CN109278369A - A kind of ultraviolet aging resistance solar cell backboard film and preparation method thereof - Google Patents
A kind of ultraviolet aging resistance solar cell backboard film and preparation method thereof Download PDFInfo
- Publication number
- CN109278369A CN109278369A CN201811385446.5A CN201811385446A CN109278369A CN 109278369 A CN109278369 A CN 109278369A CN 201811385446 A CN201811385446 A CN 201811385446A CN 109278369 A CN109278369 A CN 109278369A
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- CN
- China
- Prior art keywords
- film layer
- solar cell
- cell backboard
- aging resistance
- weathering
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- Granted
Links
- 230000032683 aging Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 130
- 230000004888 barrier function Effects 0.000 claims abstract description 69
- 239000012790 adhesive layer Substances 0.000 claims abstract description 54
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 meta-xylene glycol Chemical compound 0.000 claims abstract description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 18
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- SHQYYSIANBCJHH-UHFFFAOYSA-N bis(3-amino-4-fluorophenyl)methanone Chemical class C1=C(F)C(N)=CC(C(=O)C=2C=C(N)C(F)=CC=2)=C1 SHQYYSIANBCJHH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000440 bentonite Substances 0.000 claims abstract description 16
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004642 Polyimide Substances 0.000 claims abstract description 15
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 15
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 15
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 15
- 229920001721 polyimide Polymers 0.000 claims abstract description 15
- YEGGBYRIRLOQOP-UHFFFAOYSA-N NN1C(=NN=C1C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1 Chemical compound NN1C(=NN=C1C1=CC=C(C(=O)O)C=C1)C1=CC=C(C(=O)O)C=C1 YEGGBYRIRLOQOP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000009435 amidation Effects 0.000 claims abstract description 8
- 238000007112 amidation reaction Methods 0.000 claims abstract description 8
- 238000003475 lamination Methods 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 238000010030 laminating Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 5
- PZJSZBJLOWMDRG-UHFFFAOYSA-N furan-2-ylboronic acid Chemical compound OB(O)C1=CC=CO1 PZJSZBJLOWMDRG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- XBVURNWWURAQSY-UHFFFAOYSA-N 2,2,2-trifluoroethoxyboronic acid Chemical class OB(O)OCC(F)(F)F XBVURNWWURAQSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000003851 corona treatment Methods 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 6
- 238000011938 amidation process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- OUHVPTUNAKUCJX-UHFFFAOYSA-N N1=CC=CC=C1.CN(C=1C=CNC1)C Chemical compound N1=CC=CC=C1.CN(C=1C=CNC1)C OUHVPTUNAKUCJX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/04—Apparatus for cleaning or pickling metallic material for cleaning pipes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of ultraviolet aging resistance solar cell backboard films to pass through adhesive layer lamination adhesive including barrier film layer and the weathering film layer for being set to barrier film layer or more two sides between barrier film layer and the weathering film layer；The weathering film layer is prepared with bis- (3- amino -4- fluorophenyl) ketones through amidation polycondensation reaction by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.The invention also discloses the preparation methods of the ultraviolet aging resistance solar cell backboard film.Ultraviolet aging resistance solar cell backboard film disclosed by the invention has the advantages that cheap mechanical performance, preparation cost, anti-ultraviolet ageing performance, insulating properties, cementability, barrier property and weatherability are superior.
Description
Technical field
The invention belongs to solar cell module manufacturing technology fields, are related to a kind of solar cell module, specifically,
It is related to a kind of ultraviolet aging resistance solar cell backboard film and preparation method thereof.
Background technique
In recent years, as the representative of green energy resource, solar energy is increasingly attracted attention by people, it is a kind of energy of cleaning
Source is nearly free from any pollution when developing and utilizing, and the unlimitedness of its reserves, is the alternative energy source of ideals of human being in addition.
In the effective use to solar energy, big sun energy solar photovoltaic utilization is research field with fastest developing speed in recent years, most active.?
In being conducive to the solar photovoltaic utilization of solar energy, what is be most widely used is solar battery, in solar battery manufacturing process, is needed
The solar cell backboard film for playing structural encapsulation effect is used, this material uses the longevity for extension solar battery
Life plays a significant role, and is the indispensable component part of solar battery, is the cost important composition of solar battery
One of, while being also to restrict one of the key factor that solar battery further develops.
