CN114262557B - Photovoltaic backboard inner layer coating, photovoltaic backboard, preparation method of photovoltaic backboard and photovoltaic module - Google Patents
Photovoltaic backboard inner layer coating, photovoltaic backboard, preparation method of photovoltaic backboard and photovoltaic module Download PDFInfo
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- CN114262557B CN114262557B CN202210056950.0A CN202210056950A CN114262557B CN 114262557 B CN114262557 B CN 114262557B CN 202210056950 A CN202210056950 A CN 202210056950A CN 114262557 B CN114262557 B CN 114262557B
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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
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Abstract
The invention provides a photovoltaic backboard inner layer coating, a photovoltaic backboard, a preparation method of the photovoltaic backboard and a photovoltaic module. Wherein, photovoltaic backplate inlayer coating includes: 10 to 50 parts of epoxy acrylate resin, 40 to 80 parts of active monomer, 0.1 to 20 parts of photoinitiator and 1 to 20 parts of epoxy resin. Because the content of the active monomer in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by curing the monomer exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard and the back layer packaging adhesive film is improved; meanwhile, the inner layer penetrating through the holes has better adhesive force with the base material layer of the backboard, and the ageing resistance of the backboard is improved.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a photovoltaic backboard inner layer coating, a photovoltaic backboard, a preparation method of the photovoltaic backboard and a photovoltaic module.
Background
The solar cell is a green clean energy technology capable of generating electricity by generating current by generating photovoltaic effect only by illumination. The conventional solar cell generally comprises an upper glass cover plate, an upper adhesive film, a cell piece, a lower adhesive film and a photovoltaic backboard, wherein the photovoltaic backboard plays an important role. Because the photovoltaic module used in the photovoltaic power station must meet the requirement of long outdoor service life, the photovoltaic backboard positioned at the back of the solar cell has the effect of protecting and supporting the cell, and must have reliable electrical insulation lines, water resistance and weather resistance, and meanwhile, the photovoltaic module can have good bonding effect with the lower adhesive film, namely, the inner layer of the photovoltaic backboard has the effect of the bonding layer.
The inner layer of the photovoltaic backboard mainly plays a role in bonding, and the photovoltaic backboard maintains excellent bonding performance in long-term outdoor use, and plays a role in supporting and protecting the battery piece. In the prior art, a co-extrusion casting film or other polymer films are used as an inner layer, and the bonding performance can be problematic in the long-term outdoor use process, so that the film layers need to be modified again to strengthen the bonding reliability, and the process is complicated. If the coating is used as the bonding inner layer, and solvent paint is used as the inner layer, although the bonding performance is generally reliable, the problems of cost and environmental protection need to be considered; when a photocurable coating is selected as the inner layer, there is often a problem in that adhesion to the back sheet substrate is reduced during aging.
Disclosure of Invention
The invention mainly aims to provide a photovoltaic backboard inner layer coating, a photovoltaic backboard, a preparation method thereof and a photovoltaic module, so as to solve the problem of insufficient adhesiveness between the photovoltaic backboard inner layer and a base material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photovoltaic back sheet inner layer paint comprising, in parts by weight: 10 to 50 parts of epoxy acrylate resin, 40 to 80 parts of active monomer, 0.1 to 20 parts of photoinitiator and 1 to 20 parts of epoxy resin.
Further, the weight ratio of the epoxy acrylate resin to the reactive monomer is 1:8-1.25:1.
Further, the reactive monomer is selected from any one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, ethoxylated oxyphenyl acrylate, isobornyl acrylate, octadecyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, preferably the reactive monomer has 2 to 6 functional groups.
Further, the epoxy acrylate resin is selected from any one or more of bisphenol A epoxy acrylate resin, hydrogenated bisphenol A epoxy acrylate resin and epoxidized oil acrylate resin.
Further, the photoinitiator is selected from any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, alpha-amine alkyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethyl benzoyl) phenyl phosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer and 9-phenyl acridine.
