesin polymer alloy layer film in a casting or film blowing mode; performing double-sided corona treatment on the matrix resin layer to activate the surface of the matrix resin layer, coating the high-adhesion fluoropolymer coating liquid on one surface of the activated matrix resin layer, and heating and baking to form a high-adhesion fluoropolymer layer; coating a polymer adhesive coating liquid on the other surface of the activated matrix resin layer, and heating and baking to form a polymer adhesive layer; and attaching the super weather-proof fluororesin polymer alloy layer film subjected to double-sided corona to the other surface of the high-molecular adhesive layer, and performing curing reaction to obtain the solar cell backboard.
The modified acrylic resin has the beneficial effects that the hydroxyl value is 10-30, the acid value is not more than 4, the glass transition temperature is not lower than 30 ℃, and the weight-average molecular weight is 20000-50000 g/mol; and when the solid content is not less than 60wt%, the viscosity of the modified acrylic resin at 25 ℃ is 2000-4000 mPa & s; when the high-adhesion high-weather-resistance coating type solar back plate is used, the yellowing resistance of the solar cell back plate can be improved, and the high-weather-resistance coating type solar back plate has high weather resistance and can be used for a long time; in the high-adhesion high-weather-resistance coating type solar cell back plate, the super-weather-resistance fluororesin polymer alloy layer has super-weather resistance by adding the low-temperature-resistant toughening agent, and also has super-low temperature property, and the aging TC600 is not cracked, so that the solar cell back plate has the function of protecting a solar cell for a long time.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural view of a solar cell back sheet of the present invention.
In the figure:
1-super weather-proof fluororesin polymer alloy layer; 2-a matrix resin layer; 3-high adhesion fluoropolymer layer; 4-a polymer adhesive layer.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Although the fluorine material can improve the weather resistance of the back plate, due to the characteristics of the fluorine material, the use of a large amount of fluorine material can cause high surface energy and hydrophobic surface, which leads to poor adhesive property, so that the adhesive property between the back plate and the EVA is reduced, especially the adhesive force with a high-reflection white EVA adhesive film is extremely poor, which leads to the reduction of the peeling strength between the back plate and the EVA adhesive film, the delamination phenomenon occurs, and the service life of the assembly is influenced.
In order to solve the above technical problem, as shown in fig. 1, the present invention provides a solar cell back sheet, including: a base resin layer 2, and a super weather-resistant fluororesin polymer alloy layer 1 and a high-adhesion fluoropolymer layer 3 respectively bonded to both surfaces of the base resin layer 2.
Optionally, the high-adhesion fluoropolymer layer 3 may be, but is not limited to, coated on the surface of the base resin layer 2 by means of coating and curing, so as to improve the adhesive strength between the base resin layer and the EVA adhesive film.
Optionally, the super weather-resistant fluororesin polymer alloy layer 1 and the base resin layer 2 may be, but not limited to, attached by a high molecular adhesive layer 4; the two surfaces of the super-weather-resistant fluororesin polymer alloy layer 1 and the matrix resin layer 2 are subjected to corona treatment to improve the bonding between the super-weather-resistant fluororesin polymer alloy layer and the high-molecular adhesive layer 4 and further improve the bonding fastness of the back plate, so that the back plate with excellent barrier property, moisture resistance, electrical property and weather resistance is prepared.
Alternatively, the main component of the matrix resin layer 2 may be, but is not limited to, polyethylene terephthalate (PET), polypropylene (PP), Polyethylene (PE), or a polyolefin material in which PP and PE are blended; the thickness of the matrix resin layer 2 can be but is not limited to 0.1-10 mm; when PET is used as a matrix resin material, the thickness of the matrix resin layer 2 is preferably 0.2-0.3 mm, and the specific value can be 0.2mm, 0.22mm, 0.25mm, 0.28mm or 0.3 mm; when the polyolefin material is a matrix resin material, the thickness of the matrix resin layer 2 is preferably 1 to 3mm, and the specific value may be 1mm, 2mm or 3 mm.
