CN102504711B - Ethylene-vinyl acetate copolymer adhesive film for packaging solar batteries and preparation method thereof - Google Patents
Ethylene-vinyl acetate copolymer adhesive film for packaging solar batteries and preparation method thereof Download PDFInfo
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- CN102504711B CN102504711B CN201110334537.8A CN201110334537A CN102504711B CN 102504711 B CN102504711 B CN 102504711B CN 201110334537 A CN201110334537 A CN 201110334537A CN 102504711 B CN102504711 B CN 102504711B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Provided are an ethylene-vinyl acetate copolymer adhesive film for packaging solar batteries and a preparation method thereof. Raw materials for preparing the adhesive film are: part by weight, 100 parts of ethylene-vinyl acetate copolymer, 0.1 to 10 parts of cross-linking curing agents, 0.1 to 2 parts of ultraviolet light absorbing agents, 0.1 to 1 part of flatting agents, 0.1 to 5 parts of silane coupling agents and 0.1 to 3 parts of antioxidants. The adhesive film and a high temperature positioning tape are matched well, no bubble and no bump exist in a hygrothermal aging process after lamination, an assembly is good in sealing performance, service life of the assembly is prolonged, and the ethylene-vinyl acetate copolymer adhesive film can be widely applied to packaging of the solar batteries.
Description
Technical field
The present invention relates to solar cell package material, particularly a kind of used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film and preparation method thereof.
Background technology
Generating by solar is to utilize the semi-conductive quantum effect principles such as silicon directly solar visible light to be changed into electric energy.If silicon wafer is directly exposed in air, accept the erosion of high low temperature and steam.Its photoelectric conversion performance is easy to decay, loses use value.Encapsulation is the committed step in manufacture of solar cells, there is no good packaging process, the component palette that how good battery also be can not produce.The encapsulation of solar cell not only can make the life-span of battery be guaranteed, but also has strengthened the anti-shock strength of battery.The high quality of product and high life are to win customer satisfaction system key, so the package quality of component palette is extremely important.The encapsulation of solar cell is by crystal silicon chip group " upper cover underlay ", silicon wafer group is sealed, and and upper strata protecting materials glass, the protecting materials TPT(of lower floor fluorinated ethylene propylene composite membrane), utilize vacuum lamination technology to be bonded as one.
EVA(ethylene-vinyl acetate copolymer) be a kind of hot melt adhesive stick, inviscid and tool resistance to bond under normal temperature, just there is melting adhered and crosslinking curing in the hot pressing through certain condition, and change is completely transparent, after it and bonding glass, can improve the transmittance of glass, play a part anti-reflectionly, and the output of solar module is had to gain effect.As packaged material, EVA will have sufficiently high transmittance, and secondly the photoelectric transformation efficiency that Assurance component is higher, have remarkable ultraviolet aging resistance performance and hydrothermal aging performance, and Assurance component is the work-ing life of 25 years out of doors.In addition, EVA will with various backboards, glass and other material (as silica gel, welding, soldering flux etc.) have good bonding and matching effect, if EVA does not mate with silica gel, welding, soldering flux, understand variable color in later stage hydrothermal aging process, affect the visual appearance of assembly.Commercially available EVA glued membrane ubiquity and the unmatched problem of high temperature locating adhesive tape, can bubble after making component lamination and in hydrothermal aging process now, heaves, and causes encapsulation unreal, affects the work-ing life of assembly.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of good used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film that mates with high temperature locating adhesive tape.
The present invention requires another technical problem of solution to be to provide the preparation method of this glued membrane.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film, its raw materials is: the ethylene-vinyl acetate copolymer of 100 weight parts, the crosslinking and curing agent of 0.1～10 weight part, the ultraviolet absorbers of 0.1～2 weight part, the flow agent of 0.1～1 weight part, the oxidation inhibitor of the silane coupling agent of 0.1～5 weight part and 0.1～3 weight part.
Described flow agent is the mixture that silicone based flow agent and acrylic acid or the like flow agent form, wherein: the part by weight of silicone based flow agent and acrylic acid or the like flow agent is 1:1～1:20.
Described silicone based flow agent is poly-methyl alkyl siloxane or the poly-methyl alkyl siloxane of aralkyl modification; Described acrylic acid or the like flow agent is acrylate copolymer, fluorin modified crylic acid ester copolymer or phosphate modified acrylate copolymer.