Further, the epoxy resin is selected from any one or more of bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin, preferably the photovoltaic back sheet inner layer coating further comprises 0.1-10 parts of epoxy curing agent, preferably the epoxy curing agent is selected from any one or more of aliphatic amine curing agent, aromatic amine curing agent, imidazole curing agent and latent curing agent.
According to another aspect of the present invention, there is provided a photovoltaic backsheet comprising an inner layer and a substrate layer, wherein the inner layer is cured from the photovoltaic backsheet inner layer coating of any of the above, the inner layer has through voids, the through voids have a specific area of 5% to 40%, preferably 15% to 35%, preferably the through voids have a pore diameter of between 100 mesh and 15000 mesh, more preferably between 600 mesh and 12000 mesh.
Further, the photovoltaic backsheet inner layer coating forms an inner layer by photo-setting and thermal setting.
Further, the thickness of the inner layer is 2 to 8 μm, preferably the substrate layer is any one of polyethylene naphthalate film, polypropylene terephthalate film, polyethylene terephthalate film, polybutylene terephthalate film, polycarbonate film, copolymerized silicon modified polycarbonate film, polymethyl methacrylate film, preferably the thickness of the substrate layer is 100 to 350 μm; preferably, the photovoltaic back sheet further comprises an air weather-resistant layer, preferably the main resin of the air weather-resistant layer is fluorocarbon resin, and preferably the thickness of the air weather-resistant layer is 10-30 mu m.
According to another aspect of the present invention, there is provided a method for preparing any one of the above photovoltaic back sheet, the method comprising: arranging the photovoltaic backboard inner layer coating on the substrate layer to form a first precoating layer; photo-curing the first precoat layer to form a preparation inner layer; optionally, setting an air weather-resistant layer raw material on the surface of the substrate layer far away from the preparation inner layer to form a second precoat layer; optionally, the second pre-coat layer and the preliminary inner layer are thermally cured to provide an air weatherable layer and an inner layer.
Further, ultraviolet light curing is adopted for photo-curing, the photo-curing time is 1-120 s, and the preferable heat curing temperature is 100-200 ℃ and the time is 1-10 min.
According to still another aspect of the present invention, there is provided a photovoltaic module including a front transparent packaging board, a front packaging adhesive film, a solar cell unit, a back packaging adhesive film and a back sheet, wherein the back sheet is any one of the above photovoltaic back sheets, and an inner layer of the photovoltaic back sheet is bonded to the back packaging adhesive film.
By applying the technical scheme of the invention, as the content of the active monomer in the photovoltaic backboard inner layer coating is more and the shrinkage capacity of the monomer is stronger during curing, more through holes formed by curing the monomer exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background of the present application, the prior art photo-cured coatings as an inner layer often suffer from reduced adhesion to the backsheet during aging. In order to solve the problem, the application provides a photovoltaic backboard inner layer coating, a photovoltaic backboard, a preparation method of the photovoltaic backboard and a photovoltaic module.
In one exemplary embodiment of the present application, there is provided a photovoltaic backsheet inner layer coating comprising, in parts by weight: 10 to 50 parts of epoxy acrylate resin, 40 to 80 parts of active monomer, 0.1 to 20 parts of photoinitiator and 1 to 20 parts of epoxy resin.
Because the active monomer content in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by monomer curing exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
The epoxy acrylate resin is used as a macromolecular substance to provide strength support for the film layer after being crosslinked, the active monomer generates through pores due to shrinkage when being crosslinked with the epoxy acrylate resin, and preferably, the weight ratio of the epoxy acrylate resin to the active monomer is 1:8-1.25:1, so that the pore structure is further enriched, and the strength of the film is enhanced.
The comparison shows that the smaller the molecular weight of the active monomer is, the more obvious the shrinkage of the active monomer is when the active monomer is cured; the more the functional groups of the active monomer are, the more the curing shrinkage is about obvious, but the more the functional groups are, the more the three-dimensional network formed by curing is difficult to release stress, and in order to form more through pores as much as possible and ensure the sufficient release of stress, the active monomer is preferably selected from any one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and hexanediol diacrylate; the active monomers have high through pore generation and can release stress more. In addition, monofunctional reactive monomers such as ethoxylated oxyphenyl acrylate, isobornyl acrylate, stearyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, and the like may also be selected, as these monofunctional reactive monomers may also perform better in the formulation system.
