CN102911612B - Fluorescent EVA (Ethylene vinyl acetate) glue film - Google Patents
Fluorescent EVA (Ethylene vinyl acetate) glue film Download PDFInfo
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- CN102911612B CN102911612B CN201210450694.XA CN201210450694A CN102911612B CN 102911612 B CN102911612 B CN 102911612B CN 201210450694 A CN201210450694 A CN 201210450694A CN 102911612 B CN102911612 B CN 102911612B
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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
- Y02E10/52—PV systems with concentrators
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Abstract
The invention relates to a fluorescent EVA (Ethylene vinyl acetate) glue film. The formula of the fluorescent EVA glue film comprises EVA of which the vinyl acetate content is 26wt%-35wt% and a polymerizable fluorescent monomer, wherein the polymerizable fluorescent monomer is a mixture formed by any one or at least two of acrylates or methylacrylates of Eu, Y, Sm, Ce, Tb, Dy, Gd, La and Sc or organic metal chelates of acrylates and methylacrylates according to any proportion. The formula of the fluorescent EVA glue film can further comprise additive components, i.e., oxide crosslinking agent, assistant crosslinking agent, hindered amine light stabilizer, assistant antioxidant, tackifier, plasticizer and antacid. According to the fluorescent EVA glue film, not only the package efficiency of components can be obviously improved, but also the aging function of ultraviolet light to photovoltaic components can be greatly reduced, and therefore, the fluorescent EVA glue film can be widely used for the package of various photovoltaic components.
Description
Technical field
The present invention relates to the EVA glued membrane for the solar module encapsulation, especially a kind of fluorescence EVA glued membrane.
Background technology
EVA is Ethylene(ethene), the Vinyl(vinyl), the Acetate(acetic ester) abbreviation, be commonly referred to ethylene-vinyl acetate copolymer, it is the sticking glued membrane of a kind of thermoset, for being placed in the middle of doubling glass, because it has during significant superiority is applied to electric current assembly and various optical articles more and more widely at aspects such as clinging power, weather resistance, optical characteristics.As: CN 102504715A discloses a kind of EVA solar cell glued membrane, multipolymer, silane coupling agent, crosslinking and curing agent, crosslinking curing promotor, thermo-stabilizer, tackifier, oxidation inhibitor, ultraviolet absorbers, hindered amine light stabilizer by ethene-vinyl acetate form, the EVA glued membrane of this invention improves working life, the fast setting performance strengthens, and also can solve auxiliary agent in production process and mixes the uneven quality problems that cause with pellet and reduce the battery crushing probability in the cell package process; CN 102140314A discloses a kind of EVA glued membrane with high reflecting rate, its main ingredient is EVA resin, reflective filler, peroxide cross-linking agent and antiaging agent, described reflective filler is selected the inorganic material powders that reflecting rate is high, peroxide cross-linking agent is organo-peroxide, antiaging agent is ultraviolet ageing agent and/or resistant to thermal aging decomposition agent, this invention can improve the reflectivity of sunlight, can be used as the EVA of lower floor glued membrane in crystal silicon class solar module or the EVA glued membrane in Thinfilm solar cell assembly; CN102533141A discloses a kind of EVA glued membrane and manufacture method thereof, with after composite antioxidant, UV light absorber and crosslinking and curing agent and tackifier fully mix by EVA, through the casting method explained hereafter, effectively improve the transparency and the ageing-resistant performance of EVA glued membrane, improved light conversion efficiency and the work-ing life of solar module; CN 102504713A discloses a kind of novel solar battery EVA glued membrane, its main component is ethene-vinyl acetate fat, peroxide linking agent, lipid oxidation inhibitor, hindered amine light stabilizer, tackifier and novel ultraviolet absorbers 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, the EVA glued membrane of this invention has the ultraviolet luminous energy of strong absorption, has extended the work-ing life of packaged material.
Yet, the above-mentioned EVA glued membrane of mentioning is to prevent that sunlight medium ultraviolet light from making the macromolecular material ageing failures such as EVA in assembly, backboard, all adopted the mode direct filtration that adds ultraviolet absorbers in formula to fall UV-light, make high-octane UV-light can not effectively be applied to conventional photovoltaic module and produce electric power, also make component package efficiency can't obtain substantial raising all the time.