Alternatively, the super weatherable fluororesin polymer alloy layer 1 may include, but is not limited to, the following components in parts by mass: 30-70 parts of PVDF resin; 1-20 parts of an inorganic filler A; 1-20 parts of a low temperature resistant toughening agent; and 0.1-2 parts of functional auxiliary agent.
Optionally, the super-weather-resistant fluororesin polymer alloy layer 1 is suitable for a fluorine-containing thin film prepared by mixing PVDF resin, an inorganic filler, a low-temperature-resistant toughening agent and a functional auxiliary agent, then extruding and granulating, and then casting or blowing a film. The thickness of the super weather-proof fluororesin polymer alloy layer 1 can be but not limited to 0.01-0.05 mm, and can be specifically selected from 0.01mm, 0.02mm, 0.03mm, 0.04mm or 0.05 mm.
Optionally, the low temperature resistant toughening agent is a toughening agent with a core-shell structure, and may be one or more of the following toughening agents: (i) the core layer is butadiene-styrene rubber, and the shell is a polymethyl methacrylate toughening agent; (ii) the core layer is organic silicon, and the shell is a toughening agent of methyl methacrylate; (iii) the core layer is acrylate and the shell is methyl methacrylate toughening agent.
The low temperature resistant toughening agent is a toughening agent with a core-shell structure, wherein a core layer can provide excellent low temperature resistance and weather resistance, and a shell layer can provide compatibility and thermal stability.
Alternatively, the PVDF resin may be, but is not limited to, a vinylidene fluoride homopolymer; the functional assistant may include, but is not limited to, one or more of an antioxidant, an anti-aging agent, a light stabilizer, a light absorber, and a coupling agent, so that the super-weatherproof fluororesin polymer alloy layer has the properties of oxidation resistance, ultraviolet resistance, aging resistance, and the like, and the weatherability thereof is improved. Wherein the antioxidant can be hindered phenols, the light stabilizer can be hindered amines, the light absorber can be benzophenones or benzotriazoles, and the coupling agent can be silane coupling agent.
Optionally, the inorganic filler a may include, but is not limited to, one or more of titanium dioxide, zinc sulfide, barium sulfate, calcium carbonate, and silicon dioxide; the inorganic filler has an average particle diameter of 0.01 to 20 μm. The inorganic filler can play a role in reinforcing and can also improve the weather resistance.
Optionally, the high adhesion fluoropolymer layer 3 may include, but is not limited to, the following components in parts by mass: 25-45 parts of fluorine-containing resin; 15-40 parts of modified acrylic resin; 3-10 parts of adhesion promoting resin; 10-30 parts of an inorganic filler B; 0.1-5 parts of an auxiliary agent; 1-10 parts of a curing agent; and 15-50 parts of a solvent.
Optionally, the modified acrylic resin comprises: an alkoxysilane group located on a side chain of the modified acrylic resin; and a reactive group comprising at least one of a hydroxyl group or an amine group.
Specifically, the alkoxysilane groups are hydrolyzable groups, and the alkoxysilane groups are partially hydrolyzed during a short baking and curing process during preparation of the back sheet to generate silicon hydroxyl groups, and a condensation reaction is generated among the silicon hydroxyl groups to generate a siloxane structure of silicon-oxygen-silicon, so that the weather resistance and acid resistance of the bonded fluoropolymer layer can be improved; in the lamination process of the back plate, the alkoxy silane groups which are not hydrolyzed can form hydrogen bonds with hydroxyl on the surface of titanium dioxide in the white EVA adhesive film, so that the high-adhesion fluoropolymer layer has high adhesion to white EVA.
Optionally, the structural formula of the modified acrylic resin is as follows:
Optionally, the hydroxyl value of the modified acrylic resin can be but is not limited to 10-30, and the acid value is not more than 4.
Optionally, the glass transition temperature of the modified acrylic resin is not lower than 30 ℃, and the weight average molecular weight can be, but is not limited to, 20000-50000 g/mol.
Alternatively, when the solid content is not less than 60wt%, the viscosity of the modified acrylic resin at 25 ℃ may be, but is not limited to, 2000 to 4000 mPa · s.