The epoxy acrylate resin used in the present application may be selected from among epoxy acrylate resins commonly used in the prior art, and in order to achieve the fit with commonly used EVA back layer adhesive films, it is preferable that the above epoxy acrylate resin is selected from any one or more of bisphenol a epoxy acrylate resin, hydrogenated bisphenol a epoxy acrylate resin, and epoxidized oil acrylate resin.
Photoinitiators useful in the present application are selected from photoinitiators commonly used in the art of photocuring, such as the photoinitiators described above including, but not limited to, any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α -aminoalkylphenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 9-phenylacridine.
Further, the epoxy resin is also selected from the group of epoxy resins having excellent thermosetting properties, for example, the epoxy resin is selected from one or more of bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, aliphatic epoxy resin, and alicyclic epoxy resin.
In some embodiments, to further facilitate stress relief of the photovoltaic backsheet inner layer, it is preferred that the photovoltaic backsheet inner layer coating further comprises 0.1 to 10 parts of an epoxy curing agent, preferably selected from any one or more of fatty amine curing agents, imidazole curing agents, latent curing agents. The epoxy resin and the epoxy acrylate resin have thermosetting property, so that after the inner layer coating of the photovoltaic backboard is photo-cured to form the inner layer with the through holes, when the photovoltaic backboard with the inner layer coating is used for laminating and packaging the solar cell, the inner layer can be further thermally cured, further the inner layer stress is further released, and the adhesive force between the inner layer and the substrate layer is improved; meanwhile, the resin of the inner layer can be crosslinked with the EVA material back layer packaging adhesive film, so that the adhesive force between the inner layer and the back layer packaging adhesive film is improved.
In another exemplary embodiment of the present application, a photovoltaic back sheet is provided, including an inner layer and a substrate layer, where the inner layer is formed by curing any of the photovoltaic back sheet inner layer coatings, and the inner layer has a through pore, where the through pore occupies 5% -40% of the area, and the pore diameter of the through pore is between 100 mesh and 15000 mesh.
Because the active monomer content in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by monomer curing exist in the coating of the photovoltaic backboard inner layer coating, namely the formed photovoltaic backboard inner layer has rich holes. The back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical role, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
The above-mentioned through-holes have a specific area and pore size that affect the anchoring effect with the packaging film, and preferably have a specific area of 15% -35%, for example 20%, 25%, 30%, and pore diameters of 600 mesh-12000 mesh, for example 800 mesh, 1000 mesh, 2000 mesh, 5000 mesh, 7000 mesh, 11000 mesh.
In some embodiments, the photovoltaic backsheet inner layer coating described above forms the inner layer by photo-setting and thermal setting. The heat curing may further release the coating film stress.
The thickness of the inner layer of the present application may be in reference to the prior art, and since the inner layer of the present application has through voids, its thickness may be relatively reduced relative to the prior art to achieve sufficient shrinkage of the photo-curing process, in some embodiments of the present application, the thickness of the inner layer is 2-8 μm.
The substrate layer used in the present application may be referred to in the art, for example, the substrate layer is any one of a polyethylene naphthalate film, a polypropylene terephthalate film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polycarbonate film, a copolymerized silicon modified polycarbonate film, and a polymethyl methacrylate film. The thickness of the substrate layer is preferably 100 to 350 μm to provide sufficient support and protection for the photovoltaic module.
In some embodiments of the present application, the photovoltaic back sheet further has an air weather-resistant layer, so as to improve the weather-resistant capability of the photovoltaic back sheet and prolong the service life of the photovoltaic back sheet. The material and thickness of the air weather-resistant layer can be referred to the prior art, for example, the main resin of the air weather-resistant layer is fluorocarbon resin, and the thickness of the air weather-resistant layer is preferably 10-30 mu m.