In described ethylene-vinyl acetate copolymer, vinyl acetate content is 26-33wt%, melt index values 25-45g/10min.
Described crosslinking and curing agent is 2,5-dimethyl-2, two (t-butyl peroxy) hexanes, 1 of 5-, the tertiary hexyl of 1-bis-peroxidation-3, the mixture of one or both in 3,5-trimethyl-cyclohexane, tert-butyl peroxide-2-ethylhexyl monocarbonate.
Described ultraviolet absorbers is 2,2'-dihydroxyl-4,4'-dimethoxy-benzophenone, 2-[4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-yl]-5-(octyloxy) phenol, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) mixture of one or both in sebate.
Described silane coupling agent is gamma-methyl allyl acyloxypropyl trimethoxysilane.
Described oxidation inhibitor is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or both mixture compound in the two octadecyl esters of pentaerythritol ester, the positive octadecanol ester of β-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid, distearyl pentaerythritol diphosphite, thio-2 acid, tricresyl phosphite (single nonyl benzene and dinonyl benzene) mixed ester.
A preparation method for used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film, described method comprises the steps:
(1), in weight part, the ethylene-vinyl acetate copolymer of 100 parts, the ultraviolet absorbers of 0.1～2 part and the flow agent of 0.1～1 part are mixed;
(2), in weight part, the silane coupling agent of the crosslinking and curing agent of 0.1～10 part, the oxidation inhibitor of 0.1～3 part and 0.1～5 part is added in mixture prepared by step (1), and mix;
(3) mixture of being prepared by step (2) is poured forcing machine into and is carried out blending extrusion, extruder die head temperature is controlled at 90-100 ℃, extrudate through curtain coating, cooling, traction, winding process, obtains used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film.
Compared with prior art, tool of the present invention has the following advantages:
In glued membrane by adding the flow agent mixture being formed by silicone based flow agent and acrylic acid or the like flow agent, and the part by weight of controlling machine silicon class flow agent and acrylic acid or the like flow agent is between 1:1～1:20, make silicone based flow agent principal security EVA melt the levelling at initial stage, levelling after acrylic acid or the like flow agent principal security EVA melts before lamination and degassed, two kinds of flow agents are also used, make to mate between glued membrane and high temperature locating adhesive tape good, after lamination and non-foaming, not bulge in hydrothermal aging process, component sealing is good, has extended the work-ing life of assembly.
2. the inventive method is by controlling the addition sequence of auxiliary agent, between the glued membrane that guarantees to obtain and high temperature locating adhesive tape, mate good in, keep good ultraviolet light and aging, hot and humid and thermal-oxidative aging property.
Embodiment
Embodiment 1:
By mass parts:
Vinyl acetate content is 30%, the EVA 100 that melt index values is 45g/10min,
2,2'-dihydroxyl-4,4'-dimethoxy-benzophenone 0.5,
Two (2,2,6,6-tetramethyl--4-piperidyl) sebate 1,
Aralkyl modification gathers methyl alkyl siloxane 0.01,
Fluorin modified crylic acid ester copolymer 0.2,
Tert-butyl peroxide-2-ethylhexyl monocarbonate 5,
The positive octadecanol ester 1 of β-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid,
Tricresyl phosphite (single nonyl benzene and dinonyl benzene) mixed ester 0.2,
Gamma-methyl allyl acyloxypropyl trimethoxysilane 0.5,
By 100 mass parts vinyl acetate contents, be 30%, melt index values is 2 of the EVA of 45g/10min and 0.5 mass parts, 2'-dihydroxyl-4, two (2 of 4'-dimethoxy-benzophenone, 1 mass parts, 2,6,6-tetramethyl--4-piperidyl) the fluorin modified crylic acid ester copolymer of the poly-methyl alkyl siloxane of the aralkyl modification of sebate, 0.01 mass parts and 0.2 mass parts mixes; Tricresyl phosphite (single nonyl benzene and the dinonyl benzene) mixed ester of the positive octadecanol ester of the β of tert-butyl peroxide-2-ethylhexyl monocarbonate of 5 mass parts, 1 mass parts-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid, 0.2 mass parts and the gamma-methyl allyl acyloxypropyl trimethoxysilane of 0.5 mass parts are added in said mixture; Mixed EVA masterbatch melting mixing, extruder die head temperature in forcing machine are controlled to 92 ℃, and extrudate, through curtain coating, cooling, traction, rolling, obtains EVA film adhesive for solar cell package, surveys its performance.