Specifically, the hydroxyl value of the modified acrylic resin is 10-30, the acid value is not more than 4, the glass transition temperature is not lower than 30 ℃, and the weight-average molecular weight is 20000-50000 g/mol; and when the solid content is not less than 60wt%, the viscosity of the modified acrylic resin at 25 ℃ is 2000 to 4000 mPa · s. The modified polyvinyl chloride resin composition is used for a solar cell, can improve the yellowing resistance of a solar cell back plate, has high weather resistance, and can be used for a long time.
Alternatively, the adhesion promoting resin may be, but is not limited to, a modified chlorinated polyolefin or a rosin resin; may be a silicone-free polymer solution, preferably ADK adhesion promoter, manufactured by hamming squat corporation.
Optionally, the inorganic filler B may include, but is not limited to, one or more of titanium dioxide, carbon black, calcium carbonate, nano-silica, and kaolin.
Optionally, the auxiliary agent may include, but is not limited to, one or more of a dispersant, a catalyst, a coupling agent, and a matting agent; wherein the dispersant may be, but not limited to, a pigment affinity group-containing block copolymer-based dispersant, an acrylic block copolymer-based dispersant, or an acidic group-containing copolymer-based dispersant; the catalyst may be, but is not limited to, dibutyltin dilaurate, dioctyltin dilaurate, monobutyltin oxide, or stannous octoate; the coupling agent may be, but is not limited to, a silane-based coupling agent; the matting powder may be, but is not limited to, a silica matting powder.
Optionally, the curing agent can include but is not limited to one or more of aliphatic isocyanate, amino resin, blocked isocyanate and blocked isocyanate; the solvent may be, but is not limited to, xylene, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate.
Optionally, the thickness of the polymer adhesive layer may be, but not limited to, 0.005 to 0.03mm, preferably 0.01 to 0.02mm, and specifically may be selected from 0.005mm, 0.01mm, 0.015mm, 0.02mm, 0.025mm, or 0.03 mm.
Further, the invention also provides a preparation method of the solar cell back plate, which comprises the following steps: mixing the raw materials of the high-adhesion fluoropolymer layer 3, grinding and dispersing to obtain a high-adhesion fluoropolymer coating liquid; mixing the raw materials of the super weather-proof fluororesin polymer alloy layer 1, extruding and granulating, and preparing a super weather-proof fluororesin polymer alloy layer film in a casting or film blowing mode; performing double-sided corona treatment on the matrix resin layer 2 to activate the surface of the matrix resin layer, coating the high-adhesion fluoropolymer coating liquid on one surface of the activated matrix resin layer 2, and heating and baking to form a high-adhesion fluoropolymer layer 3; coating a polymer adhesive coating liquid on the other surface of the activated matrix resin layer 2, and heating and baking to form a polymer adhesive layer 4; and attaching the super weather-proof fluororesin polymer alloy layer film subjected to double-sided corona to the other surface of the high-molecular adhesive layer 4, and performing curing reaction to obtain the solar cell backboard.
Specifically, after the fluorine-containing resin, the modified acrylic resin, the dispersant and the solvent in the raw material of the high-adhesion fluorine-containing polymer layer 3 are stirred and pre-dispersed in a container, the inorganic filler B is added, and then the mixture is ground by a sand mill until the particle fineness is less than or equal to 2 microns; adding adhesion promoting resin and an auxiliary agent, adding a curing agent after dispersing and stirring, and dispersing and filtering to obtain a high-adhesion fluoropolymer layer coating liquid; mixing the PVDF resin, the inorganic filler, the low-temperature resistant toughening agent and the functional auxiliary agent in the raw material of the super-weather-resistant fluororesin polymer alloy layer 1, then extruding and granulating, and preparing the super-weather-resistant fluororesin polymer alloy layer film in a casting or film blowing mode; performing double-sided corona treatment on the matrix resin layer 2 to activate the surface of the matrix resin layer, coating the high-adhesion fluoropolymer coating liquid on one surface of the matrix resin layer 2, and heating and baking at 80-170 ℃ for 20-200 s to form a high-adhesion fluoropolymer layer 3; coating a polymer adhesive coating liquid on the other surface of the activated matrix resin layer 2, and heating and baking at 80-170 ℃ for 20-200 s to form a polymer adhesive layer 4; and (3) attaching the super weather-proof fluororesin polymer alloy layer film subjected to double-sided corona to the other surface of the high-molecular adhesive layer 4, and carrying out curing reaction at 45-60 ℃ for 48-72 hours to obtain the solar cell backboard.