The raw materials of the air weather-resistant layer are schematically illustrated below to enable a person skilled in the art to conveniently manufacture the air weather-resistant layer, and comprise 100 parts of main resin, 0.1-30 parts of modified resin, 1-50 parts of curing agent, 1-60 parts of inorganic filler, 0.1-10 parts of auxiliary agent and 10-200 parts of solvent. The main resin of the air weather-resistant layer is fluorocarbon resin, and the modified resin is any one of butanol etherified amino resin, butanol etherified urea resin, epoxy resin, C5 petroleum resin, terpene resin, organic silicon resin and the like; the curing agent is selected from any one or a combination of a plurality of hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret, diphenylmethane diisocyanate trimer, isophorone diisocyanate prepolymer, isophorone diisocyanate-trimethylol propane methanol compound, imidazole modified isocyanate curing agent and the like; the inorganic filler is selected from titanium dioxide or glass beads or a mixture of titanium dioxide and glass beads, etc.; the auxiliary agent is formed by mixing one or more of dispersing agent, flatting agent, coupling agent and the like according to any proportion; the solvent is selected from xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, butanone, ethanol, isopropanol, N-methylpyrrolidone, dimethyl sulfoxide, etc.
In another exemplary embodiment of the present application, there is provided a method for preparing a photovoltaic backsheet of any one of the above, the method comprising: arranging the photovoltaic backboard inner layer coating on the substrate layer to form a first precoating layer; photo-curing the first precoat layer to form a preparation inner layer; optionally, setting an air weather-resistant layer raw material on the surface of the substrate layer far away from the preparation inner layer to form a second precoat layer; optionally, the second pre-coat layer and the preliminary inner layer are thermally cured to provide an air weatherable layer and an inner layer.
Because the active monomer content in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by monomer curing exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
When the air weather-resistant layer is not arranged, the prepared inner layer formed after the first precoat layer is subjected to photo-curing can be used as an inner layer, and the prepared inner layer is further subjected to heat curing when the photovoltaic module is laminated. When the air weather-proof layer is arranged, the air weather-proof layer is thermally cured, and meanwhile, the preparation inner layer is thermally cured, and at the moment, the preparation inner layer further releases stress, so that the adhesive force with the base material layer is better. Because the through holes are formed in the curing process, the thickness of the first precoat layer basically does not change, that is to say, the thickness of the first precoat layer is the thickness of the inner layer of the photovoltaic backboard.
In some embodiments, the photo-curing is performed by ultraviolet light for 1s to 120s to achieve curing of the epoxy acrylate resin and the reactive monomer at a proper rate as sufficiently as possible, further enriching the porosity and improving the stress release. For the same reason, the heat curing is preferably carried out at a temperature of 100 to 200℃for a time of 1 to 10 minutes.
In yet another exemplary embodiment of the present application, a photovoltaic module is provided, including a front transparent packaging board, a front packaging adhesive film, a solar cell unit, a back packaging adhesive film, and a back sheet, where the back sheet is any one of the above photovoltaic back sheets, and an inner layer of the photovoltaic back sheet is bonded with the back packaging adhesive film.
Because the content of the active monomer in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by curing the monomer exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
The advantageous effects of the present application will be further described below in conjunction with examples and comparative examples.
Example 1
An inner coating was prepared by mixing 20 parts of bisphenol a type epoxy acrylate resin (EB 600), 70 parts of dipentaerythritol hexaacrylate, 3 parts of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 6.5 parts of aliphatic epoxy resin (UVR 6105), and 0.5 part of N, N-dimethylaniline.
100 parts of fluorocarbon resin, 20 parts of butanol etherified urea formaldehyde resin (Cymel UI-38-1) and 25 parts of hexamethylene diisocyanate trimer
N3300), 50 parts by mass ratio of 4:1, a mixture of titanium dioxide (R996) and glass beads, 5 parts of auxiliary agent and 150 parts of propylene glycol methyl ether acetate.
Coating the inner layer paint on one side of a white PET film with the thickness of 260 mu m to form a first precoat layer with the thickness of 3 mu m; the first precoat layer was irradiated with ultraviolet light for 30s to form a preliminary inner layer. And coating the other side of the PET film with an air weather-resistant layer coating to form a second precoat with the thickness of 20 mu m, and then curing for 5min at 180 ℃ to obtain the photovoltaic backboard of the example 1.
