CN101820001B - Packaging adhesive film for solar cell - Google Patents
Packaging adhesive film for solar cell Download PDFInfo
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- CN101820001B CN101820001B CN2010101605893A CN201010160589A CN101820001B CN 101820001 B CN101820001 B CN 101820001B CN 2010101605893 A CN2010101605893 A CN 2010101605893A CN 201010160589 A CN201010160589 A CN 201010160589A CN 101820001 B CN101820001 B CN 101820001B
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- solar cell
- adhesive film
- packaging adhesive
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 41
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 41
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 52
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 51
- 238000004132 cross linking Methods 0.000 claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 18
- -1 pentaerythritol ester Chemical class 0.000 claims description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 9
- 229940123457 Free radical scavenger Drugs 0.000 claims description 9
- 235000019260 propionic acid Nutrition 0.000 claims description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 9
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical class CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- HEJCZAMFVMNFLC-UHFFFAOYSA-N 10-oxo-10-(2,2,6,6-tetramethylpiperidin-4-yl)oxydecanoic acid Chemical compound CC1(C)CC(OC(=O)CCCCCCCCC(O)=O)CC(C)(C)N1 HEJCZAMFVMNFLC-UHFFFAOYSA-N 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 150000005690 diesters Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- LUQZKEZPFQRRRK-UHFFFAOYSA-N 2-methyl-2-nitrosopropane Chemical compound CC(C)(C)N=O LUQZKEZPFQRRRK-UHFFFAOYSA-N 0.000 claims description 3
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 3
- LRVCBZUHYJVCGF-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.C(O)(O)=O.C(C)(C)(C)OO Chemical compound N(=O)OC(C)CCCCCC.C(O)(O)=O.C(C)(C)(C)OO LRVCBZUHYJVCGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 claims description 2
- IPMMQJSVSDXQQQ-UHFFFAOYSA-N OC1=CC=C(C=C1)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)C)C(C(=O)O)C Chemical compound OC1=CC=C(C=C1)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)C)C(C(=O)O)C IPMMQJSVSDXQQQ-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 claims description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 claims 1
- XZEXIWMRKRHNFZ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate carbonic acid Chemical compound OC(O)=O.CCCCC(CC)C(=O)OC(C)(C)C XZEXIWMRKRHNFZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 abstract description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000010030 laminating Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HGADUVPRBJQDLZ-UHFFFAOYSA-N carbonic acid;2-ethylhexanoic acid Chemical compound OC(O)=O.CCCCC(CC)C(O)=O HGADUVPRBJQDLZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a packaging adhesive film for a solar cell, which can effectively prolong scorch time T2 and improve the processing and packaging properties of an EVA adhesive film on the basis of small change on total cross-linking time TC. The packaging adhesive film for the solar cell contains a copolymer of ethylene-vinyl acetate (EVA), a cross-linking agent, a cross-linking inhibitor and a radical trap, wherein, the masses of the cross-linking inhibitor and the radical trap are respectively 0.1-1.0% and 0-0.3% of the mass of the ethylene-vinyl acetate copolymer, and the cross-linking time of the packaging adhesive film for the solar cell is 10-30min. In the invention, the cross-linking inhibitor and the radical trap are added based on the formula of the existing packaging adhesive film for the solar cell to form a stable molecular structure with active radicals generated in the peroxide cross-linking agent, thus effectively preventing early-stage cross-linking and over cross-linking, and effectively prolonging the scorch time T2 on the basis of guaranteeing the total cross-linking time TC to meet the requirements.
Description
Technical field
The present invention relates to a kind of packaging adhesive film for solar cell, particularly relating to the ethylene-vinyl acetate copolymer is the solar cell heat-sealing glued membrane of primary raw material.
Background technology
Toughened glass 1, packaging adhesive film 2, battery sheet 3, packaging adhesive film 2, TPT backboard 4 are stacked in order,,, promptly can be made into thin-film solar cells with laminating machine vacuum lamination 15min～30min curing molding at 130 ℃～170 ℃.The structure of the solar module of process packaging adhesive film for solar cell encapsulation as shown in Figure 1.
Packaging adhesive film for solar cell, be to be primary raw material with EVA, cooperate function additives such as peroxide cross-linking agent, assistant crosslinking agent, coupling agent, antioxidant, ultra-violet stabilizer, process through technical processs such as melting mixing, curtain coating casting sheet, side cut rollings.The primary raw material of packaging adhesive film for solar cell itself is thermoplastic macromolecule, after the peroxide crosslinking reaction, has then become all very excellent elastomeric material of elasticity, mechanical property, adhesive property.