Optionally, the preparation method of the modified acrylic resin comprises the following steps: s1, uniformly mixing the acrylic resin composition and the chain transfer agent, and adding the mixture into a dropping container to prepare a first dropping solution; adding an initiator into a second dripping container to prepare second dripping liquid; s2, adding xylene, toluene and butyl acetate into a reaction container, and dropwise adding the first drop of liquid into the reaction container to obtain a reaction mixed liquid; and S3, heating the reaction mixed solution, preserving heat, cooling, adding an initiator, performing reflux reaction, and cooling to obtain the modified acrylic resin.
Specifically, the acrylic resin composition and the chain transfer agent are uniformly mixed and added into a first titration funnel; adding an initiator to a second titration funnel; and (2) filling xylene, toluene and butyl acetate into a glass reaction flask with a stirring reflux condenser, heating to 140 ℃ under a stirring state, preserving heat for 0.5h, then slowly dropwise adding the first addition liquid in the first titration funnel, controlling the dropwise adding time to be 3h, preserving heat for 0.5h after dropwise adding is finished, cooling to 80 ℃, dropwise adding an initiator in the second titration funnel, and carrying out reflux reaction for 2 h.
Wherein, optionally, the acrylic resin composition can include, but is not limited to, the following components in parts by mass: methyl methacrylate: 1-35 parts; acrylic acid: 1-25 parts; butyl methacrylate: 1-40 parts; and hydroxypropyl methacrylate: 1-15 parts; and vinyl group-containing alkoxysilane compounds: 1-10 parts.
Optionally, the feeding sequence of the acrylic resin composition is as follows: methyl methacrylate, acrylic acid, butyl methacrylate, hydroxypropyl methacrylate and vinyl-containing alkoxysilane compounds.
Alternatively, the vinyl group-containing alkoxysilane compound may include, but is not limited to: at least one of vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane and oligomers thereof.
Specifically, the reaction formula for preparing the modified acrylic resin is
Preparation example of modified acrylic resin
Sequentially mixing 29 parts by mass of methyl methacrylate, 13 parts by mass of acrylic acid, 18 parts by mass of butyl methacrylate, 15 parts by mass of hydroxypropyl methacrylate, 10 parts by mass of vinyl methyl dimethoxysilane and 12 parts by mass of mercaptoethanol uniformly, and adding the mixture into a first titration funnel; adding an initiator to a second titration funnel; placing dimethylbenzene, methylbenzene and butyl acetate into a glass reaction flask with a stirring reflux condenser, heating to 140 ℃ under a stirring state, preserving heat for 0.5h, then slowly dropwise adding a first addition liquid in a first dropping funnel, controlling the dropwise adding time to be 3h, preserving heat for 0.5h after dropwise adding is finished, cooling to 80 ℃, adding azobisisobutyronitrile, and continuing to carry out reflux reaction for 2 h; the hydroxyl value of the reaction solution was checked to be 18, the acid value was 2, the molecular weight was 33000g/mol, the viscosity was 2700 mPas, and the glass transition temperature was 37 ℃ to obtain a modified acrylic resin.
Preparation example 1 of super weather-resistant fluororesin polymer alloy layer
65 parts by mass of PVDF resin, 14 parts by mass of nano titanium dioxide, 3 parts by mass of nano calcium carbonate, 1 part by mass of nano silicon dioxide, 15 parts by mass of low temperature resistant toughening agent (the core is acrylic ester and the shell is methyl methacrylate), 0.5 part by mass of antioxidant, 0.3 part by mass of light stabilizer, 0.6 part by mass of light absorbent and 0.6 part by mass of coupling agent are mixed and then extruded for granulation, and then the super weather-resistant fluororesin polymer alloy layer film is prepared in a tape casting manner.