Example 2
The difference from example 1 is that dipentaerythritol pentaacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 3
The difference from example 1 is that trimethylolpropane tetraacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 4
The difference from example 1 is that trimethylolpropane triacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 5
The difference from example 1 is that hexanediol diacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 6
The difference from example 1 is that ethoxylated trimethylol propane triacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 7
The difference from example 1 is that pentaerythritol tetraacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 8
The difference from example 1 is that pentaerythritol triacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 9
The difference from example 1 is that isobornyl acrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 10
The difference from example 1 is that tripropylene glycol diacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 11
The difference from example 1 is that ethoxylated pentaerythritol tetraacrylate is used instead of dipentaerythritol hexaacrylate as reactive monomer.
Example 12
Unlike example 1, an inner coating was prepared by mixing 20 parts of bisphenol a type epoxy acrylate resin (CN 104), 72.9 parts of dipentaerythritol hexaacrylate, 0.1 part of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 6.5 parts of aliphatic epoxy resin (UVACURE 1500), and 0.5 parts of N, N-dimethylaniline.
Example 13
The inner coating was prepared by mixing 16 parts of bisphenol A type epoxy acrylate resin (EB 600), 58 parts of dipentaerythritol hexaacrylate, 20 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 5.6 parts of aliphatic epoxy resin (UVACURE 1500), and 0.4 part of N, N-dimethylaniline, as in example 1.
Example 14
Unlike example 1, an inner coating was prepared by mixing 20 parts of bisphenol a type epoxy acrylate resin (EB 600), 55 parts of dipentaerythritol hexaacrylate, 3 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 20 parts of aliphatic epoxy resin (UVR 6105), and 2 parts of N, N-dimethylaniline.
Example 15
Unlike example 1, an inner coating was prepared by mixing 10 parts of bisphenol a type epoxy acrylate resin (EB 600), 80 parts of dipentaerythritol hexaacrylate, 3 parts of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 6.5 parts of aliphatic epoxy resin (UVR 6105), and 0.5 part of N, N-dimethylaniline.
Example 16
Unlike example 1, an inner coating was prepared by mixing 21.5 parts of bisphenol a type epoxy acrylate resin (EB 600), 74.4 parts of dipentaerythritol hexaacrylate, 3 parts of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 1 part of aliphatic epoxy resin (UVR 6105), and 0.1 part of N, N-dimethylaniline.
Example 17
The difference from example 1 is that the photo-curing was 1s.
Example 18
The difference from example 1 is that the photo-curing was 120s.
Example 19
The difference from example 1 is that the heat curing is carried out at 100℃for 10min.
Example 20
The difference from example 1 is that the heat curing is carried out at 200℃for 1min.
Example 21
The difference from example 1 is that the first precoat layer has a thickness of 2 μm.
Example 22
The difference from example 1 is that the first precoat layer has a thickness of 8. Mu.m.
Example 23
The difference from example 1 was that 50 parts of bisphenol a type epoxy acrylate resin (EB 600), 40 parts of dipentaerythritol hexaacrylate, 3 parts of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 6.5 parts of aliphatic epoxy resin (UVR 6105), and 0.5 parts of N, N-dimethylaniline were mixed to prepare an inner coating material.
Example 24
The inner coating was prepared by mixing 13 parts of bisphenol A type epoxy acrylate resin (EB 600), 80 parts of dipentaerythritol hexaacrylate, 2 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 4.5 parts of aliphatic epoxy resin (UVR 6105), and 0.5 part of N, N-dimethylaniline, as in example 1.
Example 25
Unlike example 1, an inner coating was prepared by mixing 40 parts of bisphenol a type epoxy acrylate resin (EB 600), 40 parts of dipentaerythritol hexaacrylate, 6 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 13 parts of aliphatic epoxy resin (UVR 6105), and 1 part of N, N-dimethylaniline.