CN 101353558A discloses a kind of EVA glued membrane that does not add the ultraviolet light absorption agent, mainly by the quality proportioning, following raw material is made: 100 parts of ethylene-vinyl acetate copolymers, peroxide linking agent 0.1-10 part, phenols or phosphite ester kind antioxidant 0.05-5 part, hindered amine light stabilizer 0.01-5 part.Owing to not using ultraviolet absorbers, do not produce the UV-light cut-off so obtain the EVA glued membrane, make solar module can receive the luminous energy of ultraviolet region, thereby there is higher photoelectric transformation efficiency.Its shortcoming is that the uvioresistant ageing resistance is poor, and the risk that the photovoltaic module long-term aging lost efficacy greatly increases, and the work-ing life of assembly is short.
CN 102093628A discloses a kind of EVA glued membrane with light conversion characteristic and preparation method thereof.It is characterized in that: use luminophor to replace ultraviolet absorbers and the stablizer in common EVA glued membrane, obtain Novel EVA adhesive film, the mishmetal title complex that described luminophor is beta-diketon and pyridine derivatives.Because can absorbing UV-light, luminophor launches visible ray, thereby this is invented related Novel EVA adhesive film and has the light conversion characteristic, convert by the UV-light that the solar module utilization ratio is low the visible ray that utilization ratio is high to, thereby make solar module there is higher efficiency, there is more excellent anti-ultraviolet ageing performance simultaneously.Its shortcoming is that the chemically reactive of beta-diketon and pyridine derivatives is too high, after this EVA uses in photovoltaic module, no matter be the long-term reliability of assembly, or with the consistency of unclassified stores in assembly, all there is very large Problem of Failure, as EVA xanthochromia, the variable color of cell piece silver grating line, the problems such as welding bus-bar corrosion.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, by add a kind of polymerisable fluorescent monomer in the EVA formula system, a kind of fluorescence EVA glued membrane that turns the light function that has is provided, the visible ray that it can absorb the UV-light of specific band in sunlight and send specific band, the latter can be produced electric power by the assembly utilization, thereby improve largely the packaging efficiency of assembly, can reduce again the solarization of UV-light to photovoltaic module, can be widely used for the encapsulation of conventional photovoltaic module simultaneously.
For achieving the above object, the present invention adopts following technical scheme:
A kind of fluorescence EVA glued membrane, described glued membrane comprises EVA and polymerisable fluorescent monomer.
Described EVA(ethylene-vinyl acetate copolymer) for preparing the main raw material of fluorescence EVA glued membrane, wherein the content of vinyl acetate is preferably 26wt%-35wt%, can be for example 26wt%-30.5wt%, 29.3wt%-32.7wt%, 31.2wt%-35wt%, 26wt%, 27.5wt%, 28wt%, 30wt%, 31.1wt%, 33wt%, 34.6wt%, 35wt%; 28wt%-33wt% more preferably; Most preferably be 30wt%.
Preferably, the weight percent (wt%) of described EVA in fluorescence EVA glued membrane of the present invention is 93.80wt%-99.53wt%, can be for example 93.80wt%-95.06wt%, 94.03wt%-98.17wt%, 96.12wt%-99.53wt%, 93.80wt%, 94wt%, 94.75wt%, 95wt%, 95.08wt%, 95.50wt%, 96wt%, 96.11wt%, 96.84wt%, 97wt%, 97.26wt%, 97.50wt%, 97.79wt%, 98wt%, 98.43wt%, 99.02wt%, 99.53wt%; 95.35wt%-98.45wt% more preferably; Most preferably be 96.50wt%.
Any one in acrylate, methacrylate or both organic metal chelate complexs that described polymerisable fluorescent monomer is europium (Eu), yttrium (Y), samarium (Sm), cerium (Ce), terbium (Tb), dysprosium (Dy), gadolinium (Gd), lanthanum (La), scandium (Sc) or at least two kinds of mixtures that form with arbitrary proportion; Be preferably a kind of or at least two kinds of mixtures that form with arbitrary proportion in europium acrylate, methacrylic acid europium, vinylformic acid yttrium, methacrylic acid yttrium; Most preferably be the compound that vinylformic acid yttrium and methacrylic acid yttrium mix according to the mass ratio of 1:1.Described polymerisable fluorescent monomer plays the effect of light-converting agent in fluorescence EVA glued membrane of the present invention, and can be converted into visible ray to the most of UV-light that enters EVA and be absorbed by cell piece, thus the packaging efficiency of raising assembly; On the other hand, in the component lamination process, this polymerisable fluorescent monomer can be crosslinked the agent initiated polymerization with together with additional crosslinker in EVA, after lamination, be fixed on the macromolecular three-dimensional framework of EVA, thereby make can not move consumption in assembly life-time service process out of doors, ageing-resistant performance greatly improves.