Ideal solar cell backboard film needs while having reliable insulating properties, water preventing ability, mechanical performance, resistance to ultraviolet
Ultraviolet aging and heat and moisture aging resistance.However main backboard membrane to be used is MULTILAYER COMPOSITE knot in existing solar battery
Structure is all with polyester film (BOPET) for base material film, laminating fluorine material such as pvf film (PVF), PVDF membrane
(PVDF) or coating fluorocarbon resin (FEVE) etc. is fabricated, fluorine material price is more expensive, production technology is complicated, with sandwich layer material
The interlaminar strength of material is poor, is easy to fall off, and the backboard membrane cementability of preparation is poor, electrical insulating property is low, is easy embrittlement, tearing, resists
Ultraviolet ageing performance is poor, is unable to satisfy high-end product requirement.
It is disclosed in Chinese invention patent application CN102365172A and a kind of novel is added to Titanium Dioxide Rutile Top grade grain
The layered polyester film of son, but the cohesive force of itself and adjacent EVA adhesive film not can guarantee, and due to material structure feature, gather
Contain a large amount of ester group in ester molecular resin main chain, there is good compatibility with water, is easy to produce water plasticising, while even if micro-
The moisture of amount also results in the degradation of molecular backbone, so be difficult to overcome water absorption rate high, heat and moisture aging resistance poor (embrittlement)
Defect, adhesive property is bad between Titanium Dioxide Rutile Top grade particle and polymer film, easily occurs mutually to separate, is extremely difficult to solar energy
The performance requirement of backboard membrane.
Therefore, a kind of cheap preparation cost, anti-ultraviolet ageing performance, insulating properties, cementability and barrier property are developed more
Excellent solar cell backboard film accords with the demands of the market, and has extensive market value and application prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of ultraviolet aging resistance solar cell backboard film, should
Ultraviolet aging resistance solar cell backboard film overcomes conventional solar cell backboard membrane, and more or less existing price is more expensive, raw
Production. art is complicated, interlaminar strength is poor, is easy to fall off, the backboard membrane cementability of preparation is poor, electrical insulating property is low, it is brittle to be easy,
The technical issues of tearing, resistance to UV aging is poor, is unable to satisfy high-end product requirement has mechanical performance, preparation cost
Cheap, anti-ultraviolet ageing performance, insulating properties, cementability, barrier property and the superior advantage of weatherability；The present invention also mentions simultaneously
The preparation method of the ultraviolet aging resistance solar cell backboard film is supplied.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of ultraviolet aging resistance solar battery back
Plate film including barrier film layer and is set to the weathering film layers of barrier film layer or more two sides, the barrier film layer and weathering film layer it
Between pass through adhesive layer lamination adhesive；The weathering film layer is by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyl) hexichol
Formic acid is prepared with bis- (3- amino -4- fluorophenyl) ketones through amidation polycondensation reaction；The barrier film layer is by 2,7- naphthalene
Diacid, which is reacted with meta-xylene glycol through esterifying polycondensation, to be prepared；The adhesive layer is by polyvinyl butyral, ethyl vinyl acetate
What ethylene copolymer, polyimides and bentonite were prepared.
Wherein, one kind of the weathering film layer is preferably the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,
5- diyl) dibenzoic acid, bis- (3- amino -4- fluorophenyl) ketones, N, N- diisopropylethylamine, 4-dimethylaminopyridine are dissolved in height
Solution is formed in boiling point solvent, then solution is added in reaction kettle, with air in nitrogen or inert gas replacement kettle, is sealed, in
Then catalyst I is added thereto, is depressurized to 200-300Pa for 2-3 hours progress amidation process of 170-180 DEG C of back flow reaction,
Polycondensation reaction 8-10 hours at 250-270 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation
After ethanol washing 3-5 times, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight, after product is added 220-250 DEG C
It melts, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll resistance to a thickness of 25-30 μm in extruder
Wait film layer；
Preferably, 4,4'- (4- amino -4H-1,2,4- triazole -3, the 5- diyls) dibenzoic acid, bis- (3- amino -4-
Fluorophenyl) ketone, N, N- diisopropylethylamine, 4-dimethylaminopyridine, high boiling solvent, catalyst I mass ratio be 1.3:
1:(0.4-0.6):0.3:(10-15):0.5。
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of；The inert gas is selected from one or more of helium, neon, argon gas；
Preferably, the catalyst I is in 2- furan boronic acid, three (2,2,2- trifluoroethyl) borates, zinc chloride
It is one or more of.
