CN113563814A - Multilayer foamed photovoltaic adhesive film and preparation method thereof - Google Patents
Multilayer foamed photovoltaic adhesive film and preparation method thereof Download PDFInfo
- Publication number
- CN113563814A CN113563814A CN202110816551.5A CN202110816551A CN113563814A CN 113563814 A CN113563814 A CN 113563814A CN 202110816551 A CN202110816551 A CN 202110816551A CN 113563814 A CN113563814 A CN 113563814A
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- Prior art keywords
- parts
- foaming
- multilayer
- surface layer
- agent
- Prior art date
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- Granted
Links
- 239000002313 adhesive film Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000012792 core layer Substances 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 230000003139 buffering effect Effects 0.000 claims abstract description 5
- 238000005187 foaming Methods 0.000 claims description 119
- 239000002344 surface layer Substances 0.000 claims description 99
- 239000002105 nanoparticle Substances 0.000 claims description 60
- 239000003963 antioxidant agent Substances 0.000 claims description 57
- 230000003078 antioxidant effect Effects 0.000 claims description 57
- 239000000872 buffer Substances 0.000 claims description 46
- 239000002994 raw material Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 32
- 239000003504 photosensitizing agent Substances 0.000 claims description 32
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 239000002250 absorbent Substances 0.000 claims description 26
- 230000002745 absorbent Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 21
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 21
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 239000012754 barrier agent Substances 0.000 claims description 17
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 4-methylthiophenyl Chemical group 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- PDQDVWQFXLXTGU-UHFFFAOYSA-N 2-[1-carboxy-2-(3,5-ditert-butyl-4-hydroxyphenyl)ethyl]sulfanyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(=CC(=C1O)C(C)(C)C)CC(C(=O)O)SC(CC2=CC(=C(C(=C2)C(C)(C)C)O)C(C)(C)C)C(=O)O PDQDVWQFXLXTGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical compound NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- CYPKLFLFMZVKJE-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Na+].C(C1=C(C(=CC(=C1)CCCC)CCCC)O)C1=C(C(=CC(=C1)CCCC)CCCC)O.[Na+].[Na+] Chemical group P(=O)([O-])([O-])[O-].[Na+].C(C1=C(C(=CC(=C1)CCCC)CCCC)O)C1=C(C(=CC(=C1)CCCC)CCCC)O.[Na+].[Na+] CYPKLFLFMZVKJE-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 210000002615 epidermis Anatomy 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 5
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 38
- 210000004027 cell Anatomy 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 20
- 239000005038 ethylene vinyl acetate Substances 0.000 description 11
- 239000004156 Azodicarbonamide Substances 0.000 description 10
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 10
- 235000019399 azodicarbonamide Nutrition 0.000 description 10
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 238000010030 laminating Methods 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- BSWPEGCWMCHQJP-UHFFFAOYSA-L disodium [2,4-dibutyl-6-[(3,5-dibutyl-2-hydroxyphenyl)methyl]phenyl] phosphate Chemical group P(=O)([O-])([O-])OC1=C(C=C(C=C1CCCC)CCCC)CC1=C(C(=CC(=C1)CCCC)CCCC)O.[Na+].[Na+] BSWPEGCWMCHQJP-UHFFFAOYSA-L 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 210000003850 cellular structure Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- SFDGJDBLYNJMFI-UHFFFAOYSA-N 3,1-benzoxazin-4-one Chemical compound C1=CC=C2C(=O)OC=NC2=C1 SFDGJDBLYNJMFI-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- LUCJEPREDVDXKU-UHFFFAOYSA-N ethene silane Chemical compound [SiH4].C=C LUCJEPREDVDXKU-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 description 2
- 239000006173 Good's buffer Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Classifications
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
- B29C44/24—Making multilayered articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
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- 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
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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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
Abstract
The invention relates to the field of photovoltaic materials, and discloses a multilayer foamed photovoltaic adhesive film and a preparation method thereof. The core layer of the multilayer foamed photovoltaic adhesive film disclosed by the invention has a developed cell structure, so that the adhesive film has good buffering performance and elasticity. In addition, the three-layer material is formed in one step through melt co-extrusion, compared with the traditional processing mode, the method has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
Description
Technical Field
The invention relates to the field of photovoltaic materials, in particular to a multilayer foaming photovoltaic adhesive film and a preparation method thereof.