Preferably, the weight percent (wt%) of described polymerisable fluorescent monomer in fluorescence EVA glued membrane of the present invention is 0.02wt%-0.2wt%, can be for example 0.02wt%-0.06wt%, 0.03wt%-0.17wt%, 0.12wt%-0.2wt%, 0.02wt%, 0.04wt%, 0.05wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.11wt%, 0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.18wt%, 0.19wt%, 0.2wt%; 0.05wt%-0.15wt% more preferably; Most preferably be 0.1wt%.
Further, can also comprise following additive component in fluorescence EVA glued membrane of the present invention: peroxide cross-linking agent, additional crosslinker, hindered amine light stabilizer, auxiliary antioxidant, tackifier, softening agent, antacid.
Described peroxide cross-linking agent can, for this area various peroxide cross-linking agents commonly used when the preparation EVA glued membrane, be preferably tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, 1,1-bis-(tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane, dicumyl peroxide, two (2-tert-butyl hydroperoxide sec.-propyl) benzene, the tert-butyl peroxide isopropyl benzene, ditertiary butyl peroxide, the peroxybenzoic acid tert-pentyl ester, 2,5-dimethylhexane-2, the 5-ditertiary butyl peroxide, 2,5-dimethyl-2, two (benzoyl the peroxide)-hexanes of 5-, two (tert-pentyl the peroxide)-butane of 2,2-, two t-amyl peroxy things, tert butyl peroxy benzoate, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, the dibenzoyl superoxide, two (4-chlorobenzene formacyl) superoxide, two (2,4 dichloro benzene formyl radical) superoxide, two (4-methyl benzoyl) superoxide, normal-butyl-4,4-bis-(tert-butyl hydroperoxide) valerate, ethyl-3,3-bis-(tert-butyl hydroperoxide) butyric ester, tert-butyl hydroperoxide-sec.-propyl carbonic ether, the combination of any one in tert-butyl hydroperoxide-2-ethylhexyl carbonic ether or at least two kinds, most preferably be tert-butyl hydroperoxide carbonic acid-2-ethylhexyl.
Preferably, the weight percent (wt%) of described peroxide cross-linking agent in fluorescence EVA glued membrane of the present invention is 0.1wt%-2wt%, can be for example 0.1wt%-0.6wt%, 0.3wt%-1.7wt%, 1.25wt%-2wt%, 0.1wt%, 0.4wt%, 0.5wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.62wt%, 1.8wt%, 1.9wt%, 2wt%; 0.5wt%-1.5wt% more preferably; Most preferably be 1wt%.
Described additional crosslinker is that the present invention is that auxiliary crosslinking agent plays a role, promotes the additive component that crosslinking curing is used better, is preferably in the present invention the combination of any one or at least two kinds in cyanacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate; More preferably cyanacrylate, trimethylolpropane trimethacrylate or compound that the two mixes according to the mass ratio of 1:1; Most preferably be the compound that cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1.
Preferably, the weight percent (wt%) of described additional crosslinker in fluorescence EVA glued membrane of the present invention is 0.1wt%-2wt%, can be for example 0.1wt%-0.6wt%, 0.3wt%-1.7wt%, 1.25wt%-2wt%, 0.1wt%, 0.4wt%, 0.5wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.62wt%, 1.8wt%, 1.9wt%, 2wt%; 0.5wt%-1.5wt% more preferably; Most preferably be 1wt%.
Described hindered amine light stabilizer can, for this area various hindered amine light stabilizers commonly used when the preparation EVA glued membrane, be preferably two (2,2,6,6 tetramethyl-s-4 piperidines) sebate, 3,5-di-t-butyl-4-hydroxy-benzoic acid cetyl ester, three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester, two-1-alkoxyl group in the last of the ten Heavenly stems-2,2, the combination of any one in 6,6-tetramethyl piperidine-4-alcohol sebate or at least two kinds; Most preferably be two (2,2,6,6 tetramethyl--4 piperidines) sebates.