With regard to producing solar cell, if laminating temperature is low more, the lamination time is short more, production efficiency is just high more so.So can the glued membrane that be used for solar cell package be claimed, promptly curing temperature low more good more, The faster the better for curing cross-linking reaction.Satisfy this requirement, need in the packaging adhesive film prescription, use at laminating temperature half-life short peroxide and vulcanization accelerator.
With regard to producing packaging adhesive film for solar cell, if use at laminating temperature half-life short peroxide and vulcanization accelerator, be easy to so under temperature and the strong double action of shearing of screw extruder, because the crosslinked material that causes loses flowability, thereby in screw extruder and die head, form putty and make the course of processing interrupt.
As seen, glued membrane machine-shaping is crossed range request and can not be taken place crosslinkedly in early days, takes place perhaps that long more, degree of early stage crosslinked time is light more then to help machine-shaping more; And glued membrane use requirement, material, to finish sulfuration as early as possible after long sulfuration induction period in experience, can improve manufacture of solar cells efficient like this.
In material extrusion molding process, because early stage crosslinked generation is arranged, moment of torsion can be increasing.In general, moment of torsion increases by 2 moment of torsion units on the minimum value basis, and at this moment material is owing to the crosslinked flowability that lost, and the pairing time is the yardstick of weighing material flowability, is referred to as process safety time or time of scorch, uses T
2Expression, it is a parameter of weighing the EVA processing characteristics.When producing the EVA glued membrane, need experience melting mixing, curtain coating casting sheet step usually, may cause cross-linking reaction, if time of scorch T
2Longer, then reduced the possibility that cross-linking reaction takes place greatly, be not prone to the curing phenomenon in the production, be beneficial to the EVA glued membrane that obtains good fluidity, be used for the encapsulation of solar cell.And when solar cell package, time of scorch T
2Longer, EVA keeps time of fluidity longer, then is beneficial to the vacuumize degassing in early stage.
In order product to be reached meet the degree of cross linking of service condition, need to add (with respect to 100 mass parts EVA) crosslinking agent of 0.4～1.5 mass parts, in this scope, under the laminating temperature of producing solar cell, there are the relation as Fig. 1 in crosslinking time and mixing moment of torsion.Among Fig. 1: there is minimum torque value ML at A point place.B point place torque value is located big 2 units than A point, is ML+2, and time corresponding is T
2There is the highest torque value MH at C point place, and the used time is total crosslinking time T
cBefore the time point Z is warm-up time.As can be seen, arrive warm-up time after, moment of torsion is along with the variation of crosslinking time is first reduction, the back raises, the melting stage of corresponding EVA of decline stage, the crosslinking curing stage of the corresponding EVA of ascent stage.
In order to enhance productivity, people wish to reduce total crosslinking time T as far as possible
CCrosslinking time depends on half-life, consumption and the lamination curing temperature of crosslinking agent, and the half-life of crosslinking agent is long more, and crosslinking time is long more; The lamination curing temperature is high more, and crosslinking time is short more; Dosage of crosslinking agent increases, and crosslinking rate is accelerated, and crosslinking time shortens, but excessive use crosslinking agent easily produces bubble, has reduced light transmittance.No matter adopt above-mentioned which kind of means to shorten crosslinking time, T
2And T
CThe capital changes synchronously, i.e. T
CShorten, simultaneously T
2Also can shorten.
This is a pair of contradiction, because the existence of this problem, the speed that causes making at present the packaging adhesive film for solar cell production line is lower.
Therefore, the processing of EVA glued membrane, encapsulation performance and production efficiency have formed the contradiction that is difficult to be in harmonious proportion, and still find no the effect means at present, can both guarantee the production efficiency of solar cell package, can effectively improve processing, the encapsulation performance of EVA glued membrane again.
In addition, the protective layer material in the solar cell is generally glass and TPT film, and glass is inorganic material and surface smoothing, and TPT is the difficult sticking material of macromolecule, and this makes that adhesive strength and persistence between EVA glued membrane and the protective layer are not high.
Summary of the invention
The invention provides a kind of packaging adhesive film for solar cell, can guarantee total crosslinking time T
CChange under the little prerequisite, effectively prolong time of scorch T
2, processing, the encapsulation performance of raising EVA glued membrane.