Wherein, preferably the preparation method comprises the following steps: by 2,7- naphthalene diacid and meta-xylene glycol are added one kind of the barrier film layer
Solution is formed in n,N-Dimethylformamide, then solution is added in polymerization reaction kettle, with air in nitrogen displacement kettle, is sealed,
It is stirred to react 3-4 hours progress esterifications in 280-300 DEG C, catalyst II is then added, is depressurized to 150-200Pa,
Polycondensation reaction 6-10 hours at 260-280 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, the polymer of precipitation is used
After ethanol washing 3-5 times, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight, after product be added 220-240 DEG C squeeze
It is melted in machine out, and obtains the barrier with a thickness of 25-30 μm by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll
Film layer.
Preferably, the mass ratio of 2, the 7- naphthalene diacid, meta-xylene glycol, n,N-Dimethylformamide, catalyst II
It is 1.57:1:(10-15): 0.5.
Preferably, the catalyst II is selected from one or more of antimony oxide, antimony acetate or antimony glycol.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight as a preferred implementation manner,
: 20-30 parts of polyvinyl butyral, 30-50 parts of ethylene-vinyl acetate copolymer, 20-30 parts of polyimides and bentonite 5-10
Part.
Preferably, the adhesive layer the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer mix it is equal
It is even, it adds in 200-230 DEG C of extruder and melts, and obtained by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll
To the adhesive layer with a thickness of 10-20 μm.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer intracavitary, the electricity in the case where power is 120-150W that is respectively put into plasma
Dizzy processing 10-20min, then 3-4h is heated at 120-130 DEG C；Then pass through laminating machine for weathering film layer, adhesive layer, barrier film
Layer, adhesive layer, weathering film layer are stacked gradually from top to bottom, are suppressed, and obtain composite membrane, and composite membrane is hardened 20- at 60-80 DEG C
Then 30min hardens 24-36h at room temperature again, obtain solar cell backboard film.
The beneficial effects of adopting the technical scheme are that
1) preparation method of ultraviolet aging resistance solar cell backboard film provided by the invention, operation is simple, raw material
It is easy to get, cheap, not high to device dependence, reaction condition is mild, and it is practical, it is suitble to large-scale production.
2) ultraviolet aging resistance solar cell backboard film provided by the invention, overcome conventional solar cell backboard membrane or
Price is more expensive, production technology is complicated, interlaminar strength is poor, is easy to fall off existing for more or few, the backboard membrane cementability of preparation
Difference, electrical insulating property are low, are easy embrittlement, tearing, and resistance to UV aging is poor, and the technology for being unable to satisfy high-end product requirement is asked
Topic has cheap mechanical performance, preparation cost, anti-ultraviolet ageing performance, insulating properties, cementability, barrier property and weatherability more
Excellent advantage.
3) ultraviolet aging resistance solar cell backboard film provided by the invention, weathering film layer use 4,4'- (4- amino -4H-
1,2,4- triazole -3,5- diyl) dibenzoic acid, condensation polymer is prepared made of bis- (3- amino -4- fluorophenyl) ketone polycondensations,
Triazole and Benzophenone structure are had on main polymer chain, the two synergistic effect improves the resistance to ultraviolet old of solar cell backboard film
Change performance, and the functional group of two kinds of different structures makes absorbent ultraviolet wavelength range wider, ultraviolet aging resistance ability
It is stronger, and the two while improving anti-ultraviolet ageing performance, in turn ensures that weathering film layer is good on polymer molecule backbone
Good insulation performance, mechanical strength, weatherability and water vapor barrier property；It avoids compatibility caused by addition auxiliary agent and infiltration is asked
Topic；Fluorine is introduced on film layer structure, and it is (anti-to make it have fluorinated polymer material weatherability, self-cleaning (pollution resistance), anti-corrosive properties
Salt, Acid Rain), washability, water vapor barrier property etc., it is low and do not glue that the amide groups and triazolyl of introducing overcome fluorine material surface energy
The shortcomings that property, avoids removing between conventional backing plate and adhesive layer and backboard itself between layers to a certain extent
Separation improves film layer barrier property.
4) ultraviolet aging resistance solar cell backboard film provided by the invention, barrier film layer is using 2,7- naphthalene diacid and two
Toluene glycol polycondensation is made, and has the excellent barrier property more excellent than PET material, and itself and weathering film layer base adhesive layer
Describing property is more preferable, is less prone to layer separation, the strong guarantee service life of solar cell backboard film.
5) ultraviolet aging resistance solar cell backboard film provided by the invention, adhesive layer are multiple using a variety of adhesive function ingredients
Close, and nanoscale bentonite be added, enable adhesion more preferably, itself weatherability more preferably, strong guarantee solar energy
The comprehensive performance of battery back-sheet film.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is purchased from shellfish (Shanghai) Biotechnology Co., Ltd that rubs；Under the present invention
State the EXCELAM-PLUS655RM laminating machine that laminating machine used in embodiment is GMP company.