Preferably, the weight percent (wt%) of described hindered amine light stabilizer in fluorescence EVA glued membrane of the present invention is 0.05wt%-0.4wt%, can be for example 0.05wt%-0.16wt%, 0.13wt%-0.37wt%, 0.25wt%-0.4wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, 0.24wt%, 0.25wt%, 0.26wt%, 0.3wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.4wt%; 0.1wt%-0.3wt% more preferably; Most preferably be 0.2wt%.
Described auxiliary antioxidant can be this area various phenols or phosphite ester kind antioxidant commonly used when the preparation EVA glued membrane, be preferably tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, three (4-nonyl phenol) phosphorous acid ester, 2, 2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol), 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, the combination of any one in distearyl pentaerythrityl diphosphite or at least two kinds, more preferably three (4-nonyl phenol) phosphorous acid ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester or compound that the two mixes according to the mass ratio of 1:1, most preferably be the compound that three (4-nonyl phenol) phosphorous acid esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester mix according to the mass ratio of 1:1.
Preferably, the weight percent (wt%) of described auxiliary antioxidant in fluorescence EVA glued membrane of the present invention is 0.05wt%-0.4wt%, can be for example 0.05wt%-0.16wt%, 0.13wt%-0.37wt%, 0.25wt%-0.4wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, 0.24wt%, 0.25wt%, 0.26wt%, 0.3wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.4wt%; 0.1wt%-0.3wt% more preferably; Most preferably be 0.2wt%.
Described tackifier can be this area various tackifier commonly used when the preparation EVA glued membrane, are preferably the combination of any one or at least two kinds in γ-methacryloxypropyl trimethoxy silane, γ-aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, ester gum; Most preferably be γ-methacryloxypropyl trimethoxy silane.
Preferably, the weight percent (wt%) of described tackifier in fluorescence EVA glued membrane of the present invention is 0.05wt%-0.4wt%, can be for example 0.05wt%-0.16wt%, 0.13wt%-0.37wt%, 0.25wt%-0.4wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, 0.24wt%, 0.25wt%, 0.26wt%, 0.3wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.4wt%; 0.1wt%-0.3wt% more preferably; Most preferably be 0.2wt%.
Described softening agent can, for this area various softening agent commonly used when the preparation EVA glued membrane, be preferably trioctyl phosphate.
Preferably, the weight percent (wt%) of described softening agent in fluorescence EVA glued membrane of the present invention is 0.05wt%-0.4wt%, can be for example 0.05wt%-0.16wt%, 0.13wt%-0.37wt%, 0.25wt%-0.4wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, 0.24wt%, 0.25wt%, 0.26wt%, 0.3wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.4wt%; 0.1wt%-0.3wt% more preferably; Most preferably be 0.2wt%.
Described antacid can be this area various antacids commonly used when the preparation EVA glued membrane, is preferably the combination of any one or at least two kinds in calcium stearate, calcium carbonate, sodium bicarbonate, magnesium oxide, aluminium hydroxide, Magnesium Trisilicate; Most preferably be calcium stearate.
Preferably, the weight percent (wt%) of described antacid in fluorescence EVA glued membrane of the present invention is 0.05wt%-0.4wt%, can be for example 0.05wt%-0.16wt%, 0.13wt%-0.37wt%, 0.25wt%-0.4wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, 0.24wt%, 0.25wt%, 0.26wt%, 0.3wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.4wt%; 0.1wt%-0.3wt% more preferably; Most preferably be 0.2wt%.
In sum, the technical scheme after optimization of the present invention is:
A kind of fluorescence EVA glued membrane, according to weight percent (wt%) comprise following component: EVA(wherein the content of vinyl acetate be 26wt%-35wt%) 93.80wt%-99.53wt%, polymerisable fluorescent monomer 0.02wt%-0.2wt%, peroxide cross-linking agent 0.1wt%-2wt%, additional crosslinker 0.1wt%-2wt%, hindered amine light stabilizer 0.05wt%-0.4wt%, auxiliary antioxidant 0.05wt%-0.4wt%, tackifier 0.05wt%-0.4wt%, softening agent 0.05wt%-0.4wt% and antacid 0.05wt%-0.4wt%.