Background
With the vigorous development of the photovoltaic industry in China, the requirements on the use performance of the packaging material in the solar cell module are higher and higher. The photovoltaic adhesive film is mainly used for the packaging link of a photovoltaic module and is a key material of the photovoltaic module. The adhesive film bonds the photovoltaic cell, the photovoltaic glass and the back plate, protects the cell and packages the cell into a photovoltaic module capable of outputting direct current. The photovoltaic module has higher requirements on the performances of weather resistance, bonding strength, aging resistance and the like of an adhesive film used for packaging. Currently, ethylene-vinyl acetate (EVA) polymers or ethylene-octene (POE) copolymers are used as substrates for encapsulating materials. There are also some problems that need to be solved:
1) after the POE or EVA adhesive film forms a multi-layer adhesive film, the multi-layer adhesive film has no buffering performance, and is easy to extrude with a solar cell panel in the packaging process, so that the solar cell panel is brittle. The invention patent CN111682082A discloses a packaging adhesive film and a photovoltaic module, wherein the adhesive film comprises an upper bonding layer, a foaming layer and a lower bonding layer, and the packaging adhesive film with a cellular structure has a lower modulus compared with a common adhesive film, so that the risks of breaking, subfissure, breaking grid and the like of a battery piece during packaging and using processes are greatly reduced, but some problems also exist: 1. the foaming layer is prepared by adopting an extrusion foaming process, and the POE (or EVA) melt strength is low, so that the foam pore morphology is difficult to uniform and stable after extrusion foaming; 2. secondly, the upper layer and the lower layer are coated by adopting a spraying mode and are crosslinked by irradiation, and the process becomes more complicated.
2) The photovoltaic adhesive film is a multilayer material, and for the production of the multilayer material, the traditional preparation process is to respectively form materials of different layers and then realize multilayering by adopting the traditional methods of laminating adhesion or sheet extending-laminating lamination and the like. The process is still adopted at present, and has the defects of multiple working procedures, large investment and low production efficiency.
In summary, how to enhance the buffer performance of the multi-layer photovoltaic adhesive film, how to simplify the preparation process thereof, and how to reduce the cost are the key points of the current research.
Disclosure of Invention
In order to solve the technical problems, the invention provides a multilayer foamed photovoltaic adhesive film and a preparation method thereof. In addition, the three-layer material is formed in one step through melt co-extrusion, compared with the traditional processing mode, the method has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a multilayer foamed photovoltaic adhesive film, which comprises an upper surface layer, a foamed buffer core layer and a lower surface layer which are sequentially overlapped. Wherein:
the upper surface layer and the lower surface layer comprise the following raw materials in parts by weight: 100 parts of POE colloidal particles and/or EVA colloidal particles, 1-5 parts of gas barrier agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent;
the foaming buffer core layer comprises the following raw materials in parts by weight: 100 parts of POE colloidal particles or EVA colloidal particles, 1-5 parts of foaming agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.1-3 parts of modified porous inorganic nanoparticles, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent.
Firstly, the multilayer foaming photovoltaic adhesive film has a three-layer structure, wherein the core layer has a developed cellular structure, so that the adhesive film has good buffering performance and elasticity, and the solar cell piece can be prevented from being broken due to mutual extrusion with a hard adhesive film in the sealing process. In addition, the three-layer material is formed at one time through melt coextrusion, compared with the traditional processing mode (laminating adhesion or sheet extending-laminating lamination and the like), the method has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
And secondly, the foaming buffer core layer contains modified porous inorganic nano particles which can generate a crosslinking reaction with active groups on POE (EVA) and a photosensitizer after irradiation to form a three-dimensional network structure, so that the overall melt strength of the material is effectively improved. In addition, the existence of the modified porous inorganic nano particles can promote the core layer to further perform heterogeneous nucleation and increase the cell density.
On the other hand, the gas barrier agent is added in the upper surface layer and the lower surface layer, so that the gas can be effectively prevented from leaking in the foaming process of the core layer, and the core layer forms uniform cells. Meanwhile, the invention also contains assistant cross-linking agent and photosensitizer in the upper and lower surface layers, and the cross-linking density of the upper and lower surface layers is enhanced after irradiation, thus further improving the gas barrier property of the upper and lower surface layers. In addition, a cross-linking structure can be formed between adjacent layers after irradiation, and the interlayer bonding force can be effectively improved.
Preferably, the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
Preferably, the preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) dispersing the porous inorganic nanoparticles in the mixed solution, stirring for reaction, taking the precipitate, and drying to prepare the modified porous inorganic nanoparticles.
The invention adds modified porous inorganic nano particles in a foaming buffer core layer. After the modification treatment, carbon-carbon double bonds are grafted on the surfaces of the porous inorganic nanoparticles. Therefore, under the irradiation condition, the double bond not only can be used as an active site to generate a crosslinking reaction with active groups on POE (ethylene vinyl acetate) (EVA) and a photosensitizer to form a three-dimensional network structure, higher crosslinking density is shown, the network formed by winding between chains is more complex, the acting force between molecular chain segments is enhanced, the integral melt strength of the material is effectively improved, the foaming multiplying power and the stability of a foam structure in the foaming process are further increased, and the existence of the modified porous inorganic nano particles can promote the core layer to further perform heterogeneous nucleation. The introduction of modified porous inorganic nanoparticles provides heterogeneous surfaces, the Gibbs free energy barrier for nucleation is reduced compared to homogeneous nucleation, the cells nucleate first at these surfaces, i.e. the polymer-inorganic nanoparticle interface, while initiating nucleation within the polymer matrix, resulting in a narrower pore size distribution.