Embodiment 1
A kind of ultraviolet aging resistance solar cell backboard film including barrier film layer and is set to barrier film layer or more two sides
Weathering film layer passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer is by 4,4'-
(4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones are through amidation polycondensation
Reaction is prepared；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；
The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.
Wherein, the weathering film layer the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyls)
Dibenzoic acid 1.3kg, bis- (3- amino -4- fluorophenyl) ketone 1kg, N, N- diisopropylethylamine 0.4kg, 4-dimethylaminopyridine
0.3kg, which is dissolved in dimethyl sulfoxide 10kg, forms solution, then solution is added in reaction kettle, with air in nitrogen displacement kettle, seals,
In 170 DEG C of back flow reactions, 2 hours progress amidation process, 2- furan boronic acid 0.5kg is then added thereto, is depressurized to 200Pa,
Polycondensation reaction 8 hours at 250 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer ethyl alcohol of precipitation
After washing 3 times, then be placed at 80 DEG C of vacuum oven and dry to constant weight, after product is added in 220 DEG C of extruder melt, and
The weathering film layer with a thickness of 25 μm is obtained by equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer rolls；
Wherein, the barrier film layer the preparation method comprises the following steps: by 2,7- naphthalene diacid 1.57kg and meta-xylene glycol 1kg are added
Solution is formed in n,N-Dimethylformamide 10kg, then solution is added in polymerization reaction kettle, it is close with air in nitrogen displacement kettle
Envelope, 3 hours progress esterifications are stirred to react in 280 DEG C, and antimony oxide 0.5kg is then added, 150Pa is depressurized to, 260
Polycondensation reaction 6 hours at DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation ethanol washing 3
After secondary, then be placed at 80 DEG C of vacuum oven and dry to constant weight, after product be added in 220 DEG C of extruder melt, and pass through
The equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll obtain the barrier film layer with a thickness of 25 μm.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight: 20 parts of polyvinyl butyral,
30 parts of ethylene-vinyl acetate copolymer, 20 parts of polyimides and 5 parts of bentonite.
The adhesive layer is uniformly mixed the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer, then plus
Enter and melted in 200 DEG C of extruder, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll with a thickness of 10 μ
The adhesive layer of m.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer to be respectively put into plasma intracavitary, in the case where power is 120W at corona
10min is managed, then heats 3h at 120 DEG C；Then by laminating machine by weathering film layer, adhesive layer, barrier film layer, adhesive layer, resistance to
It waits film layer to stack gradually, suppress from top to bottom, obtains composite membrane, composite membrane is hardened into 20min at 60 DEG C, then again in room temperature
Lower hardening for 24 hours, obtains solar cell backboard film.
Embodiment 2
A kind of ultraviolet aging resistance solar cell backboard film including barrier film layer and is set to barrier film layer or more two sides
Weathering film layer passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer is by 4,4'-
(4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones are through amidation polycondensation
Reaction is prepared；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；
The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.
Wherein, the weathering film layer the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyls)
Dibenzoic acid 1.3kg, bis- (3- amino -4- fluorophenyl) ketone 1kg, N, N- diisopropylethylamine 0.45kg, 4- dimethylamino pyrrole
Pyridine 0.3kg, which is dissolved in n,N-Dimethylformamide 12kg, forms solution, then solution is added in reaction kettle, in helium replacement kettle
Then three (2,2,2- trifluoro second are added in 173 DEG C of back flow reactions, 2.3 hours progress amidation process in air, sealing thereto
Base) borate 0.5kg, be depressurized to 220Pa, polycondensation reaction 8.5 hours at 255 DEG C, after be cooled to room temperature, be adjusted to normal pressure,
Be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then be placed at 83 DEG C of vacuum oven and dry to constant weight, after will
Product is added in 230 DEG C of extruder and melts, and obtains thickness by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll
The weathering film layer that degree is 27 μm；
Wherein, the barrier film layer the preparation method comprises the following steps: by 2,7- naphthalene diacid 1.57kg and meta-xylene glycol 1kg are added
Solution is formed in n,N-Dimethylformamide 12kg, then solution is added in polymerization reaction kettle, it is close with air in nitrogen displacement kettle
Envelope, 3.2 hours progress esterifications are stirred to react in 285 DEG C, and antimony acetate 0.5kg is then added, 170Pa is depressurized to, at 265 DEG C
Lower polycondensation reaction 7 hours, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation with ethanol washing 4 times
Afterwards, then be placed at 83 DEG C of vacuum oven and dry to constant weight, after product is added in 225 DEG C of extruder melt, and pass through clothing
The equipment such as frame type T- mould, the stack of chromium plating, dryer roll obtain the barrier film layer with a thickness of 27 μm.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight: 23 parts of polyvinyl butyral,
35 parts of ethylene-vinyl acetate copolymer, 23 parts of polyimides and 7 parts of bentonite.
