CN103131336B - Preparation method of silane crosslinked ethylene-vinyl acetate copolymer adhesive film - Google Patents
Preparation method of silane crosslinked ethylene-vinyl acetate copolymer adhesive film Download PDFInfo
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- CN103131336B CN103131336B CN201310094732.7A CN201310094732A CN103131336B CN 103131336 B CN103131336 B CN 103131336B CN 201310094732 A CN201310094732 A CN 201310094732A CN 103131336 B CN103131336 B CN 103131336B
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- adhesive film
- vinyl acetate
- silane
- preparation
- ethylene vinyl
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- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 111
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 111
- 239000002313 adhesive film Substances 0.000 title claims abstract description 80
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 17
- 238000010030 laminating Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 19
- 230000008878 coupling Effects 0.000 claims description 18
- 238000010168 coupling process Methods 0.000 claims description 18
- 238000005859 coupling reaction Methods 0.000 claims description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 11
- 238000007766 curtain coating Methods 0.000 claims description 9
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- AKFOUVKOUGMNAW-UHFFFAOYSA-N cumene;2-hydroperoxy-2-methylpropane Chemical compound CC(C)(C)OO.CC(C)C1=CC=CC=C1 AKFOUVKOUGMNAW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 150000001451 organic peroxides Chemical class 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000003475 lamination Methods 0.000 description 11
- 239000004971 Cross linker Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- -1 2,2,6,6-tetramethyl--4-piperidyl Chemical group 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229950002083 octabenzone Drugs 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method of a silane crosslinked ethylene-vinyl acetate copolymer adhesive film, which comprises the following steps: evenly mixing a composition, extruding, casting, cooling, drawing, and coiling to obtain the silane crosslinked ethylene-vinyl acetate copolymer adhesive film, wherein the extruding processing temperature is 100-150 DEG C; and the composition comprises the following components in parts by mass: 100 parts of ethylene-vinyl acetate copolymer, 0.1-2 parts of silane coupling agent A, 0.1-2 parts of silane coupling agent B and 0.01-0.2 part of organic peroxide. According to the invention, silane crosslinking is late crosslinking, crosslinking reaction does not need to be performed in a laminating machine, and the packaging of an assembly can be finished by simply pressurizing for 5-8 minutes under conventional treatment conditions in the vacuum laminating machine, thus greatly improving the laminating efficiency and saving the production cost.
Description
Technical field
The present invention relates to a kind of preparation method of ethylene vinyl acetate adhesive film of crosslinked with silicane.
Background technology
At present, solar electrical energy generation is becoming most important new forms of energy.Solar cell is the core in solar power system, is also to be worth the highest part in solar power system, and its effect converts solar energy into electrical energy, or is sent in store battery and stores, or promotes loaded work piece.The quality of solar cell and cost will directly determine quality and the cost of whole system.
Conventional solar cell encapsulation structure is as follows: upper strata is toughened glass, middle layer is cell piece, lower floor is backboard, at glass and cell piece, respectively has one deck or double-deck ethylene vinyl acetate adhesive film (EVA adhesive film) to be firmly bonded together by layers of material between cell piece and backboard.EVA adhesive film is the important packaged material of solar cell, in order to ensure the outwork that the solar cell after encapsulating is permanently effective, EVA adhesive film must have sufficiently high transmittance, with assembly material glass, cell piece, backboard etc., there is permanently effective high-adhesive-strength, excellent weathering resistance (resistance to ultraviolet, high-low temperature resistant, resistance to high humidity) and good encapsulation process.
Ethylene vinyl acetate resin (EVA) is a kind of polymkeric substance of linear structure, and its thermotolerance, creep resistance and elasticity are all poor, can not be directly used in the encapsulation of solar module.Existing method adopts linking agent to make EVA resin generation crosslinking reaction generate 3-D solid structure, thus realize material transformation to the thermosetting polymer of " insoluble do not melt " from the thermoplastic polymer of " solvable melt ".Crosslinked EVA resin use properties there occurs significant change, and comprise mobility and decline, intensity, consistency and elasticity increase, and mechanical property, thermotolerance, weathering resistance, chemical resistance ability improve, and work-ing life extends.At present, crosslinked EVA adhesive film can meet the requirement that solar module long-term outdoor uses completely, and work-ing life can reach more than 25 years.