Described packaging adhesive film for solar cell contains ethylene-vinyl acetate copolymer, crosslinking agent, cross-linked inhibitor and free radical scavenger, wherein the quality of cross-linked inhibitor and free radical scavenger is respectively 0.1%～1.0% of ethylene-vinyl acetate copolymer quality, 0～0.3%, the crosslinking time of described packaging adhesive film for solar cell is 10～30 minutes.
Described cross-linked inhibitor is anhydrous acrylate metal salt, anhydrous methacrylate slaine, stearic acid, polyethylene glycol, ethene polymers, ethylene propylene copolymer, ethylene, propylene butylene copolymer, butadiene polymer and derivative or polymeric cyclopentadiene and derivative thereof; Described free radical scavenger is 3, the 4-4-dihydroxy benzaldehyde, 1,1-diphenyl-2-trinitrophenyl-hydrazine, 2-methyl-2-nitroso methane, 2-methyl-2-nitroso propane, 3-aryl benzofuranone or 5,5-dimethyl-1-oxidation pyrrolin, be preferably ethene polymers, ethylene propylene copolymer, the ethylene, propylene butylene copolymer, the butadiene polymer or derivatives thereof, or polymeric cyclopentadiene or derivatives thereof, be preferably ethene polymers, ethylene propylene copolymer, the ethylene, propylene butylene copolymer, the butadiene polymer or derivatives thereof, or polymeric cyclopentadiene or derivatives thereof, ethene polymers more preferably, ethylene propylene copolymer, butadiene polymer or polymeric cyclopentadiene are as Tissuemat E; Described free radical scavenger is 3,4-4-dihydroxy benzaldehyde, 1,1-diphenyl-2-trinitrophenyl-hydrazine, 2-methyl-2-nitroso methane, 2-methyl-2-nitroso propane, 3-aryl benzofuranone or 5,5-dimethyl-1-oxidation pyrrolin.
The quality of described crosslinking agent is 0.4%～1.5% of an ethylene-vinyl acetate copolymer quality.Described crosslinking agent can adopt the crosslinking agent commonly used of EVA glued membrane, as 2,2-two (tert-butyl hydroperoxide) butane, 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 1,1-(two tert-butyl peroxide)-3,3, the 5-trimethyl-cyclohexane, peroxidized t-butyl perbenzoate, peroxidating carbonic acid-2 ethyl hexanoic acid the tert-butyl ester, tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite, di-t-butyl peroxide or 1, the 1-cyclohexane di-tert-butyl peroxide, the preferred crosslinking agent that adopts is 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite or 1,1-(two tert-butyl peroxide)-3,3, the 5-trimethyl-cyclohexane.
The content of vinyl acetate is 25%～40% in the described ethylene-vinyl acetate copolymer.
Can also contain ultra-violet absorber, antioxidant, light stabilizer and tackifier according to prior art in the described packaging adhesive film for solar cell.
Described ultra-violet absorber is 2-hydroxyl-4-methoxy benzophenone, 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-just-dodecyloxy benzophenone, UV-531 or 2,2-dihydroxy-4,4-dimethoxy-benzophenone.
Described antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphite ester, tricresyl phosphite (single nonyl benzene and dinonyl benzene mixed ester), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or β-positive octadecanol ester of (4-hydroxy phenyl-3,5 di-tert-butyl-phenyl) propionic acid.
Described light stabilizer is tricresyl phosphite (1,2,2,6,6-pentamethyl piperidines ester), two (2,2,6,6-tetramethyl-4-piperidyl) sebacate or two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) diester in the last of the ten Heavenly stems.
Described silane coupler is vinyl Ethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, vinyl trichlorosilane, vinyltriacetoxy silane or gamma-aminopropyl-triethoxy-silane.
If the crosslinking agent among the EVA is long in the laminating temperature half-life, so the lamination time elongated, be unfavorable for promoting production efficiency.Therefore, wish in the short as far as possible time, to obtain the higher degree of cross linking, generally use at the short crosslinking agent of laminating temperature half-life for this reason, generally under 130～170 ℃, carry out laminated into type to improve crosslinking rate.
There are the relation as Fig. 2 in dosage of crosslinking agent and crosslinking time.Along with the increase of dosage of crosslinking agent, crosslinking rate is accelerated, and crosslinking time shortens, but the too short easy generation bubble of crosslinking time has reduced light transmittance, and desirable crosslinking time is 15～20 minutes.