Technical scheme after the present invention further optimizes is:
A kind of fluorescence EVA glued membrane, according to weight percent (wt%) comprise following component: EVA(wherein the content of vinyl acetate be 28wt%-33wt%) 95.35wt%-98.45wt%, polymerisable fluorescent monomer 0.05wt%-0.15wt%, peroxide cross-linking agent 0.5wt%-1.5wt%, additional crosslinker 0.5wt%-1.5wt%, hindered amine light stabilizer 0.1wt%-0.3wt%, auxiliary antioxidant 0.1wt%-0.3wt%, tackifier 0.1wt%-0.3wt%, fire retardant 0.1wt%-0.3wt% and antacid 0.1wt%-0.3wt%.
The optimized technical scheme of the present invention is:
A kind of fluorescence EVA glued membrane, according to weight percent (wt%) comprise following component: EVA(wherein the content of vinyl acetate be 30wt%) 96.90wt%, the compound 0.1wt% that vinylformic acid yttrium and methacrylic acid yttrium mix according to the mass ratio of 1:1, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl 1wt%, the compound 1wt% that cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1, two (2, 2, 6, 6 tetramethyl-s-4 piperidines) sebate 0.2wt%, three (4-nonyl phenol) phosphorous acid ester and tricresyl phosphites (2, the 4-di-tert-butyl-phenyl) the compound 0.2wt% that ester mixes according to the mass ratio of 1:1, γ-methacryloxypropyl trimethoxy silane 0.2wt%, trioctyl phosphate 0.2wt% and calcium stearate 0.2wt%.
" comprising " of the present invention, mean it except described component, can also contain other components, these other components are given described fluorescence EVA glued membrane with different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... make ".No matter which kind of composition fluorescence EVA glued membrane of the present invention comprises, the weight percent sum of described fluorescence EVA glued membrane is 100%.
Fluorescence EVA glued membrane of the present invention, can prepare according to stir-the extrude technical process of curtain coating-temper-rolling vanning of various auxiliary agent mixing-heating for dissolving-auxiliary agent mixed solution and EVA mix particles.
The present invention joins in EVA glued membrane formula by the polymerisable fluorescent monomer that will play the light-converting agent effect, make fluorescence EVA glued membrane of the present invention to be converted into visible ray to the most of UV-light that enters EVA and absorbed by cell piece, thereby improved the packaging efficiency of assembly; On the other hand, in the component lamination process, this polymerisable fluorescent monomer can be crosslinked the agent initiated polymerization with together with additional crosslinker in EVA, after lamination, be fixed on the macromolecular three-dimensional framework of EVA, thereby make can not move consumption in assembly life-time service process out of doors, ageing-resistant performance greatly improves.Simultaneously, the multiple additives compositions such as rational proportion linking agent, oxidation inhibitor, make over-all properties be further enhanced.Fluorescence EVA film thickness of the present invention is 0.4-0.6mm, spectrophotofluorimetry light turnover ratio is at 0.06%(254nm) and 0.04%(365nm), the ultraviolet spectrophotometry transmittance is 92%, with the clinging power of glass in the 10KN/m left and right, with the clinging power of backboard in the 8KN/m left and right.In the IEC61215 standard test condition, two 85 hydrothermal aging 1500h after yellowings are below 4, ultraviolet pre-treatment 60Kwh/m
2after yellowing is below 3.5.Fluorescence EVA glued membrane of the present invention both can significantly improve the packaging efficiency of assembly, can greatly reduce the solarization of UV-light to photovoltaic module again, therefore can be widely used for the encapsulation of multiple photovoltaic module.
Below in conjunction with embodiment, the present invention is described in further detail.But following embodiment is only simple and easy example of the present invention, does not represent or limit the scope of the present invention, and interest field of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1:
A kind of fluorescence EVA glued membrane, comprise following component according to weight percent (wt%): the EVA 96.90wt% that the content of vinyl acetate is 30wt%, the compound 0.1wt% that vinylformic acid yttrium and methacrylic acid yttrium mix according to the mass ratio of 1:1, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl 1wt%, the compound 1wt% that cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1, two (2, 2, 6, 6 tetramethyl-s-4 piperidines) sebate 0.2wt%, three (4-nonyl phenol) phosphorous acid ester and tricresyl phosphites (2, the 4-di-tert-butyl-phenyl) the compound 0.2wt% that ester mixes according to the mass ratio of 1:1, γ-methacryloxypropyl trimethoxy silane 0.2wt%, trioctyl phosphate 0.2wt% and calcium stearate 0.2wt%.