In prior art, conventional linking agent is organo-peroxide.The organo-peroxide of widespread use is dialkyl peroxide, tert-butylperoxy benzoate and peroxy esters class.Organic peroxide decomposes generation free radical has captured the hydrogen in polymkeric substance, and produces the free radical of polymkeric substance thus, forms the C-C key combined again, completes chemically crosslinked.In crosslinked polymer reaction, the free polymer readical that additional crosslinker can promptly be produced with hydrogen abstraction reaction reacts, improve the stability of free polymer readical, reach the object improving cross-linking effect, comprise reduction crosslinking temperature, accelerate crosslinking time, improve binding property, improve thermotolerance, improve the physical property such as compression tension set.Therefore, in organo-peroxide is crosslinked, additional crosslinker has important effect.In general, mostly the compound being used as additional crosslinker is the unsaturated compound with more than one or two double bond.At present, the additional crosslinker being applicable to EVA crosslinking reaction mainly contains: triallyl cyanurate, triallyl isocyanurate, ethyleneglycol dimethyacrylate, trimethacrylate acid trishydroxymethyl propyl ester, Vinylstyrene, Phthalic acid, diallyl ester etc.For the compound of conventional use at present, organo-peroxide is tert-butyl hydroperoxide carbonic acid-2-ethylhexyl (TBEC), additional crosslinker is triallyl isocyanurate, by mass parts, general 100 parts of ethylene vinyl acetate resins need add organo-peroxide tert-butyl hydroperoxide carbonic acid-2-ethylhexyl 0.5 ~ 1.0% and additional crosslinker triallyl isocyanurate 1.0 ~ 2.0%, above-mentioned composition is mixed, through extruding, curtain coating, cooling, drawing, the operation such as to batch and be processed into EVA adhesive film.After this EVA adhesive film is put into solar module, in vacuum laminator, carry out lamination, temperature 140 ~ 145 DEG C, vacuumize 5 minutes, pressurize 10 ~ 13 minutes, moulding pressure 0.5 ~ 1.0kg/cm
2under condition, ethylene vinyl acetate resin generation crosslinking reaction, degree of crosslinking can reach 80 ~ 90%.
But, practical application finds, there are the following problems for the EVA adhesive film of above-mentioned peroxide crosslinking: (1) is owing to adding a large amount of organo-peroxides and additional crosslinker, EVA adhesive film is easily impelled to produce xanthochromia, and cause component power to decline due to EVA adhesive film xanthochromia, in addition, a large amount of organic peroxide decomposes produces small molecules and easily produces bubble, affects quality product; (2) because ethylene vinyl acetate resin, in lamination process, crosslinking reaction occurs, thus, in order to ensure certain degree of crosslinking, lamination times longer (generally at 10 ~ 13 minutes), result in the shortcomings such as production efficiency is low; (3) adding due to a large amount of organo-peroxide and additional crosslinker, strict production control processing temperature 90 DEG C should be no more than in the middle of EVA adhesive film production process, otherwise very easily produce sizing material, cause stopping production, inventory disposal etc. to lose, thus processing condition are comparatively harsh.
Therefore, develop a kind of preparation method of new EVA adhesive film, to be more suitable for solar module, there is positive realistic meaning.
In prior art, in solar module, silane coupling agent generally adds in EVA multipolymer as tackiness agent, namely to combine with EVA itself, form good combination with the glass in assembly, cell piece and back veneer material again, it has excellent bonding strength and water-fast, weather resistance.
Be applicable to organo-peroxide of the present invention as initiator, be not particularly limited, preferably from following organo-peroxide: tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, peroxidized t-butyl perbenzoate, 4,4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, dicumyl peroxide, two (t-tutyl cumyl peroxide), 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane etc.
The present invention is not particularly limited for the kind of ultraviolet absorbers and photostabilizer.Preferred UV light absorber is Octabenzone, and preferred photostabilizer is two (2,2,6,6-tetramethyl--4-piperidyl) sebates.In the present invention, photostabilizer coordinates ultraviolet absorbers and other components to use together, single use ultraviolet absorbers can be played to be beyond one's reach best effect, effectively prevent xanthochromia and the blocker rationality loss of energy of EVA adhesive film, suppress or weaken photodegradation, improving the light aging resisting property of EVA adhesive film.