Comparative example 1
The difference from example 1 is that 30 parts of trimethylolpropane triacrylate was used instead of 70 parts of dipentaerythritol hexaacrylate as reactive monomer, and 60 parts of epoxy acrylate resin (LR 9022) was used instead of 20 parts of bisphenol a type epoxy acrylate resin.
Comparative example 2
The difference from example 1 is that an inner layer coating was prepared by mixing 20 parts of bisphenol A type epoxy acrylate resin (CN 104), 70 parts of dipentaerythritol hexaacrylate, and 3 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer.
Comparative example 3
The difference from example 1 was that 5 parts of bisphenol a type epoxy acrylate resin (EB 600), 90 parts of dipentaerythritol hexaacrylate, 4.4 parts of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 0.5 part of aliphatic epoxy resin (UVR 6105), and 0.1 part of N, N-dimethylaniline were mixed to prepare an inner coating.
Performance test:
1. peel strength with EVA: test methods refer to GB/T2790 adhesive 180 peel Strength test method flexible vs. rigid materials, i.e. PCT peel Strength.
2. Adhesion force: test methods refer to GB/T31034 insulating back sheet for crystalline silicon solar cell module, PCT adhesion.
3. Pore diameter and through hole area ratio: the test method uses SEM scanning electron microscope to analyze the area ratio of the through holes on the surface of the coating film.
The test results are recorded in table 1.
TABLE 1
As is clear from the data of examples and comparative examples in Table 1, a higher proportion of the reactive monomer can better form a sufficiently porous layer of through holes to provide better adhesion. Further, the active monomers are different, and the results are different, which shows that the active monomers with large curing shrinkage can form better through pore layers and are excellent in adhesive performance, and when the shrinkage of the active monomers is smaller, the formed through pore layers occupy smaller through Kong Zhanbi, and the internal stress caused by curing of the through pore layers cannot be fully released due to the formation of the through holes, so that the inner layer cannot form a photovoltaic back sheet adhesive layer with complete point distribution, and the adhesive performance of the through pore layers is poor after PCT aging.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: because the active monomer content in the photovoltaic backboard inner layer coating is more, the shrinkage capacity of the monomer is stronger during curing, more through holes formed by monomer curing exist in the coating of the photovoltaic backboard inner layer coating, the back layer packaging adhesive film can be completely filled into the through holes to play an anchoring role in the lamination process, and meanwhile, the surface of the through hole layer and the adhesive film still have a physical and chemical effect, so that the bonding performance of the photovoltaic backboard with the through holes and the back layer packaging adhesive film is ensured; meanwhile, the coating formed by the coating releases stress in the curing shrinkage and cracking process, so that the formed inner layer with through holes has better adhesive force with the substrate layer of the backboard, and the ageing resistance of the backboard is improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. The photovoltaic back plate inner layer coating is characterized by comprising the following components in parts by weight:
10-50 parts of epoxy acrylate resin, 40-80 parts of active monomer, 0.1-20 parts of photoinitiator and 1-20 parts of epoxy resin;
the epoxy acrylate resin is selected from any one or more of bisphenol A epoxy acrylate resin, hydrogenated bisphenol A epoxy acrylate resin and epoxidized oil acrylate resin;
the photoinitiator is selected from any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, alpha-amine alkyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethyl benzoyl) phenyl phosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer and 9-phenylacridine;
the weight ratio of the epoxy acrylate resin to the active monomer is 1:8-1.25:1;
the active monomer is selected from any one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, ethoxylated oxyphenyl acrylate, isobornyl acrylate, octadecyl acrylate, methyl methacrylate, butyl methacrylate and hydroxyethyl acrylate.
2. The photovoltaic backsheet inner layer coating of claim 1 wherein the reactive monomer has 2 to 6 functional groups.
3. The photovoltaic backsheet inner layer coating of claim 1 wherein the epoxy resin is selected from any one or more of bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin.
4. The photovoltaic backsheet inner layer coating of claim 1, further comprising 0.1-10 parts of an epoxy curing agent.
5. The photovoltaic backsheet inner layer coating of claim 4 wherein the epoxy curing agent is selected from any one or more of fatty amine curing agents, aromatic amine curing agents, imidazole curing agents.