The adhesive layer is uniformly mixed the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer, then plus
Enter and melted in 210 DEG C of extruder, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll with a thickness of 13 μ
The adhesive layer of m.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer to be respectively put into plasma intracavitary, in the case where power is 130W at corona
13min is managed, then heats 3.3h at 123 DEG C；Then by laminating machine by weathering film layer, adhesive layer, barrier film layer, adhesive layer,
Weathering film layer is stacked gradually from top to bottom, is suppressed, and obtains composite membrane, composite membrane is hardened 23min at 65 DEG C, then again in room
Temperature is lower to harden 28h, obtains solar cell backboard film.
Embodiment 3
A kind of ultraviolet aging resistance solar cell backboard film including barrier film layer and is set to barrier film layer or more two sides
Weathering film layer passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer is by 4,4'-
(4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones are through amidation polycondensation
Reaction is prepared；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；
The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.
Wherein, the weathering film layer the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyls)
Dibenzoic acid 1.3kg, bis- (3- amino -4- fluorophenyl) ketone 1kg, N, N- diisopropylethylamine 0.5kg, 4-dimethylaminopyridine
0.3kg, which is dissolved in N-Methyl pyrrolidone 13kg, forms solution, then solution is added in reaction kettle, with sky in neon displacement kettle
Then zinc chloride 0.5kg is added thereto, is depressurized in 175 DEG C of back flow reactions, 2.5 hours progress amidation process for gas, sealing
250Pa, polycondensation reaction 9 hours at 260 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation
After ethanol washing 4 times, then be placed at 85 DEG C of vacuum oven and dry to constant weight, after product is added in 235 DEG C of extruder
Melting, and the weathering film layer with a thickness of 28 μm is obtained by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll；
Wherein, the barrier film layer the preparation method comprises the following steps: by 2,7- naphthalene diacid 1.57kg and meta-xylene glycol 1kg are added
Solution is formed in n,N-Dimethylformamide 13kg, then solution is added in polymerization reaction kettle, it is close with air in nitrogen displacement kettle
Envelope, 3.6 hours progress esterifications are stirred to react in 290 DEG C, and antimony glycol 0.5kg is then added, 180Pa is depressurized to, 270
Polycondensation reaction 8 hours at DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation ethanol washing 4
After secondary, then be placed at 86 DEG C of vacuum oven and dry to constant weight, after product be added in 230 DEG C of extruder melt, and pass through
The equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll obtain the barrier film layer with a thickness of 28 μm.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight: 25 parts of polyvinyl butyral,
40 parts of ethylene-vinyl acetate copolymer, 25 parts of polyimides and 8 parts of bentonite.
The adhesive layer is uniformly mixed the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer, then plus
Enter and melted in 220 DEG C of extruder, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll with a thickness of 15 μ
The adhesive layer of m.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer to be respectively put into plasma intracavitary, in the case where power is 140W at corona
17min is managed, then heats 3.6h at 126 DEG C；Then by laminating machine by weathering film layer, adhesive layer, barrier film layer, adhesive layer,
Weathering film layer is stacked gradually from top to bottom, is suppressed, and obtains composite membrane, composite membrane is hardened 26min at 70 DEG C, then again in room
Temperature is lower to harden 30h, obtains solar cell backboard film.
Embodiment 4
A kind of ultraviolet aging resistance solar cell backboard film including barrier film layer and is set to barrier film layer or more two sides
Weathering film layer passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer is by 4,4'-
(4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones are through amidation polycondensation
Reaction is prepared；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；
The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.
Wherein, the weathering film layer the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyls)
Dibenzoic acid 1.3kg, bis- (3- amino -4- fluorophenyl) ketone 1kg, N, N- diisopropylethylamine 0.55kg, 4- dimethylamino pyrrole
Pyridine 0.3kg, which is dissolved in high boiling solvent 14kg, forms solution, then solution is added in reaction kettle, with air in argon gas displacement kettle,
Then I 0.5kg of catalyst is added thereto, is depressurized in 178 DEG C of back flow reactions, 2.8 hours progress amidation process for sealing
290Pa, polycondensation reaction 9.5 hours at 265 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymerization of precipitation
Object is with after ethanol washing 5 times, then is placed at 88 DEG C of vacuum oven and dries to constant weight, after product is added to 240 DEG C of extruder
Middle melting, and the weathering film layer with a thickness of 28 μm is obtained by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll；
The high boiling solvent is dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone 1:2:2 in mass ratio
The mixture mixed；The catalyst I is 2- furan boronic acid, three (2,2,2- trifluoroethyl) borates, zinc chloride by matter
Measure the mixture mixed than 2:3:5.