Embodiment 2
By mass parts:
Vinyl acetate content is 26%, the EVA 100 that melt index values is 30g/10min,
Two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) sebate 0.1,
Poly-methyl alkyl siloxane 0.02,
Phosphate modified acrylate copolymer 0.3,
2,5-dimethyl-2, two (t-butyl peroxy) hexanes 1 of 5-,
The tertiary hexyl of 1,1-bis-peroxidation-3,3,5-trimethyl-cyclohexane 0.05,
The two octadecyl esters 0.5 of thio-2 acid,
Gamma-methyl allyl acyloxypropyl trimethoxysilane 2,
By 100 mass parts vinyl acetate contents, be 26%, melt index values is the EVA of 30g/10min and two (1-octyloxy-2 of 0.1 mass parts, 2,6,6-tetramethyl--4-piperidyl) the phosphate modified acrylate copolymer of the poly-methyl alkyl siloxane of sebate, 0.02 mass parts and 0.3 mass parts mixes; By 2 of 1 mass parts, 5-dimethyl-2,1 of two (t-butyl peroxy) hexanes of 5-, 0.05 mass parts, the tertiary hexyl of 1-bis-peroxidation-3, the two octadecyl esters of thio-2 acid of 3,5-trimethyl-cyclohexane, 0.5 mass parts, the gamma-methyl allyl acyloxypropyl trimethoxysilane of 2 mass parts add in said mixture; Mixed EVA masterbatch melting mixing, extruder die head temperature in forcing machine are controlled to 90 ℃, and extrudate, through operations such as curtain coating, cooling, traction, rollings, finally obtains EVA film adhesive for solar cell package, surveys its performance.
Embodiment 3
By mass parts:
Vinyl acetate content is 30%, the EVA 100 that melt index values is 45g/10min,
2-[4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-]-5-(octyloxy) phenol 2,
Aralkyl modification gathers methyl alkyl siloxane 0.03,
Acrylate copolymer 0.15,
2,5-dimethyl-2, two (t-butyl peroxy) hexanes 0.2 of 5-,
Tert-butyl peroxide-2-ethylhexyl monocarbonate 1.5,
Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.5,
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2.5,
Gamma-methyl allyl acyloxypropyl trimethoxysilane 5,
By 100 mass parts vinyl acetate contents, be 30%, melt index values is the EVA of 46g/10min and the 2-[4 of 2 mass parts, 6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazine-2-yl] the poly-methyl alkyl siloxane of aralkyl modification of-5-(octyloxy) phenol, 0.03 mass parts and the acrylate copolymer of 0.15 mass parts mix; By 2 of 0.2 mass parts, 5-dimethyl-2, three (2 of tert-butyl peroxide-2-ethylhexyl monocarbonate of two (t-butyl peroxy) hexanes of 5-, 1.5 mass parts, 0.5 mass parts, 4-di-tert-butyl-phenyl) gamma-methyl allyl acyloxypropyl trimethoxysilane of four of phosphorous acid ester, 2.5 mass parts [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 5 mass parts adds in said mixture; Mixed EVA masterbatch melting mixing, extruder die head temperature in forcing machine are controlled to 96 ℃, and extrudate, through operations such as curtain coating, cooling, traction, rollings, finally obtains EVA film adhesive for solar cell package, surveys its performance.