Preparation example 2 of super weather-resistant fluororesin polymer alloy layer
70 parts by mass of PVDF resin, 11 parts by mass of nano titanium dioxide, 4 parts by mass of barium sulfate, 0.5 part by mass of nano silicon dioxide, 12.5 parts by mass of low temperature resistant toughening agent (acrylic ester as a core and methyl methacrylate as a shell), 0.3 part by mass of antioxidant, 0.2 part by mass of anti-aging agent, 0.4 part by mass of light stabilizer, 0.4 part by mass of light absorber and 0.7 part by mass of coupling agent are mixed, extruded and granulated, and then the super weather-resistant fluororesin polymer alloy layer film is prepared by a tape casting mode.
Preparation example 1 of highly adhesive fluoropolymer layer
40 parts by mass of a fluorine-containing resin GK570 (Japan gold), 30 parts by mass of a modified acrylic resin prepared in the preparation example of the modified acrylic resin, 3 parts by mass of a dispersant BYK111 (Germany Bike chemical), 30 parts by mass of butyl acetate and 5 parts by mass of xylene are stirred and pre-dispersed in a container for 10min, 20 parts by mass of titanium dioxide R960 (U.S. DuPont) is added, the mixture is ground for 3h by a sand mill until the particle fineness is less than or equal to 2 μm, 3 parts by mass of an adhesion promoting resin ADK (Hamming Siemens de Mount), 1 part by mass of a coupling agent KH560 (Germany Bikko Haichi), 0.5 part by mass of a catalyst dibutyltin dilaurate (Allantin reagent) and 0.1 part by mass of an extinction powder TSA250 (Guangzhou Ling) are added, 5 parts by mass of a curing agent Z4470 (Germany Bayer) is added after high-speed dispersion and stirring at 3000rpm, and high-speed dispersion is carried out, and then the high-adhesion fluorine-containing polymer layer coating liquid is obtained by filtration, storing in a dry sealed container for later use.
Preparation example 2 of highly adhesive fluoropolymer layer
25 parts by mass of a fluorine-containing resin ZHM-2 (Shanghai Dongfeng fluorine), 40 parts by mass of the modified acrylic resin obtained in the preparation example of the modified acrylic resin, 3 parts by mass of a dispersant BYK163 (Germany Bikk chemical), 45 parts by mass of butyl acetate were stirred in a vessel and pre-dispersed for 10 minutes, adding 15 parts by mass of titanium pigment CR506 (in the Jinzhou titanium industry), grinding for 3 hours by using a sand mill until the particle fineness is less than or equal to 2 mu m, adding 5 parts by mass of adhesion promoting resin ADK (Hamming modesty), 0.5 part by mass of coupling agent KH550 (Nanjing austic), 0.3 part by mass of catalyst dioctyltin dilaurate (Aladdin reagent) and 0.2 part by mass of extinction powder TSA230 (Guangzhou Ling), dispersing and stirring at a high speed of 3000rpm, finally adding 5 parts by mass of curing agent N3390 (Germany Bayer), dispersing at a high speed of 1000rpm, filtering to obtain a high-adhesion fluoropolymer layer coating liquid, and storing in a dry sealed container for later use.
Preparation example 3 of highly adhesive fluoropolymer layer
30 parts by mass of fluorine-containing resin ZHM-5 (Shanghai Dongfeng), 25 parts by mass of modified acrylic resin prepared in the preparation example of the modified acrylic resin, 2.5 parts by mass of dispersant BYK163 (Germany Bike chemical), 45 parts by mass of butyl acetate and 10 parts by mass of propylene glycol methyl ether acetate are stirred and pre-dispersed for 10min in a container, 10 parts by mass of titanium dioxide R-5566 (Oriental titanium industry) are added, then a sand mill is used for grinding for 3h until the particle fineness is less than or equal to 2 mu m, 5 parts by mass of adhesion promoting resin ADK (Hamming Sommed), 1 part by mass of coupling agent KH560 (Germany Bikko Culcite), 0.1 part by mass of curing agent dibutyltin dilaurate (Allatin reagent) and 0.15 parts by mass of extinction powder OK412 (Yinggugsai) are added, 5 parts by mass of curing agent D120N (Japan Triwell) are added after high-speed dispersion and stirring at 3000rpm, and high-viscosity fluoropolymer layer coating liquid is obtained by filtering after high-speed dispersion at 1000rpm, storing in a dry sealed container for later use.