6. A photovoltaic back sheet comprising an inner layer and a substrate layer, wherein the inner layer is formed by curing the photovoltaic back sheet inner layer coating according to any one of claims 1 to 5, the inner layer has through pores, and the through pores occupy 5% -40% of the area.
7. The photovoltaic backsheet of claim 6 wherein the through voids comprise 15% -35% of the total area.
8. The photovoltaic backsheet of claim 6 wherein the through-voids have a pore size between 100 mesh and 15000 mesh.
9. The photovoltaic backsheet of claim 8 wherein the through-voids have a pore size between 600 mesh and 12000 mesh.
10. The photovoltaic backsheet according to any one of claims 6 to 9, characterized in that the photovoltaic backsheet inner layer coating forms the inner layer by photo-and thermal curing.
11. The photovoltaic backsheet according to any one of claims 6 to 9, wherein the thickness of the inner layer is 2-8 μm.
12. The photovoltaic backsheet of any one of claims 6 to 9 wherein the substrate layer is any one of a polyethylene naphthalate film, a polypropylene terephthalate film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polycarbonate film, a copolymerized silicon modified polycarbonate film, a polymethyl methacrylate film.
13. The photovoltaic backsheet according to any one of claims 6 to 9, wherein the thickness of the substrate layer is 100-350 μm.
14. The photovoltaic backsheet according to any one of claims 6 to 9, further comprising an air weatherable layer.
15. The photovoltaic backsheet of claim 14 wherein the air weatherable layer primary resin is a fluorocarbon resin.
16. The photovoltaic backsheet of claim 14 wherein the air weatherable layer has a thickness of 10-30 μm.
17. A method of making a photovoltaic backsheet as claimed in any one of claims 6 to 16, comprising:
arranging the photovoltaic backboard inner layer coating on the substrate layer to form a first precoating layer;
photo-curing the first precoat layer to form a preparation inner layer;
optionally, setting an air weather-resistant layer raw material on the surface of the substrate layer far away from the preparation inner layer to form a second precoat;
optionally, the second precoat layer and the preliminary inner layer are thermally cured to obtain the air weatherable layer and the inner layer.
18. The method of claim 17, wherein the photo-curing is performed by ultraviolet light for 1-120 s.
19. The method according to claim 17, wherein the heat curing is performed at a temperature of 100 to 200 ℃ for a time of 1 to 10 minutes.
20. A photovoltaic module comprising a front transparent packaging board, a front packaging adhesive film, a solar cell unit, a back packaging adhesive film and a back panel, wherein the back panel is the photovoltaic back panel according to any one of claims 6 to 16, and an inner layer of the photovoltaic back panel is bonded with the back packaging adhesive film.
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| CN202210056950.0A CN114262557B (en) | 2022-01-18 | 2022-01-18 | Photovoltaic backboard inner layer coating, photovoltaic backboard, preparation method of photovoltaic backboard and photovoltaic module |
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| CN202210056950.0A CN114262557B (en) | 2022-01-18 | 2022-01-18 | Photovoltaic backboard inner layer coating, photovoltaic backboard, preparation method of photovoltaic backboard and photovoltaic module |
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| CN104910758A (en) * | 2015-05-11 | 2015-09-16 | 广德美涂士化工有限公司 | High-strength antibacterial ultraviolet-curable coating |
| CN104830211B (en) * | 2015-05-18 | 2017-07-21 | 惠州德斯坤实业有限公司 | UV offset printing gloss oils and preparation method thereof |
| CN109054531B (en) * | 2018-07-12 | 2020-11-20 | 杭州福斯特应用材料股份有限公司 | Weather-resistant transparent coating and application thereof |
| CN112625480B (en) * | 2020-12-02 | 2022-03-04 | 杭州福斯特应用材料股份有限公司 | Photocuring transparent coating |
| CN112812694B (en) * | 2020-12-31 | 2022-02-25 | 福斯特(滁州)新材料有限公司 | Heat preservation encapsulation glued membrane and photovoltaic module |
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