The present invention is on existing packaging adhesive film for solar cell prescription basis, add a class cross-linked inhibitor and a free radical scavenger, can form the stable molecule structure with the living radical that produces in the peroxide cross-linking agent, effectively prevention is early stage crosslinked and excessively crosslinked, thereby guarantees total crosslinking time T
COn the basis that meets the demands, effectively prolong time of scorch T
2
Compared with prior art, the present invention has the following advantages:
(1) under the prerequisite that does not influence other performance of EVA glued membrane, adjust the degree of cross linking by the addition of regulating cross-linked inhibitor and free radical scavenger, improved processing characteristics, can guarantee the production efficiency of solar cell package.
(2) by adding cross-linked inhibitor, at the crosslinked total time T that finishes of EVA glued membrane
CUnder the constant situation, can prolong the time of scorch T of EVA
2, more help the production of EVA glued membrane.
(3) compare with the EVA glued membrane that does not add cross-linked inhibitor, the EVA glued membrane adhesive strength that the present invention relates to increases to some extent, has more effectively protected solar cell device, has completely cut off oxygen, moisture better, has prolonged the useful life of solar cell.
Description of drawings
Fig. 1 is the solar module structure chart;
Fig. 2 is mixing moment of torsion-crosslinking time figure;
Fig. 3 is crosslinking time-crosslinked spirogram of using;
Fig. 4 is the rheological curve of homemade commercially available prod;
Fig. 5 is the rheological curve of comparative example 2;
Fig. 6 is the rheological curve of embodiment 1.
Embodiment
The present invention will be described in more detail below in conjunction with example, and the evaluation method of using in the implementation example is as follows:
(1) degree of cross linking
Crosslinked EVA glued membrane is cut into fractionlet, be put in formation sample bag in the 120 order stainless steel mesh bags after accurately taking by weighing appropriate mass, weighing mesh bag and sample gross weight, the sample bag is suspended in the flask of reflux with copper wire, with dimethylbenzene is that solvent boiling reflux 5 hours are (for preventing the crosslinked once again of sample, the antioxidant that can add mass fraction 1%), cooling, take out sample bag, hang to remove excessive solvent, put into vacuum drying oven again and dried by the fire 3 hours down, take out sample bag and in drier, cooled off 15 minutes at 140 ℃, take out weighing, calculate the degree of cross linking.
(2) adhesive strength
Detect according to standard GB/T 2790-1995.
(3) mixing moment of torsion
The EVA glued membrane is cut into granular, takes by weighing an amount of sample, use torque rheometer, obtain its rheological curve under laminating temperature.
Comparative example 1
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 0.8 part 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 0.25 part of 2-hydroxyl-4-methoxy benzophenone, 0.25 part of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2 part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.3 part of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane mix under 80 ℃, make the EVA packaging adhesive film for solar cell.
Comparative example 2
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 0.25 part of 2-hydroxyl-4-methoxy benzophenone, 0.25 part of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2 part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.3 part of gamma-aminopropyl-triethoxy-silane mix under 80 ℃, make the EVA packaging adhesive film for solar cell.
Comparative example 3
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.4 part 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 0.25 part 2,4-dihydroxy benaophenonel, 0.25 part of three (2, the 4-di-tert-butyl-phenyl) phosphite ester, 0.2 part of two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) last of the ten Heavenly stems, diester, 0.3 part of gamma-aminopropyl-triethoxy-silane mixed under 80 ℃, made the EVA packaging adhesive film for solar cell.
Comparative example 4
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 1,1-(two tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane, 0.25 part 2,4-dihydroxy benaophenonel, 0.25 part of four [(β-3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2 part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate mixes under 80 ℃, makes the EVA packaging adhesive film for solar cell.
Embodiment 1
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 0.25 part 2, the 4-dihydroxy benaophenonel, 0.25 part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2 part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.3 part γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 0.3 part polymeric cyclopentadiene, 0.1 part 1,1-diphenyl-2-trinitrophenyl-hydrazine mixes under 80 ℃, makes the EVA packaging adhesive film for solar cell.
Embodiment 2
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 0.25 part 2,4-dihydroxy benaophenonel, 0.25 part of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2 part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.3 part of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 0.2 part of butadiene polymer, 0.2 part 1,1-diphenyl-2-trinitrophenyl-hydrazine mixes under 80 ℃, makes the EVA packaging adhesive film for solar cell.