Example 1
Selecting a 275-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 1 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 2min at 170 ℃ by using a circulating oven, and primarily drying and curing to obtain a 5-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Weiston, Changzhou) is coated, drying is carried out for 3min at 100 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 8 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 1 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain the solar backboard product A.
Example 2
Selecting a 275-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 2 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 2min at 160 ℃ by using a circulating oven, and primarily drying and curing to obtain a 10-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Wuhan Daorhui) is coated, the PET basal membrane is dried for 2min at 110 ℃ by a circulating oven to prepare a high molecular adhesive layer with the thickness of 9 mu m, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 2 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together to prepare a finished product of the solar backboard. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product B.
Example 3
Selecting a 275-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 3 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 1min at 170 ℃ by using a circulating oven, and primarily drying and curing to obtain a 15-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Shanghai product eagle) is coated, the drying is carried out for 2min at 100 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 10 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 1 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product C.
Example 4
Selecting a 280-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 1 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 1.5min by using a circulating oven at 170 ℃, and carrying out primary drying and curing to obtain a 10-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Weiston, Changzhou) is coated, the drying is carried out for 2min at 110 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 8 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 1 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product D.
Example 5
Selecting a PET film with the thickness of 250 microns, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 1 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 2min at 160 ℃ by using a circulating oven, and primarily drying and curing to obtain a 5-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other side of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Weiston, Changzhou) is coated, drying is carried out for 2min at 130 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 10 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 2 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product E.
Comparative example 1
Referring to example 1, a PET base film having a thickness of 275 μm was used in comparative example 1, and the modified acrylic resin was replaced with a conventional acrylic resin in the formulation of the high adhesion fluoropolymer layer, with the other parameters being unchanged;
(1) preparation of high-adhesion fluoropolymer layer coating liquid
40 parts by mass of a fluorine-containing resin GK570 (Japan gold), 30 parts by mass of an acrylic resin (Allantin reagent), 3 parts by mass of a dispersant BYK111 (Germany Bikk chemical), 30 parts by mass of butyl acetate and 5 parts by mass of xylene were stirred in a vessel and predispersed for 10 minutes, adding 20 parts by mass of titanium dioxide R960 (DuPont, USA), grinding for 3h with a sand mill until the particle fineness is less than or equal to 2 μm, adding 3 parts by mass of adhesion promoting resin ADK (Hamming modesty), 1 part by mass of coupling agent KH560 (Nanjing Ouchi, Beike, Germany), 0.5 part by mass of catalyst dibutyltin dilaurate (Allatin reagent), 0.1 part by mass of matting powder TSA250 (Ling, Guangzhou), dispersing and stirring at a high speed of 3000rpm, finally adding 5 parts by mass of a curing agent Z4470 (German Bayer), dispersing at a high speed of 1000rpm, filtering to obtain a high-adhesion fluoropolymer layer coating liquid, and storing in a dry sealed container for later use.
(2) Making a backing plate
Selecting a 275-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting a corona device, coating the high-adhesion fluorine-containing polymer layer coating liquid prepared in the comparative example 1 on the corona-treated surface of the PET base film, and drying the PET base film coating liquid for 2min at 170 ℃ by using a circulating oven for primary drying and curing to prepare a 5-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Weiston, Changzhou) is coated, drying is carried out for 3min at 100 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 8 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the preparation example 1 of the super weather-resistant fluororesin polymer alloy layer which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product F.
Comparative example 2
Referring to example 4, a PET base film with a thickness of 280 μm is adopted in comparative example 2, and a low temperature resistant toughening agent in the formula of the super weather-resistant fluororesin polymer alloy layer is replaced by a conventional fluorine film toughening agent PMMA, and other parameters are unchanged;
(1) preparation of super weather-proof fluororesin polymer alloy layer
Mixing 65 parts by mass of PVDF resin, 14 parts by mass of nano titanium dioxide, 3 parts by mass of nano calcium carbonate, 1 part by mass of nano silicon dioxide, 15 parts by mass of a fluorine film toughening agent PMMA, 0.5 part by mass of an antioxidant, 0.3 part by mass of a light stabilizer, 0.6 part by mass of a light absorber and 0.6 part by mass of a coupling agent, extruding and granulating, and then preparing the super-weather-resistant fluorine resin polymer alloy layer film in a casting manner.