The barrier film layer the preparation method comprises the following steps: N, N- is added in 2,7- naphthalene diacid 1.57kg and meta-xylene glycol 1kg
Solution is formed in dimethylformamide 14.5kg, then solution is added in polymerization reaction kettle, it is close with air in nitrogen displacement kettle
Envelope, 3.8 hours progress esterifications are stirred to react in 295 DEG C, and catalyst II 0.5kg is then added, 190Pa is depressurized to, 275
Polycondensation reaction 9 hours at DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation ethanol washing 5
After secondary, then be placed at 89 DEG C of vacuum oven and dry to constant weight, after product be added in 235 DEG C of extruder melt, and pass through
The equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll obtain the barrier film layer with a thickness of 29 μm.
The catalyst II is the mixing that antimony oxide, antimony acetate, antimony glycol 3:2:5 in mass ratio are mixed
Object.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight: 28 parts of polyvinyl butyral,
45 parts of ethylene-vinyl acetate copolymer, 28 parts of polyimides and 9 parts of bentonite.
The adhesive layer is uniformly mixed the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer, then plus
Enter and melted in 225 DEG C of extruder, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll with a thickness of 19 μ
The adhesive layer of m.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer to be respectively put into plasma intracavitary, in the case where power is 145W at corona
19min is managed, then heats 3.8h at 128 DEG C；Then by laminating machine by weathering film layer, adhesive layer, barrier film layer, adhesive layer,
Weathering film layer is stacked gradually from top to bottom, is suppressed, and obtains composite membrane, composite membrane is hardened 29min at 78 DEG C, then again in room
Temperature is lower to harden 35h, obtains solar cell backboard film.
Embodiment 5
A kind of ultraviolet aging resistance solar cell backboard film including barrier film layer and is set to barrier film layer or more two sides
Weathering film layer passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer is by 4,4'-
(4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones are through amidation polycondensation
Reaction is prepared；The barrier film layer is to be reacted to be prepared through esterifying polycondensation with meta-xylene glycol by 2,7- naphthalene diacid；
The adhesive layer is prepared by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite.
Wherein, the weathering film layer the preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyls)
Dibenzoic acid 1.3kg, bis- (3- amino -4- fluorophenyl) ketone 1kg, N, N- diisopropylethylamine 0.6kg, 4-dimethylaminopyridine
0.3kg, which is dissolved in dimethyl sulfoxide 15kg, forms solution, then solution is added in reaction kettle, with air in nitrogen displacement kettle, seals,
In 180 DEG C of back flow reactions, 3 hours progress amidation process, 2- furan boronic acid 0.5kg is then added thereto, is depressurized to 300Pa,
Polycondensation reaction 10 hours at 270 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer ethyl alcohol of precipitation
After washing 5 times, then be placed at 90 DEG C of vacuum oven and dry to constant weight, after product is added in 250 DEG C of extruder melt, and
The weathering film layer with a thickness of 30 μm is obtained by equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer rolls；
Wherein, the barrier film layer the preparation method comprises the following steps: by 2,7- naphthalene diacid 1.57kg and meta-xylene glycol 1kg are added
Solution is formed in n,N-Dimethylformamide 15kg, then solution is added in polymerization reaction kettle, it is close with air in nitrogen displacement kettle
Envelope, 4 hours progress esterifications are stirred to react in 300 DEG C, and antimony acetate 0.5kg is then added, 200Pa is depressurized to, at 280 DEG C
Polycondensation reaction 10 hours, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation with ethanol washing 5 times
Afterwards, then be placed at 90 DEG C of vacuum oven and dry to constant weight, after product is added in 240 DEG C of extruder melt, and pass through clothing
The equipment such as frame type T- mould, the stack of chromium plating, dryer roll obtain the barrier film layer with a thickness of 30 μm.
The adhesive layer is prepared after being sufficiently mixed by the raw material of following parts by weight: 30 parts of polyvinyl butyral,
50 parts of ethylene-vinyl acetate copolymer, 30 parts of polyimides and 10 parts of bentonite.
The adhesive layer is uniformly mixed the preparation method comprises the following steps: the raw material is proportionally added into high-speed mixer, then plus
Enter and melted in 230 DEG C of extruder, and obtains by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll with a thickness of 20 μ
The adhesive layer of m.