In technique scheme, thickness 0.5 mm of the ethylene vinyl acetate adhesive film of described crosslinked with silicane, width is 1000 mm.
Preferably, the melting index of described ethylene vinyl acetate is 4 ~ 30 grams/10 minutes, and DSC fusing point is 70 ~ 90 DEG C; Wherein the mass content of vinyl acetate between to for plastic is 14 ~ 28%.
Above-mentioned preferred ethylene vinyl acetate is combined with specified proportion the EVA adhesive film process for processing obtained with other component and is very easy to, shelf stability is excellent, even if be also not easy adhesion, distortion at damp and hot weather glued membrane, not easily bubble is produced when laminating operation, and the shrinking percentage of glued membrane is minimum, therefore there will not be starved and cell-slice displacement, substantially improve the accepted product percentage of assembly.
In technique scheme, described organo-peroxide is selected from tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, peroxidized t-butyl perbenzoate, 4,4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, dicumyl peroxide, two (tert-butyl hydroperoxide isopropyl) benzene and 2, one or more in 5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane.
The present invention asks the ethylene vinyl acetate adhesive film of the crosslinked with silicane protecting above-mentioned preparation method to obtain simultaneously.
A kind of preparation method of solar module, after the ethylene vinyl acetate adhesive film of the ethylene vinyl acetate adhesive film of glass substrate, crosslinked with silicane according to claim 1, cell piece, crosslinked with silicane according to claim 1, backboard is stacked from top to bottom, put into laminating machine and carry out laminating operation, can solar module be obtained;
The processing condition of described laminating operation are: temperature 140 ~ 150 DEG C, vacuumize 5 minutes, and pressurize 5 ~ 8 minutes, moulding pressure 0.5 ~ 1.0kg/cm
2.
Test proves, when composition extrude processing temperature reach 150 DEG C time, silane coupling A can react with EVA multipolymer and generate grafting EVA adhesive film, such EVA adhesive film is when lamination, lamination times can shorten to 140 DEG C, vacuumizes 5 minutes, pressurizes 5 minutes.
The present invention asks the solar module protecting above-mentioned preparation method to obtain simultaneously.
Working mechanism of the present invention is: mixed by the composition containing ethylene vinyl acetate, silane coupling A, silane coupling agent B, organo-peroxide etc., through extruding, curtain coating, cooling, drawing, batch, obtain ethylene vinyl acetate adhesive film; Then above-mentioned ethylene vinyl acetate adhesive film is put into solar module and carry out laminating operation, obtained solar module; Wherein, extruding in operation, silane coupling A can react with EVA multipolymer and generate grafting EVA; Then can there is crosslinking reaction at normal temperatures in grafting EVA and silane coupling A; Namely silane coupling A participates in crosslinking reaction as linking agent, and vinyl one end of silane coupling A is grafted in EVA copolymer chain in the reaction, and the alkoxyl group of the other end again the EVA that crosslinking reaction forms crosslinked with silicane occurs at normal temperatures; The first step is graft reaction, and be that silane coupling A is grafted in EVA copolymer chain at 140 ~ 150 DEG C, second step is crosslinking reaction, is that the alcoxyl cardinal extremity of silane coupling agent occurs at normal temperatures.
Due to the employing of technique scheme, compared with prior art, tool of the present invention has the following advantages:
1. this invention exploits a kind of preparation method of ethylene vinyl acetate adhesive film of a kind of crosslinked with silicane newly, crosslinked with silicane is cross-linked in the later stage, do not need to realize crosslinking reaction in laminating machine, same in vacuum laminator with under the treatment condition of routine (temperature 140 ~ 145 DEG C, vacuumize 5 minutes), as long as pressurization can complete the encapsulation of assembly for 5 ~ 8 minutes, thus substantially increase laminating efficiency, save production cost.