Embodiment 3
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 1,1-(two tert-butyl peroxide)-3,3, the 5-trimethyl-cyclohexane, 0.25 part 2, the 4-dihydroxy benaophenonel, 0.25 part β-(4-hydroxy phenyl-3,5 di-tert-butyl-phenyls) the positive octadecanol ester of propionic acid, 0.2 part two (1-octyloxies-2,2,6,6-tetramethyl-4-piperidyl) last of the ten Heavenly stems diester, 0.3 part γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 0.4 part Tissuemat E, 0.05 part 3, the 4-4-dihydroxy benzaldehyde mixes under 80 ℃, makes the EVA packaging adhesive film for solar cell.
Embodiment 4
In mass fraction, with 100 parts of VA content is 30% EVA material grain, 1.1 part 1,1-(two tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane, 0.25 part 2,4-dihydroxy benaophenonel, 0.25 part of β-(4-hydroxy phenyl-3,5 di-tert-butyl-phenyls) the positive octadecanol ester of propionic acid, 0.2 part of two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) last of the ten Heavenly stems, diester, 0.3 part of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 0.4 part of ethylene propylene copolymer mixed under 80 ℃, made the EVA packaging adhesive film for solar cell.
The present invention detects the prepared crosslinked back of EVA glued membrane the adhesive strength of the degree of cross linking and glass, and testing result sees Table 1.
The table 1EVA glued membrane degree of cross linking reaches the adhesive strength with glass
| The EVA glued membrane | The degree of cross linking (%) | Adhesive strength (N/cm) with glass |
| Comparative example 1 | 85.3 | 36.6 |
| Comparative example 2 | 88.2 | 39.5 |
| Comparative example 3 | 92.0 | 43.1 |
| Comparative example 4 | 87.5 | 30.5 |
| Embodiment 1 | 82.7 | 51.9 |
| Embodiment 2 | 83.6 | 53.1 |
| Embodiment 3 | 80.2 | 54.8 |
| Embodiment 4 | 80.6 | 54.2 |
Obtain vulcanizing data according to the rheological curve of Fig. 4-6 and see Table 2.
Table 2EVA glued membrane sulfuration data
| The EVA glued membrane | ML(Nm) | T 2 | T C(containing preheating) |
| Homemade commercially available prod | 4.6 | 5′20″ | 15′25″ |
| Comparative example 1 | 5.1 | 4′55″ | 14′09″ |
| Comparative example 2 | 5.9 | 4′0″ | 12′15″ |
| Comparative example 3 | 6.2 | 3′34″ | 10′32″ |
| Comparative example 4 | 5.8 | 3′55″ | 12′17″ |
| Embodiment 1 | 4.2 | 10′29″ | 15′18″ |
| Embodiment 2 | 4.5 | 9′12″ | 14′24″ |
| Embodiment 3 | 4.3 | 10′40″ | 15′51″ |
| Embodiment 4 | 4.3 | 10′43″ | 15′46″ |
Getting homemade commercially available prod, comparative example 2 and embodiment 1 uses torque rheometer to detect the acquisition rheological curve respectively.The above only is an inventive embodiments, be not that the present invention is done any pro forma restriction, any personnel that are familiar with this technology can utilize above-mentioned technology contents to be changed or be modified to the equivalent embodiment of equivalent variations, every content that does not break away from technical solution of the present invention all belongs to the technical solution of the present invention scope.
Claims (10)
1. packaging adhesive film for solar cell, it is characterized in that, it contains ethylene-vinyl acetate copolymer, crosslinking agent, cross-linked inhibitor and free radical scavenger, wherein the quality of cross-linked inhibitor and free radical scavenger is respectively 0.1%～1% of ethylene-vinyl acetate copolymer quality, 0～0.3%, the crosslinking time of described packaging adhesive film for solar cell is 10～30 minutes, and described cross-linked inhibitor is ethene polymers, ethylene propylene copolymer, ethylene, propylene butylene copolymer, butadiene polymer or derivatives thereof or polymeric cyclopentadiene or derivatives thereof.
2. packaging adhesive film for solar cell as claimed in claim 1, it is characterized in that, described free radical scavenger is 3,4-4-dihydroxy benzaldehyde, 1,1-diphenyl-2-trinitrophenyl-hydrazine, 2-methyl-2-nitroso methane, 2-methyl-2-nitroso propane, 3-aryl benzofuranone or 5,5-dimethyl-1-oxidation pyrrolin.
3. packaging adhesive film for solar cell as claimed in claim 1 or 2 is characterized in that, the quality of described crosslinking agent is 0.4～1.5% of an ethylene-vinyl acetate copolymer quality.