According to another aspect of the present invention, a method of preparing above-mentioned ultraviolet aging resistance solar cell backboard film, wrap
Include following steps: first will barrier film layer and weathering film layer to be respectively put into plasma intracavitary, in the case where power is 150W at corona
20min is managed, then heats 4h at 130 DEG C；Then by laminating machine by weathering film layer, adhesive layer, barrier film layer, adhesive layer, resistance to
It waits film layer to stack gradually, suppress from top to bottom, obtains composite membrane, composite membrane is hardened into 30min at 80 DEG C, then again in room temperature
Lower hardening 36h, obtains solar cell backboard film.
Comparative example
Commercially available solar cell backboard film, polyester film (BOPET) are base material film, the laminating pvf film in top and bottom (PVF)
It forms.
Correlated performance test, test are carried out to above-described embodiment 1-5 and the resulting solar cell backboard film of comparative example
As a result 1 is shown in Table with test method.
Table 1
| Detection project | Anti- UV aging | Film bond strength between layers | Weather resistance | Insulation performance | Moisture-vapor transmission |
| Unit | KJ/m2 | N/10mm | 85 DEG C × 85%RH, h | KV/mm | g/m2.d |
| Examination criteria | SAEJ1344 | GB/T2790-1995 | IEC61215 | ASTMD149 | ASTMF1249 |
| Embodiment 1 | 2730 | 75 | 2320 | 100 | 0.02 |
| Embodiment 2 | 2740 | 79 | 2340 | 103 | 0.01 |
| Embodiment 3 | 2760 | 83 | 2350 | 105 | 0.01 |
| Embodiment 4 | 2770 | 85 | 2360 | 108 | 0.01 |
| Embodiment 5 | 2780 | 90 | 2380 | 110 | 0.01 |
| Comparative example | 1800 | 30 | 1300 | 60 | 4.3 |
As it can be seen from table 1 solar cell backboard film ultraviolet aging resistance disclosed by the embodiments of the present invention, weatherability
Energy, insulation performance are more preferable compared with commercial product, and film bond strength between layers are higher, and moisture-vapor transmission is lower.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of ultraviolet aging resistance solar cell backboard film, which is characterized in that including barrier film layer and be set to barrier film layer
The weathering film layer of upper and lower two sides, passes through adhesive layer lamination adhesive between barrier film layer and the weathering film layer；The weathering film layer
It is by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid and bis- (3- amino -4- fluorophenyl) ketones through acyl
Amination polycondensation reaction is prepared；The barrier film layer is with meta-xylene glycol by 2,7- naphthalene diacid through the esterifying polycondensation system of reacting
It is standby to form；The adhesive layer be by polyvinyl butyral, ethylene-vinyl acetate copolymer, polyimides and bentonite preparation and
At.
2. ultraviolet aging resistance solar cell backboard film according to claim 1, which is characterized in that the weathering film layer
The preparation method comprises the following steps: by 4,4'- (4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid, bis- (3- amino -4- fluorophenyls)
Ketone, n,N-diisopropylethylamine, 4-dimethylaminopyridine, which are dissolved in high boiling solvent, forms solution, then solution is added and is reacted
In kettle, with air in nitrogen or inert gas replacement kettle, sealing is anti-in the progress amidation in 2-3 hours of 170-180 DEG C of back flow reaction
It answers, catalyst I is then added thereto, is depressurized to 200-300Pa, it is rear cooling polycondensation reaction 8-10 hours at 250-270 DEG C
To room temperature, it is adjusted to normal pressure, is precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then is placed in vacuum oven
Dried at 80-90 DEG C to constant weight, after product is added in 220-250 DEG C of extruder melt, and pass through clothes hanger type T- mould, chromium plating
The equipment such as stack, dryer roll obtain the weathering film layer with a thickness of 25-30 μm.
3. ultraviolet aging resistance solar cell backboard film according to claim 2, which is characterized in that preferably, described 4,
4'- (4- amino -4H-1,2,4- triazole -3,5- diyl) dibenzoic acid, bis- (3- amino -4- fluorophenyl) ketones, N, N- diisopropyl
Base ethamine, 4-dimethylaminopyridine, high boiling solvent, catalyst I mass ratio be 1.3:1:(0.4-0.6): 0.3:(10-
15):0.5。
4. ultraviolet aging resistance solar cell backboard film according to claim 2, which is characterized in that the high boiling solvent
Selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone；The inert gas is selected from helium
One or more of gas, neon, argon gas.