2. the present invention is main auxiliary agent with silane, only need to add minute quantity superoxide as initiator, namely the consumption of superoxide and additional crosslinker greatly reduces, and therefore the resolvent of superoxide reduces, and not easily produces bubble and not easily causes the xanthochromia of EVA adhesive film; In addition, because the addition of superoxide is few, the process for processing temperature of EVA adhesive film can be not too harsh, processing temperature (processing temperature is increased to 100 ~ 150 DEG C) can be improved, this not only effectively can control shrinking percentage, the increase extrusion capacity of EVA adhesive film, and can not sizing material be produced, long-time continuous can be realized and produce.
3. test proves, the ethylene vinyl acetate adhesive film of crosslinked with silicane of the present invention is adopted to prepare in solar module process, greatly can shorten lamination times (foreshortening to 5 ~ 8 minutes from existing 13 minutes), thus improve production efficiency, there is positive realistic meaning.
4. adopt the ethylene vinyl acetate adhesive film of crosslinked with silicane of the present invention to prepare in solar module process, do not produce bubble during lamination and EVA adhesive film can not produce xanthochromia is conducive to reducing component power decay.
5. glued membrane of the present invention has good temperature tolerance and encapsulation process, and laminating efficiency is high; In addition, can not there is xanthochromia, transmittance conservation rate is good, component power keeps in this glued membrane and use the solar module of this glued membrane to have excellent wet and heat ageing resistant and ultraviolet aging resistance, good with the stripping strength conservation rate of glass and backboard.
Summary of the invention
The object of the invention is to provide a kind of preparation method of ethylene vinyl acetate adhesive film of crosslinked with silicane.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of ethylene vinyl acetate adhesive film of crosslinked with silicane, composition is mixed, through extruding, curtain coating, cooling, drawing, batch, the ethylene vinyl acetate adhesive film of crosslinked with silicane can be obtained;
The described processing temperature extruded is 100 ~ 150 DEG C;
Described composition comprises following component, in mass:
Ethylene vinyl acetate 100 parts
Silane coupling A 0.1 ~ 2 part
Silane coupling agent B 0.1 ~ 2 part
Organo-peroxide 0.01 ~ 0.2 part
Photostabilizer 0.01 ~ 0.2 part
Ultraviolet absorbers 0.01 ~ 0.2 part;
Wherein, described silane coupling A is selected from one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane and vinyltriacetoxy silane;
Described silane coupling agent B is selected from one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, γ-glycidoxypropyltrimewasxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane and γ-mercaptopropyl trimethoxysilane.
Above, described silane coupling agent B is selected from the silane containing vinyl-functional, and not containing the silane of vinyl-functional; The described silane containing vinyl-functional is as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane; Do not contain the silane of vinyl-functional as γ-glycidoxypropyltrimewasxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane and γ-mercaptopropyl trimethoxysilane.
Above, described silane coupling agent has two kinds of effects, wherein, silane coupling A (silane containing vinyl-functional) is the linking agent as EVA multipolymer, silane coupling A is the silane that a class has vinyl-functional, and vinyl-functional wherein reacts with EVA main chain under initiator effect.Silane coupling agent B is as tackiness agent, its action principle is that itself has two kinds of groups, the alkoxy-functional of one end can combine with by the inorganic materials such as glass, metal of gluing, the organo-functional group of the other end then can be combined with macromolecular material, thus form powerful higher chemical bond at bonding interface, substantially improve cohesive strength.
Use silane coupling agent B, the bonding strength of EVA adhesive film and glass can be greater than 80N/cm, is greater than 40N/cm with the bonding strength of fluorine material backboard.In the present invention, silane coupling agent B can identical from silane coupling A also can be different, the preferred silane coupling agent adopting combination, namely a kind of vinyl silanes (silane containing vinyl-functional) and the non-vinyl silanes of one (not containing the silane of vinyl-functional) is adopted, both can reach the degree of crosslinking required for EVA adhesive film, the bonding strength of EVA adhesive film excellence can have been realized again.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one:
100 parts of (mass parts) EVA multipolymer [VA content 28%, melting index (MI) be 25 grams/10 minutes (190 DEG C, 2.16 kilogram), dsc (DSC) fusing point is 70 DEG C, Vicat softening point is 42 DEG C, Arkema of France, 2825] 1 part of silane coupling A is added in: vinyltrimethoxy silane (Dow corning company, 6300), 1 part of silane coupling agent B: gamma-methyl allyl acyloxypropyl trimethoxysilane (Dow corning company, 6030), 0.1 part of organo-peroxide: two (t-butylperoxyisopropyl) benzene (Akzo Nobel, Perkadox 14s-fl), 0.2 part of ultraviolet absorbers: Octabenzone (Beijing addition auxiliary agent institute, GW531), 0.1 part of photostabilizer: two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate (Beijing addition auxiliary agent institute, GW480), all raw materials are mixed, add in single screw extrusion machine and melt extrude, processing temperature is 100 DEG C, then through curtain coating, cooling, traction, the operation such as to batch, obtain EVA adhesive film S1, film thickness is 0.5 mm.