Embodiment 4
By mass parts:
Vinyl acetate content is 33%, the EVA 100 that melt index values is 25g/10min,
2,2'-dihydroxyl-4,4'-dimethoxy-benzophenone 0.5,
Aralkyl modification gathers methyl alkyl siloxane 0.05,
Fluorin modified crylic acid ester copolymer 0.05,
2,5-dimethyl-2, two (t-butyl peroxy) hexanes 10 of 5-,
Distearyl pentaerythritol diphosphite 0.2,
The two octadecyl esters 0.05 of thio-2 acid,
Gamma-methyl allyl acyloxypropyl trimethoxysilane 1.2,
By 100 mass parts vinyl acetate contents, be 33%, melt index values is 2 of the EVA of 25g/10min and 0.5 mass parts, 2'-dihydroxyl-4, the poly-methyl alkyl siloxane of aralkyl modification of 4'-dimethoxy-benzophenone, 0.05 mass parts and the fluorin modified crylic acid ester copolymer of 0.05 mass parts mix; By 2 of 10 mass parts, 5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, the distearyl pentaerythritol diphosphite of 0.2 mass parts, the gamma-methyl allyl acyloxypropyl trimethoxysilane of the two octadecyl esters of the thio-2 acid of 0.05 mass parts, 1.2 mass parts add in said mixture; Mixed EVA masterbatch melting mixing, extruder die head temperature in forcing machine are controlled to 100 ℃, and extrudate, through operations such as curtain coating, cooling, traction, rollings, finally obtains EVA film adhesive for solar cell package, surveys its performance.
Embodiment 5
By mass parts:
Vinyl acetate content is 30%, the EVA 100 that melt index values is 45g/10min,
2-[4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-]-5-(octyloxy) phenol 0.5,
Two (2,2,6,6-tetramethyl--4-piperidyl) sebate 0.47,
Aralkyl modification gathers methyl alkyl siloxane 0.2,
Fluorin modified crylic acid ester copolymer 0.8,
The tertiary hexyl of 1,1-bis-peroxidation-3,3,5-trimethyl-cyclohexane 0.1,
The positive octadecanol ester 0.1 of β-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid,
Gamma-methyl allyl acyloxypropyl trimethoxysilane 0.1,
By 100 mass parts vinyl acetate contents, be 30%, melt index values is the EVA of 45g/10min and the 2-[4 of 0.5 mass parts, 6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazine-2-yl]-5-(octyloxy) phenol, 0.47 mass parts two (2,2,6,6-tetramethyl--4-piperidyl) the fluorin modified crylic acid ester copolymer of the poly-methyl alkyl siloxane of the aralkyl modification of sebate, 0.2 mass parts and 0.8 mass parts mixes; By 1 of 0.1 mass parts, the tertiary hexyl of 1-bis-peroxidation-3, the gamma-methyl allyl acyloxypropyl trimethoxysilane of the positive octadecanol ester of the β of 3,5-trimethyl-cyclohexane, 0.1 mass parts-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid, 0.1 mass parts adds in said mixture; Mixed EVA masterbatch melting mixing, extruder die head temperature in forcing machine are controlled to 93 ℃, and extrudate, through operations such as curtain coating, cooling, traction, rollings, finally obtains EVA film adhesive for solar cell package, surveys its performance.
Table 1: each embodiment glue film performance test data table:
In table, the testing method of properties is as follows:
1. the test of cohesive force:
Employing standard is GB/T2790-1995.
2. transmittance:
Adopt the test of all wave band light transmittance tester, its employing standard is GB2410-80.
3. ultraviolet light and aging:
According to the new edition IEC61215 of International Electrotechnical Commission, carry out ultraviolet pretreatment testing, temperature: 60 ± 5 ℃, wavelength: 280～385nm, illumination :≤250W/m
2, total irradiation dose is: 15KWh/m
2, its medium wavelength is that the uv irradiation of 280-320 nm is 5 KWh/m
2.
4. high temperature and humidity test:
Experiment condition: 85 ℃ of temperature, relative humidity 85%, time 1000h.
5. xanthochromia index:
Press GB2409-80 < < plastics yellowness index test method > > test.
As can be seen from the table, between EVA film adhesive for solar cell package provided by the invention and high temperature locating adhesive tape, mate well, transmittance is higher, after lamination and non-foaming, not bulge in hydrothermal aging process, component sealing is good, and Assurance component reaches the work-ing life of 30 years out of doors.
Claims (8)
1. a used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film, it is characterized in that, its raw materials is: the ethylene-vinyl acetate copolymer of 100 weight parts, the crosslinking and curing agent of 0.1～10 weight part, the ultraviolet absorbers of 0.1～2 weight part, the flow agent of 0.1～1 weight part, the oxidation inhibitor of the silane coupling agent of 0.1～5 weight part and 0.1～3 weight part;
Described flow agent is the mixture that silicone based flow agent and acrylic acid or the like flow agent form, wherein: the part by weight of silicone based flow agent and acrylic acid or the like flow agent is 1:1～1:20.