(2) Making a backing plate
Selecting a 280-micron-thick PET film, carrying out corona treatment on one surface of the PET film to 50-60 dyne/cm by adopting corona equipment, coating the high-adhesion fluorine-containing polymer prepared in the preparation example 1 of the high-adhesion fluorine-containing polymer layer on the corona-treated surface of the PET base film, drying the high-adhesion fluorine-containing polymer layer for 1.5min by using a circulating oven at 170 ℃, and carrying out primary drying and curing to obtain a 10-micron high-adhesion fluorine-containing polymer layer; corona equipment is adopted to corona the other surface of the PET basal membrane to 50-60 dyne/cm, then a high molecular adhesive coating liquid (Weiston, Changzhou) is coated, the drying is carried out for 2min at 110 ℃ by a circulating oven, a high molecular adhesive layer with the thickness of 8 mu m is prepared, and the high molecular adhesive layer and the super weather-resistant fluororesin polymer alloy layer prepared in the comparative example 2 which is corona to 50-60 dyne/cm by the corona equipment are coated together, so that a finished product of the solar backboard is prepared. And finally, curing for 48 hours by using a 50 ℃ oven to obtain a solar backboard product G.
Comparative example 3 Inshine301 type first generation white backsheet H.
Comparative example 4 InshineT01 model first generation white backsheet I.
And (3) performance testing:
the prepared solar backboard products A to I are subjected to detection of multiple indexes of yellowing index, peeling strength with EVA and damp-heat test, and the obtained results are shown in Table 1, wherein
Yellowing index: detection was carried out according to GB 2409-80.
Peel strength from EVA: the peel strength test was carried out according to GB/T2790.
And (3) damp-heat experiment: the method is carried out according to the specification of IEC 61215-. The yellowing index (. DELTA.YI) and peel strength of the samples after 1000h of aging were recorded.
Thermal cycling experiments: according to the IEC 61215-2005 regulations, a spiral welding strip twisted by a photovoltaic flat welding strip with the length of 10cm and the length of 0.35 multiplied by 2.0mm is placed between two layers of EVA during lamination, the bulge caused by welding of the welding strip during actual packaging of a photovoltaic module is simulated, and accelerated aging is carried out in a test box circulating between the temperature of minus 40 ℃ plus or minus 2 ℃ and the temperature of plus 85 ℃ plus or minus 2 ℃. The yellowing index (Δ YI) and appearance of the samples after 600 cycles of aging were recorded.
Table 1 each backplane performance test data
As can be seen from the test data of table 1, the high adhesion coating type back sheet provided by each example of the present invention has excellent adhesion property with EVA, and excellent aging resistance. In comparative example 1, the adhesion with white EVA was significantly reduced without the addition of modified acrylic resin, the adhesion was poor, and the resistance to yellowing was poor. In comparative example 2, the core-shell structure toughening agent was not added, and the backsheet TC600 cracked after cyclic aging, and low temperature resistance was poor.
In conclusion, the hydroxyl value of the modified acrylic resin is 10-30, the acid value is not more than 4, the glass transition temperature is not lower than 30 ℃, and the weight-average molecular weight is 20000-50000 g/mol; and when the solid content is not less than 60wt%, the viscosity of the modified acrylic resin at 25 ℃ is 2000-4000 mPa & s; when the high-adhesion high-weather-resistance coating type solar back plate is used, the yellowing resistance of the solar cell back plate can be improved, and the high-weather-resistance coating type solar back plate has high weather resistance and can be used for a long time; in the high-adhesion high-weather-resistance coating type solar cell back plate, the super-weather-resistance fluororesin polymer alloy layer has super-weather resistance by adding the low-temperature-resistant toughening agent, and also has super-low temperature property, and the aging TC600 is not cracked, so that the solar cell back plate has the function of protecting a solar cell for a long time.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A solar cell backsheet, comprising:
the super-weather-resistant fluorine resin polymer alloy layer and the high-adhesion fluorine polymer layer are respectively attached to the two surfaces of the matrix resin layer; wherein
The super-weather-resistant fluororesin polymer alloy layer comprises the following components in parts by mass:
PVDF resin: 30-70 parts of a solvent;
inorganic filler A: 1-20 parts;
low temperature resistant toughener: 1-20 parts;
functional auxiliary agents: 0.1-2 parts; and
the high-adhesion fluoropolymer layer comprises the following components in parts by mass:
fluorine-containing resin: 25-45 parts of a solvent;
modified acrylic resin: 15-40 parts;
adhesion promoting resin: 3-10 parts;
inorganic filler B: 10-30 parts;
auxiliary agent: 0.1-5 parts;
curing agent: 1-10 parts; and
solvent: 15-50 parts.