4. packaging adhesive film for solar cell as claimed in claim 3, it is characterized in that, described crosslinking agent is 2,2-two (tert-butyl hydroperoxide) butane, 2,5-dimethyl-2, two (t-butyl peroxy) hexanes, 1 of 5-, 1-(two tert-butyl peroxide) 3,3,5-trimethyl-cyclohexane, peroxidized t-butyl perbenzoate, the peroxidating carbonic acid-2 ethyl hexanoic acid tert-butyl ester, tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite, di-t-butyl peroxide or 1,1-cyclohexane di-tert-butyl peroxide.
5. packaging adhesive film for solar cell as claimed in claim 1 or 2 is characterized in that, the content of vinyl acetate is 25%～40% in the described ethylene-vinyl acetate copolymer.
6. packaging adhesive film for solar cell as claimed in claim 1 or 2 is characterized in that, also contains ultra-violet absorber, antioxidant, light stabilizer and tackifier in the described packaging adhesive film for solar cell.
7. packaging adhesive film for solar cell as claimed in claim 6, it is characterized in that, described ultra-violet absorber is 2-hydroxyl-4-methoxy benzophenone, 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-just-dodecyloxy benzophenone, UV-531 or 2,2-dihydroxy-4, the 4-dimethoxy-benzophenone.
8. packaging adhesive film for solar cell as claimed in claim 6, it is characterized in that, described antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphite ester, tricresyl phosphite (single nonyl benzene and dinonyl benzene mixed ester), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or β-positive octadecanol ester of (4-hydroxy phenyl-3,5 di-tert-butyl-phenyl) propionic acid.
9. packaging adhesive film for solar cell as claimed in claim 6 is characterized in that, described light stabilizer is a tricresyl phosphite (1,2,2,6,6-pentamethyl piperidines ester), two (2,2,6,6-tetramethyl-4-piperidyl) sebacate or two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) last of the ten Heavenly stems diester.
10. packaging adhesive film for solar cell as claimed in claim 6, it is characterized in that, described tackifier are vinyl Ethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, vinyl trichlorosilane, vinyltriacetoxy silane or gamma-aminopropyl-triethoxy-silane.
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| CN101942145B (en) * | 2010-09-13 | 2012-12-26 | 苏州福斯特光伏材料有限公司 | Packaging adhesive film composition and application thereof |
| CN102655181B (en) * | 2011-03-03 | 2014-11-26 | 昆山恒辉新能源有限公司 | Solar cell packaging process |
| CN102738310A (en) * | 2012-07-16 | 2012-10-17 | 中电电气（南京）光伏有限公司 | Crystalline silicon photovoltaic assembly package method capable of suppressing mutual penetration and color mixing of package films |
| CN102775939B (en) * | 2012-08-21 | 2015-02-18 | 东方电气集团东方汽轮机有限公司 | Solar battery encapsulation adhesive film |
| CN103013363B (en) * | 2012-12-26 | 2014-04-02 | 南京红宝丽新材料有限公司 | Packaging adhesive film of solar component and preparation method thereof |
| CN103642412B (en) * | 2013-12-04 | 2015-05-06 | 苏州泰科尼光伏材料有限公司 | EVA (ethylene-vinyl acetate) adhesive film for solar cell packaging and preparation method thereof |
| CN103642411B (en) * | 2013-12-04 | 2015-05-06 | 苏州泰科尼光伏材料有限公司 | EVA (ethylene-vinyl acetate) adhesive film for solar cell packaging and preparation method thereof |
| CN108239486A (en) * | 2016-12-26 | 2018-07-03 | 阿特斯阳光电力集团有限公司 | Anti- snail line EVA adhesive film |
| CN111458264A (en) * | 2019-01-18 | 2020-07-28 | 中国石油天然气股份有限公司 | Method and device for testing crosslinking time of gel type fracturing fluid |
| CN111524987B (en) * | 2020-05-27 | 2022-03-08 | 常州汉韦聚合物有限公司 | Dual glass assembly and method of laminating the same |
| CN117125714B (en) * | 2023-10-27 | 2024-03-29 | 宁德时代新能源科技股份有限公司 | Silicon-based material and preparation method thereof, negative electrode plate, battery and electric equipment |
| CN118317617A (en) * | 2024-04-02 | 2024-07-09 | 天合光能股份有限公司 | Photovoltaic module and preparation method thereof |
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