2. glued membrane according to claim 1, is characterized in that, described silicone based flow agent is poly-methyl alkyl siloxane or the poly-methyl alkyl siloxane of aralkyl modification; Described acrylic acid or the like flow agent is acrylate copolymer, fluorin modified crylic acid ester copolymer or phosphate modified acrylate copolymer.
3. glued membrane according to claim 2, is characterized in that, in described ethylene-vinyl acetate copolymer, vinyl acetate content is 26-33wt%, melt index values 25-45g/10min.
4. glued membrane according to claim 3, it is characterized in that, described crosslinking and curing agent is 2,5-dimethyl-2, two (t-butyl peroxy) hexanes, 1 of 5-, the tertiary hexyl of 1-bis-peroxidation-3, the mixture of one or both in 3,5-trimethyl-cyclohexane, tert-butyl peroxide-2-ethylhexyl monocarbonate.
5. glued membrane according to claim 4, is characterized in that, described ultraviolet absorbers is 2,2'-dihydroxyl-4,4'-dimethoxy-benzophenone, 2-[4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-yl]-5-(octyloxy) phenol, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) mixture of one or both in sebate.
6. glued membrane according to claim 5, is characterized in that, described silane coupling agent is gamma-methyl allyl acyloxypropyl trimethoxysilane.
7. glued membrane according to claim 6, it is characterized in that, described oxidation inhibitor is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or both mixture in the two octadecyl esters of pentaerythritol ester, the positive octadecanol ester of β-(4-hydroxyl-3,5 di-tert-butyl-phenyls) propionic acid, distearyl pentaerythritol diphosphite, thio-2 acid, tricresyl phosphite (single nonyl benzene and dinonyl benzene) mixed ester.
8. a method of preparing used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film as described in claim 1,2,3,4,5,6 or 7, is characterized in that, it carries out as follows:
A step, in weight part, the ethylene-vinyl acetate copolymer of 100 parts, the ultraviolet absorbers of 0.1～2 part and the flow agent of 0.1～1 part are mixed;
B step, in weight part, the silane coupling agent of the crosslinking and curing agent of 0.1～10 part, the oxidation inhibitor of 0.1～3 part and 0.1～5 part is added in mixture prepared by steps A, and mixes;
C step, mixture prepared by step B are poured forcing machine into and are carried out blending extrusion, and extruder die head temperature is controlled at 90-100 ℃, extrudate through curtain coating, cooling, traction, winding process, obtains used for encapsulation of solar battery ethylene-vinyl acetate copolymer adhesive film.
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| CN201110334537.8A CN102504711B (en) | 2011-10-30 | 2011-10-30 | Ethylene-vinyl acetate copolymer adhesive film for packaging solar batteries and preparation method thereof |
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| CN104861886B (en) * | 2015-06-04 | 2017-03-08 | 昆山天洋热熔胶有限公司 | A kind of EVA film adhesive for solar cell package and its preparation technology |
| CN107312468A (en) * | 2016-04-20 | 2017-11-03 | 东莞市永固绝缘材料有限公司 | A kind of organic-silicon-modified high transmission rate EVA solar cell module packaging adhesive films |
| CN109486446A (en) * | 2018-10-25 | 2019-03-19 | 常州合威新材料科技有限公司 | A kind of high cut-off type solar energy packaging adhesive film |
| CN110079244B (en) * | 2019-04-15 | 2021-08-27 | 杭州福斯特应用材料股份有限公司 | Solar cell packaging material, related adhesive film and solar cell module |
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| JP5177752B2 (en) * | 2007-11-29 | 2013-04-10 | 株式会社ブリヂストン | Solar cell sealing film and solar cell using the same |
| KR101063886B1 (en) * | 2009-01-16 | 2011-09-15 | 주식회사 아이에스테크 | Method for Preparing Adhesive Sheet for Solar Cell Module |
| CN102134450A (en) * | 2010-12-14 | 2011-07-27 | 上海天洋热熔胶有限公司 | High-adhesive-strength ethylene vinyl acetate adhesive film for packaging solar cells and preparation method thereof |
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