5. ultraviolet aging resistance solar cell backboard film according to claim 2, which is characterized in that the catalyst I selects
From one or more of 2- furan boronic acid, three (2,2,2- trifluoroethyl) borates, zinc chloride.
6. ultraviolet aging resistance solar cell backboard film according to claim 1, which is characterized in that the barrier film layer
Preferably the preparation method comprises the following steps: by 2,7- naphthalene diacid and meta-xylene glycol are added in n,N-Dimethylformamide and form solution one kind,
Solution is added in polymerization reaction kettle again, with air in nitrogen displacement kettle, is sealed, be stirred to react in 280-300 DEG C 3-4 hours into
Row esterification, is then added catalyst II, is depressurized to 150-200Pa, polycondensation reaction 6-10 hours at 260-280 DEG C, after
It is cooled to room temperature, is adjusted to normal pressure, is precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then be placed in vacuum drying
Dried at 80-90 DEG C of case to constant weight, after product is added in 220-240 DEG C of extruder melt, and by clothes hanger type T- mould, plating
The equipment such as stack, the dryer roll of chromium obtain the barrier film layer with a thickness of 25-30 μm.
7. ultraviolet aging resistance solar cell backboard film according to claim 6, which is characterized in that 2, the 7- naphthalene two
Acid, meta-xylene glycol, N,N-dimethylformamide, catalyst II mass ratio be 1.57:1:(10-15): 0.5；It is described to urge
Agent II is selected from one or more of antimony oxide, antimony acetate or antimony glycol.
8. ultraviolet aging resistance solar cell backboard film according to claim 1, which is characterized in that the adhesive layer be by
What the raw material of following parts by weight was prepared after being sufficiently mixed: 20-30 parts of polyvinyl butyral, ethylene-vinyl acetate copolymer
30-50 parts, 20-30 parts of polyimides and 5-10 parts of bentonite.
9. ultraviolet aging resistance solar cell backboard film according to claim 8, which is characterized in that the system of the adhesive layer
Preparation Method are as follows: the raw material is proportionally added into high-speed mixer and is uniformly mixed, adds in 200-230 DEG C of extruder and melts
Melt, and obtains the adhesive layer with a thickness of 10-20 μm by the equipment such as clothes hanger type T- mould, the stack of chromium plating, dryer roll.
10. -9 described in any item ultraviolet aging resistance solar cell backboard films according to claim 1, which is characterized in that described
The preparation method of solar cell backboard film, include the following steps: first will barrier film layer and weathering film layer be respectively put into etc. from
Daughter is intracavitary, the sided corona treatment 10-20min in the case where power is 120-150W, then heats 3-4h at 120-130 DEG C；Then pass through
Weathering film layer, adhesive layer, barrier film layer, adhesive layer, weathering film layer are stacked gradually from top to bottom, are suppressed by laminating machine, are answered
Film is closed, composite membrane is hardened into 20-30min at 60-80 DEG C, 24-36h is then hardened at room temperature again, obtains solar battery
Backboard membrane.
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| CN114613871A (en) * | 2022-04-02 | 2022-06-10 | 浙江合特光电有限公司 | Light flexible photovoltaic module |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513895A (en) * | 2002-12-18 | 2004-07-21 | ס�ѻ�ѧ��ҵ��ʽ���� | Aromatic liquid crystal polyester and its film |
| CN1608096A (en) * | 2001-12-26 | 2005-04-20 | 昭和电工株式会社 | Fluorinated polymer |
| CN108598196A (en) * | 2018-04-19 | 2018-09-28 | 山东冬瑞高新技术开发有限公司 | A kind of high-weatherability solar cell backboard and preparation method thereof |
-
2018
- 2018-11-20 CN CN201811385446.5A patent/CN109278369B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608096A (en) * | 2001-12-26 | 2005-04-20 | 昭和电工株式会社 | Fluorinated polymer |
| CN1513895A (en) * | 2002-12-18 | 2004-07-21 | ס�ѻ�ѧ��ҵ��ʽ���� | Aromatic liquid crystal polyester and its film |
| CN108598196A (en) * | 2018-04-19 | 2018-09-28 | 山东冬瑞高新技术开发有限公司 | A kind of high-weatherability solar cell backboard and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王珏等编著: "《塑料改性实用技术与应用》", 30 June 2014, 印刷工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114613871A (en) * | 2022-04-02 | 2022-06-10 | 浙江合特光电有限公司 | Light flexible photovoltaic module |
| CN114613871B (en) * | 2022-04-02 | 2024-03-12 | 浙江合特光电有限公司 | Light flexible photovoltaic module |
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