2. The solar cell backsheet according to claim 1,
the modified acrylic resin comprises:
an alkoxysilane group located on a side chain of the modified acrylic resin; and
a reactive group comprising at least one of a hydroxyl group or an amine group.
3. The solar cell backsheet according to claim 2,
the structural formula of the modified acrylic resin is as follows:
R1、R2、R3Are respectively one of alkyl or alkoxy, and R1、R2、R3At least one of which is an alkoxy group;
the values of x, y, z, w and i are respectively that x is more than or equal to 20 and less than or equal to 100, y is more than or equal to 20 and less than or equal to 100, z is more than or equal to 20 and less than or equal to 100, w is more than or equal to 20 and less than or equal to 100, and i is more than or equal to 10 and less than or equal to 50.
4. The solar cell backsheet according to claim 2,
the hydroxyl value of the modified acrylic resin is 10-30, the acid value is not more than 4, the glass transition temperature is not lower than 30 ℃, and the weight-average molecular weight is 20000-50000 g/mol; and
when the solid content is not less than 60wt%, the viscosity of the modified acrylic resin at 25 ℃ is 2000 to 4000 mPa · s.
5. A method for producing the solar cell back sheet according to claim 1, comprising the steps of:
mixing, grinding and dispersing raw materials of the high-adhesion fluorine-containing polymer layer to obtain a high-adhesion fluorine-containing polymer coating liquid;
mixing the raw materials of the super weather-proof fluororesin polymer alloy layer, extruding and granulating, and preparing the super weather-proof fluororesin polymer alloy layer film in a casting or film blowing mode;
performing double-sided corona treatment on the matrix resin layer to activate the surface of the matrix resin layer, coating the high-adhesion fluoropolymer coating liquid on one surface of the activated matrix resin layer, and heating and baking to form a high-adhesion fluoropolymer layer;
coating a polymer adhesive coating liquid on the other surface of the activated matrix resin layer, and heating and baking to form a polymer adhesive layer;
and attaching the super weather-proof fluororesin polymer alloy layer film subjected to double-sided corona to the other surface of the high-molecular adhesive layer, and performing curing reaction to obtain the solar cell backboard.
6. The method according to claim 5,
the preparation method of the modified acrylic resin comprises the following steps:
mixing an acrylic resin composition and a chain transfer agent, and adding the mixture into a first dropping container to prepare a first dropping liquid;
adding an initiator into a second dripping container to prepare second dripping liquid;
adding xylene, toluene and butyl acetate into a reaction vessel, and dropwise adding a first drop of liquid into the reaction vessel to obtain a reaction mixed liquid;
and heating the reaction mixed solution, preserving heat, cooling, adding a second dropping liquid, performing reflux reaction, and cooling to obtain the modified acrylic resin.
7. The method according to claim 6,
the acrylic resin composition comprises the following components in parts by mass:
methyl methacrylate: 1-35 parts;
acrylic acid: 1-25 parts;
butyl methacrylate: 1-40 parts;
hydroxypropyl methacrylate: 1-15 parts; and
vinyl group-containing alkoxysilane compound: 1-10 parts.
8. The method according to claim 7,
the feeding sequence of the acrylic resin composition is as follows in sequence: methyl methacrylate, acrylic acid, butyl methacrylate, hydroxypropyl methacrylate and vinyl-containing alkoxysilane compounds.
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Application publication date: 20211022 |