Gained EVA adhesive film is prepared solar module as encapsulating film, upper strata is the glass substrate of thickness 3mm, and middle layer is cell piece, and lower floor is the fluorine material backboard of thickness 0.33mm, it is EVA adhesive film between glass and cell piece, be EVA adhesive film between cell piece and backboard, after layers of material is stacked in order, put into vacuum laminator, design temperature 140 DEG C, vacuumize 5 minutes, pressurize 8 minutes, EVA adhesive film by layers of material bonding firmly, becomes solar module.
Embodiment two:
100 parts of EVA multipolymer 2825(VA content 28%) in add 2 parts of silane coupling A vinyltriethoxysilane (Dow corning companies, 6518), 1 part of silane coupling agent B6030, 0.2 part of two (t-butylperoxyisopropyl) benzene of organo-peroxide, 0.2 part of ultraviolet absorbers Octabenzone, 0.1 part of photostabilizer two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, all raw materials are mixed, add in single screw extrusion machine and melt extrude, processing temperature is 100 DEG C, then through curtain coating, cooling, traction, the operation such as to batch, obtain EVA adhesive film S2, film thickness is 0.5mm.
Gained EVA adhesive film is prepared solar module as encapsulating film, upper strata is the glass substrate of thickness 3mm, and middle layer is cell piece, and lower floor is the fluorine material backboard of thickness 0.33mm, it is EVA adhesive film between glass and cell piece, be EVA adhesive film between cell piece and backboard, after layers of material is stacked in order, put into vacuum laminator, design temperature 140 DEG C, vacuumize 5 minutes, pressurize 8 minutes, EVA adhesive film by layers of material bonding firmly, becomes solar module.
Embodiment three:
100 parts of EVA multipolymer [VA content 18%, melting index (MI) be 2.5 grams/10 minutes (190 DEG C, 2.16 kilogram), dsc (DSC) fusing point is 88 DEG C, Vicat softening point is 64 DEG C, du pont company, 460] 1 part of silane coupling A vinyltrimethoxy silane 6300 is added in, 1 part of silane coupling agent B gamma-methyl allyl acyloxypropyl trimethoxysilane 6030, 0.1 part of organo-peroxide 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane (Akzo Nobel, TRIGONOX 101), 0.2 part of ultraviolet absorbers Octabenzone, 0.1 part of photostabilizer two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, all raw materials are mixed, add in single screw extrusion machine and melt extrude, processing temperature is 150 DEG C, then through curtain coating, cooling, traction, the operation such as to batch, obtain EVA adhesive film S3, film thickness is 0.5mm.
Gained EVA adhesive film is prepared solar module as encapsulating film, upper strata is the glass substrate of thickness 3mm, and middle layer is cell piece, and lower floor is the fluorine material backboard of thickness 0.33mm, it is EVA adhesive film between glass and cell piece, be EVA adhesive film between cell piece and backboard, after layers of material is stacked in order, put into vacuum laminator, design temperature 140 DEG C, vacuumize 5 minutes, pressurize 5 minutes, EVA adhesive film by layers of material bonding firmly, becomes solar module.
Embodiment four:
100 parts of EVA multipolymer 460(VA content 18%) in add 2 parts of silane coupling A vinyltrimethoxy silanes 6300, 0.5 part of silane coupling agent B γ-glycidoxypropyltrimewasxysilane (Dow corning company, 6040), 0.1 part of organo-peroxide 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane, 0.2 part of ultraviolet absorbers Octabenzone, 0.1 part of photostabilizer two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, all raw materials are mixed, add in single screw extrusion machine and melt extrude, processing temperature is 150 DEG C, then through curtain coating, cooling, traction, the operation such as to batch, obtain EVA adhesive film S4, film thickness is 0.5mm.