Embodiment 2:
A kind of fluorescence EVA glued membrane, comprise following component according to weight percent (wt%): the EVA 99.53wt% that the content of vinyl acetate is 28wt%, europium acrylate 0.02wt%, dicumyl peroxide 0.1wt%, cyanacrylate 0.1wt%, 3,5-di-t-butyl-4-hydroxy-benzoic acid cetyl ester 0.05wt%, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester 0.05wt%, γ-aminopropyl triethoxysilane 0.05wt%, trioctyl phosphate 0.05wt% and magnesium oxide 0.05wt%.
Embodiment 3:
A kind of fluorescence EVA glued membrane, comprise following component according to weight percent (wt%): the EVA 93.80wt% that the content of vinyl acetate is 33wt%, methacrylic acid europium 0.2wt%, tert-butyl peroxide isopropyl benzene 2wt%, trimethylolpropane trimethacrylate 2wt%, three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester 0.4wt%, 2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol) 0.4wt%, vinyltrimethoxy silane 0.4wt%, trioctyl phosphate 0.4wt% and aluminium hydroxide 0.4wt%.
Embodiment 4:
A kind of fluorescence EVA glued membrane, comprise following component according to weight percent (wt%): the EVA 98.45wt% that the content of vinyl acetate is 26wt%, vinylformic acid yttrium 0.05wt%, 2,2-two (tert-pentyl peroxide)-butane 0.5wt%, triallyl cyanurate 0.5wt%, two-1-alkoxyl group in the last of the ten Heavenly stems-2,2,6,6-tetramethyl piperidine-4-alcohol sebate 0.1wt%, β-positive octadecyl ester 0.1wt% of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.1wt%, trioctyl phosphate 0.1wt% and Magnesium Trisilicate 0.1wt%.
Embodiment 5:
A kind of fluorescence EVA glued membrane, comprise following component according to weight percent (wt%): the EVA95.35wt% that the content of vinyl acetate is 35wt%, methacrylic acid yttrium 0.15wt%, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester 1.5wt%, the compound 1.5wt% that cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1, two (2, 2, 6, 6 tetramethyl-s-4 piperidines) sebate 0.3wt%, three (4-nonyl phenol) phosphorous acid ester 0.3wt%, ester gum 0.3wt%, trioctyl phosphate 0.3wt% and calcium carbonate 0.3wt%.
Should be noted that and understand, in the situation that do not break away from the desired the spirit and scope of the present invention of accompanying claim, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subject to the restriction of given any specific exemplary teachings.
Applicant's statement, above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (31)
1. a fluorescence EVA glued membrane, described glued membrane comprises EVA, it is characterized in that, also comprises the polymerisable fluorescent monomer in described glued membrane;
In described glued membrane in EVA the content of vinyl acetate be 26wt%-35wt%;
Any one in acrylate, methacrylate or both organic metal chelate complexs that described polymerisable fluorescent monomer is europium (Eu), yttrium (Y), samarium (Sm), cerium (Ce), terbium (Tb), dysprosium (Dy), gadolinium (Gd), lanthanum (La), scandium (Sc) or at least two kinds of mixtures that form with arbitrary proportion.
2. fluorescence EVA glued membrane according to claim 1, is characterized in that, in described glued membrane, the content of the vinyl acetate in EVA is 28wt%-33wt%.
3. fluorescence EVA glued membrane according to claim 1, is characterized in that, in described glued membrane, the content of the vinyl acetate in EVA is 30wt%.
4. according to the described fluorescence EVA of claim 1-3 any one glued membrane, it is characterized in that, described polymerisable fluorescent monomer is a kind of or at least two kinds of mixtures that form with arbitrary proportion in europium acrylate, methacrylic acid europium, vinylformic acid yttrium, methacrylic acid yttrium.
5. fluorescence EVA glued membrane according to claim 4, is characterized in that, the described polymerisable fluorescent monomer compound that to be vinylformic acid yttrium and methacrylic acid yttrium mix according to the mass ratio of 1:1.
6. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise peroxide cross-linking agent in described glued membrane.
7. fluorescence EVA glued membrane according to claim 6; it is characterized in that; described peroxide cross-linking agent is tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, dicumyl peroxide, two (2-tert-butyl hydroperoxide sec.-propyl) benzene, tert-butyl peroxide isopropyl benzene, ditertiary butyl peroxide, peroxybenzoic acid tert-pentyl ester, two t-amyl peroxy things, tert butyl peroxy benzoate, tert-butyl hydroperoxide-3; the combination of any one in 5,5-tri-methyl hexanoic acid ester, dibenzoyl superoxide, tert-butyl hydroperoxide sec.-propyl carbonic ether or at least two kinds.
8. fluorescence EVA glued membrane according to claim 7, it is characterized in that, described peroxide cross-linking agent is 2, 5-dimethylhexane-2, the 5-ditertiary butyl peroxide, normal-butyl-4, 4-bis-(tert-butyl hydroperoxide) valerate, ethyl-3, 3-bis-(tert-butyl hydroperoxide) butyric ester or 1, 1-bis-(tert-butyl hydroperoxide)-3, 3, the 5-trimethyl-cyclohexane, 2, two (tert-pentyl the peroxide)-butane of 2-, 2, 5-dimethyl-2, two (benzoyl the peroxide)-hexanes of 5-, two (4-chlorobenzene formacyl) superoxide, two (2, 4-dichloro-benzoyl base) superoxide or two (4-methyl benzoyl) superoxide.
9. fluorescence EVA glued membrane according to claim 7, is characterized in that, described peroxide cross-linking agent is tert-butyl hydroperoxide carbonic acid-2-ethylhexyl.
10. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise additional crosslinker in described formula.
11. fluorescence EVA glued membrane according to claim 10, is characterized in that, the combination that described additional crosslinker is any one or at least two kinds in cyanacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate.
12. fluorescence EVA glued membrane according to claim 11, is characterized in that, described additional crosslinker is cyanacrylate, trimethylolpropane trimethacrylate or compound that the two mixes according to the mass ratio of 1:1.
13. fluorescence EVA glued membrane according to claim 12, is characterized in that, the described additional crosslinker compound that to be cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1.
14. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise hindered amine light stabilizer in described glued membrane.
15. fluorescence EVA glued membrane according to claim 14, is characterized in that, described hindered amine light stabilizer is two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 3,5-di-t-butyl-4-hydroxy-benzoic acid cetyl ester, three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester, two (1-alkoxyl group in the last of the ten Heavenly stems-2,2,6,6-tetramethyl piperidine-4-alcohol) combination of any one in sebate or at least two kinds.
16. fluorescence EVA glued membrane according to claim 15, is characterized in that, described hindered amine light stabilizer is two (2,2,6,6-tetramethyl--4-piperidyl) sebates.
17. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise auxiliary antioxidant in described glued membrane.
18. fluorescence EVA glued membrane according to claim 17, it is characterized in that, described auxiliary antioxidant is tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, three (4-nonyl phenol) phosphorous acid ester, 2,2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) combination of any one in the positive octadecyl ester of propionic acid, two (2,4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite or at least two kinds.
19. fluorescence EVA glued membrane according to claim 18, it is characterized in that, described auxiliary antioxidant is for being three (4-nonyl phenol) phosphorous acid ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester or compound that the two mixes according to the mass ratio of 1:1.
20. fluorescence EVA glued membrane according to claim 19, is characterized in that, the described auxiliary antioxidant compound that to be three (4-nonyl phenol) phosphorous acid esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester mix according to the mass ratio of 1:1.
21. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise tackifier in described glued membrane.
22. fluorescence EVA glued membrane according to claim 21, it is characterized in that the combination that described tackifier are any one or at least two kinds in γ-methacryloxypropyl trimethoxy silane, γ-aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, ester gum.
23. fluorescence EVA glued membrane according to claim 22 is characterized in that described tackifier are γ-methacryloxypropyl trimethoxy silane.
24. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise softening agent in described glued membrane.
25. fluorescence EVA glued membrane according to claim 24 is characterized in that described softening agent is trioctyl phosphate.
26. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, also comprise antacid in described glued membrane.
27. fluorescence EVA glued membrane according to claim 26, is characterized in that, the combination that described antacid is any one or at least two kinds in calcium stearate, calcium carbonate, sodium bicarbonate, magnesium oxide, aluminium hydroxide, Magnesium Trisilicate.
28. fluorescence EVA glued membrane according to claim 27 is characterized in that described antacid is calcium stearate.
29. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, in described glued membrane, according to weight percent, comprise following component: the EVA93.80wt%-99.53wt% that the content of vinyl acetate is 26wt%-35wt%, polymerisable fluorescent monomer 0.02wt%-0.2wt%, peroxide cross-linking agent 0.1wt%-2wt%, additional crosslinker 0.1wt%-2wt%, hindered amine light stabilizer 0.05wt%-0.4wt%, auxiliary antioxidant 0.05wt%-0.4wt%, tackifier 0.05wt%-0.4wt%, softening agent 0.05wt%-0.4wt% and antacid 0.05wt%-0.4wt%.
30. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, in described glued membrane, according to weight percent, comprise following component: the EVA95.35wt%-98.45wt% that the content of vinyl acetate is 28wt%-33wt%, polymerisable fluorescent monomer 0.05wt%-0.15wt%, peroxide cross-linking agent 0.5wt%-1.5wt%, additional crosslinker 0.5wt%-1.5wt%, hindered amine light stabilizer 0.1wt%-0.3wt%, auxiliary antioxidant 0.1wt%-0.3wt%, tackifier 0.1wt%-0.3wt%, softening agent 0.1wt%-0.3wt% and antacid 0.1wt%-0.3wt%.
31. according to the described fluorescence EVA of one of claim 1-3 glued membrane, it is characterized in that, comprise following component according to weight percent in described glued membrane: the EVA96.90wt% that the content of vinyl acetate is 30wt%, the compound 0.1wt% that vinylformic acid yttrium and methacrylic acid yttrium mix according to the mass ratio of 1:1, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl 1wt%, the compound 1wt% that cyanacrylate and trimethylolpropane trimethacrylate mix according to the mass ratio of 1:1, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate 0.2wt%, three (4-nonyl phenol) phosphorous acid ester and tricresyl phosphites (2, the 4-di-tert-butyl-phenyl) the compound 0.2wt% that ester mixes according to the mass ratio of 1:1, γ-methacryloxypropyl trimethoxy silane 0.2wt%, trioctyl phosphate 0.2wt% and calcium stearate 0.2wt%.
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| CN201210450694.XA CN102911612B (en) | 2012-11-12 | 2012-11-12 | Fluorescent EVA (Ethylene vinyl acetate) glue film |
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| CN201210450694.XA CN102911612B (en) | 2012-11-12 | 2012-11-12 | Fluorescent EVA (Ethylene vinyl acetate) glue film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101935504B (en) * | 2010-09-02 | 2012-03-21 | 上海天洋热熔胶有限公司 | Efficient uvioresistant EVA (Ethylene-Vinyl Acetate) adhesive film for packaging solar battery and preparation method thereof |
| CN102559079A (en) * | 2012-01-09 | 2012-07-11 | 苏州泰科尼光伏材料有限公司 | Ethylene vinyl acetate (EVA) glue film for encapsulating solar battery |
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Address after: 215129 Suzhou high tech Zone, Jiangsu Province, Lu Shan Road, No. 199, No. Co-patentee after: Changshu Canadian Solar Inc. Patentee after: Artes sunshine Power Group Co. Ltd. Address before: 215028 Suzhou City, Jiangsu, Suzhou high tech Industrial Development Zone, deer mountain road No. 199 Co-patentee before: Changshu Canadian Solar Inc. Patentee before: Canadian (China) Investment Co., Ltd. |
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Address after: 215129 199 deer Road, Suzhou hi tech Development Zone, Jiangsu, Suzhou Patentee after: Atlas sunshine Power Group Co.,Ltd. Patentee after: Changshu Artes Sunshine Power Technology Co.,Ltd. Address before: 215129 199 deer Road, Suzhou hi tech Development Zone, Jiangsu, Suzhou Patentee before: CSI SOLAR POWER GROUP Co.,Ltd. Patentee before: Changshu Artes Sunshine Power Technology Co.,Ltd. |