Gained EVA adhesive film is prepared solar module as encapsulating film, upper strata is the glass substrate of thickness 3mm, and middle layer is cell piece, and lower floor is the fluorine material backboard of thickness 0.33mm, it is EVA adhesive film between glass and cell piece, be EVA adhesive film between cell piece and backboard, after layers of material is stacked in order, put into vacuum laminator, design temperature 140 DEG C, vacuumize 5 minutes, pressurize 5 minutes, EVA adhesive film by layers of material bonding firmly, becomes solar module.
Comparative example one:
100 parts of EVA multipolymer 2825(VA content 28%) in add two (t-butylperoxyisopropyl) benzene of 2 parts of organo-peroxides, 0.5 part of silane coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane, 0.2 part of ultraviolet absorbers Octabenzone, 0.1 part of photostabilizer two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, all raw materials are mixed, add in single screw extrusion machine and melt extrude, processing temperature is 90 DEG C, then through curtain coating, cooling, traction, the operation such as to batch, obtain EVA adhesive film B1-1, B1-2, B1-3, film thickness is 0.5mm.
Gained EVA adhesive film is prepared solar module as encapsulating film, upper strata is the glass substrate of thickness 3mm, and middle layer is cell piece, and lower floor is the fluorine material backboard of thickness 0.33mm, it is EVA adhesive film between glass and cell piece, be EVA adhesive film between cell piece and backboard, after layers of material is stacked in order, put into vacuum laminator, design temperature 140 DEG C, vacuumize 5 minutes, pressurize 5 ~ 13 minutes, EVA adhesive film by layers of material bonding firmly, becomes solar module.
Carry out performance test and evaluation, following standard and step as follows:
1, sample preparation:
EVA adhesive film be clipped between 1 glass substrate and 1 backboard, use vacuum laminator to make model, lamination is in table 1.Whether the outward appearance of visual observation model, there is bubble, evaluates as follows:
O: do not occur bubble
×: there is bubble
2, wet and heat ageing resistant performance:
EVA adhesive film model is carried out hydrothermal aging test, and test conditions is temperature 85 DEG C according to the requirement of International Electrotechnical Commission Standard IEC61215, relative humidity 85%, 1000 hours.
Stripping strength before and after test is tested according to GB/T2790 regulation.And be calculated as follows stripping strength conservation rate:
Yellowness index (⊿ YI before and after test) test according to GB/T2409.
3, anti-ultraviolet ageing performance:
EVA adhesive film model is carried out ultraviolet ageing test, and test conditions is ultraviolet wavelength 280 ~ 385nm according to the requirement of IEC61215, total radiation 15kWh/m
2with ultraviolet wavelength 280 ~ 320nm, total radiation 5 kWh/m
2.
By above-mentioned same method test stripping strength conservation rate and yellowness index.
By the EVA adhesive film that above-described embodiment and comparative example obtain, through aforesaid method sample preparation and test, result is as follows:
Table 1: the test conditions of various EVA adhesive film
Table 2: the sign of various EVA adhesive film
From the above results, EVA adhesive film of the present invention not easily produces bubble when lamination of solar battery components, can reduce lamination times raises the efficiency, and demonstrates excellent wet and heat ageing resistant performance and anti-ultraviolet ageing performance.And the glued membrane of comparative example one aging when lamination 8 minutes and 5 minutes after there is bubble, and the yellowness index of the glued membrane of comparative example one is all bigger than normal.Therefore, EVA adhesive film of the present invention is used also to have superior wet and heat ageing resistant performance and resistance to UV aging energy as the solar module that encapsulating film obtains.
Claims (7)
1. a preparation method for the ethylene vinyl acetate adhesive film of crosslinked with silicane, is characterized in that: mixed by composition, through extruding, curtain coating, cooling, drawing, batches, can obtain the ethylene vinyl acetate adhesive film of crosslinked with silicane;
The described processing temperature extruded is 100 ~ 150 DEG C;
Described composition comprises following component, in mass:
Ethylene vinyl acetate 100 parts
Silane coupling A 0.1 ~ 2 part
Silane coupling agent B 0.1 ~ 2 part
Organo-peroxide 0.01 ~ 0.2 part
Photostabilizer 0.01 ~ 0.2 part
Ultraviolet absorbers 0.01 ~ 0.2 part;
Wherein, described silane coupling A is selected from one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane and vinyltriacetoxy silane;
Described silane coupling agent B is selected from one or more in γ-glycidoxypropyltrimewasxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane and γ-mercaptopropyl trimethoxysilane.
2. preparation method according to claim 1, is characterized in that: thickness 0.5 mm of the ethylene vinyl acetate adhesive film of described crosslinked with silicane, width is 1000 mm.
3. preparation method according to claim 1, is characterized in that: the melting index of described ethylene vinyl acetate is 4 ~ 30 grams/10 minutes, and DSC fusing point is 70 ~ 90 DEG C; Wherein the mass content of vinyl acetate between to for plastic is 14 ~ 28%.
4. preparation method according to claim 1, it is characterized in that: described organo-peroxide is selected from tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, peroxidized t-butyl perbenzoate, 4,4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, dicumyl peroxide, two (tert-butyl hydroperoxide isopropyl) benzene and 2, one or more in 5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane.
5. the ethylene vinyl acetate adhesive film of crosslinked with silicane that preparation method obtains any one of Claims 1-4.
6. the preparation method of a solar module, it is characterized in that, after the ethylene vinyl acetate adhesive film of the ethylene vinyl acetate adhesive film of glass substrate, crosslinked with silicane according to claim 1, cell piece, crosslinked with silicane according to claim 1, backboard is stacked from top to bottom, put into laminating machine and carry out laminating operation, can solar module be obtained;
The processing condition of described laminating operation are: temperature 140 ~ 150 DEG C, vacuumize 5 minutes, and pressurize 5 ~ 8 minutes, moulding pressure 0.5 ~ 1.0kg/cm
2.
7. the solar module that obtains of preparation method according to claim 6.
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| CN103333625B (en) * | 2013-07-01 | 2015-02-18 | 江苏达胜热缩材料有限公司 | Heat-shrinkable composite insulating tape |
| JP6915544B2 (en) * | 2015-11-04 | 2021-08-04 | 昭和電工マテリアルズ株式会社 | Adhesive composition and structure |
| CN108611025A (en) * | 2018-04-10 | 2018-10-02 | 浙江祥邦科技股份有限公司 | A kind of super fast curing solar energy packaging adhesive film and preparation method thereof |
| CN109087964A (en) * | 2018-07-24 | 2018-12-25 | 合肥华盖光伏科技有限公司 | A kind of preparation method of photovoltaic module back side performance protective film |
| CN111690327B (en) * | 2019-03-11 | 2022-03-15 | 杭州福斯特应用材料股份有限公司 | Three-layer co-extrusion adhesive film |
| CN110229623A (en) * | 2019-06-28 | 2019-09-13 | 北京知淘科技有限责任公司 | A kind of solar photovoltaic assembly packaging EVA adhesive film and preparation method thereof |
| CN112457447A (en) * | 2020-11-25 | 2021-03-09 | 郑州中原思蓝德高科股份有限公司 | Modified polyolefin additive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1150357A1 (en) * | 1998-12-07 | 2001-10-31 | Bridgestone Corporation | Cover material for solar cell, sealing film and solar cell |
| CN102504713A (en) * | 2011-11-21 | 2012-06-20 | 常熟阿特斯阳光电力科技有限公司 | Novel ultraviolet-resistant EVA (Ethylene-Vinyl Acetate) glue film |
-
2013
- 2013-03-22 CN CN201310094732.7A patent/CN103131336B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1150357A1 (en) * | 1998-12-07 | 2001-10-31 | Bridgestone Corporation | Cover material for solar cell, sealing film and solar cell |
| CN102504713A (en) * | 2011-11-21 | 2012-06-20 | 常熟阿特斯阳光电力科技有限公司 | Novel ultraviolet-resistant EVA (Ethylene-Vinyl Acetate) glue film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219689A (en) * | 2016-12-19 | 2018-06-29 | 上海海优威新材料股份有限公司 | Glued membrane of photovoltaic module High-temperature Packaging and preparation method thereof |
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