Preferably, in step (1): the vinyl silane coupling agent comprises one or a mixture of gamma-methacryloxypropyl trimethoxysilane, triacetoxy vinyl silane and vinyl triethoxysilane; the concentration of the vinyl silane coupling agent in the mixed solution is 2-5 wt%.
Preferably, in step (2): the porous inorganic nano particles comprise one or more of clay, hydrotalcite and mesoporous silica; the stirring reaction time is 5-6 h; the drying temperature is 100-110 ℃.
Preferably, in step (1): the mixed solution also contains 2-5wt% of organic phosphate.
The invention also introduces organic phosphate as an organic nucleating agent while modifying the porous inorganic nano particles. The organic-inorganic compounding method can greatly reduce the cost of compounding the nucleating agent, separate and disperse the porous inorganic nano particles and the organic nucleating agent particles, promote the melt strength of the adhesive film, provide nucleation sites and improve the density of foam pores.
Preferably, the organic phosphate is sodium 2, 2' -methylene-bis (4, 6-di-n-butylphenol) phosphate.
Preferably, the gas barrier agent is one or a mixture of montmorillonite, boron nitride and molybdenum disulfide.
In the previous experiments, it was found that the gas generated by the foaming agent in the final foaming process is easy to escape from the upper and lower surface layers and to be lost due to the thin thickness of the upper and lower surface layers, resulting in very poor foaming effect. Therefore, the flaky inorganic nanoparticles are added in the upper surface layer and the lower surface layer to serve as gas blocking agents, and the flaky structure can effectively prevent gas from leaking in the foaming process of the core layer, so that uniform cells are formed in the core layer.
Preferably, the auxiliary crosslinking agent is one or a mixture of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate.
Preferably, the photosensitizer is one or a mixture of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
Preferably, the antioxidant comprises a hindered phenol antioxidant and a thioester antioxidant/phosphite antioxidant, wherein the hindered phenol antioxidant is one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2, 2' -thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the ultraviolet absorbent is benzophenone and/or benzotriazole. More preferably, the ultraviolet light absorber includes but is not limited to one or more of 2-hydroxy-4-n-octoxybenzophenone, 2-tetramethylene bis (3, 1-benzoxazine-4-one), 2- (2 ' -hydroxy-5-methylphenyl) benzotriazole, 2' -dihydroxy-4, 4 ' -dimethoxybenzophenone and the like or a mixture of several thereof.
Preferably, the foaming agent is an azo foaming agent and/or a sulfonyl hydrazide foaming agent. Preferably, the blowing agent comprises azodicarbonamide and/or 4, 4-oxybis-benzenesulfonylhydrazide.
In a second aspect, the present invention provides a method for preparing a multilayer foamed photovoltaic adhesive film, comprising the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film.
The invention adopts a multilayer co-extrusion mode to prepare the multilayer foaming photovoltaic adhesive film, has simple process and low cost compared with the traditional processing mode (laminating adhesion or sheet extrusion by extension-lamination and the like), and can effectively improve the production efficiency.
In the step (C), the invention firstly irradiates for crosslinking and then foams at high temperature
The former can make the core layer form a highly cross-linked three-dimensional network structure after treatment, thereby improving the melt strength of the core layer, and the latter can form a developed cellular structure after treatment, thereby leading the adhesive film to have good buffer performance and elasticity, and avoiding the fragmentation of the solar cell slice caused by mutual extrusion with a hard adhesive film in the sealing process.
Preferably, the irradiation intensity is 5-40kGy, the foaming temperature is 200-300 ℃, and the traction speed in the foaming process is 5-15 m/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the multilayer foamed photovoltaic adhesive film has a three-layer structure, wherein the core layer has a developed cell structure, so that the adhesive film has good buffering performance and elasticity, and the solar cell piece can be prevented from being broken due to mutual extrusion with a hard adhesive film in the sealing process.
(2) The foaming buffer core layer contains modified porous inorganic nano particles, and the modified porous inorganic nano particles can generate a crosslinking reaction with active groups on POE (EVA) and a photosensitizer after irradiation to form a three-dimensional network structure, so that the overall melt strength of the material is effectively improved. In addition, the existence of the modified porous inorganic nano particles can promote the core layer to further perform heterogeneous nucleation, thereby improving the foaming ratio.
(3) According to the invention, the gas barrier agent is added in the upper surface layer and the lower surface layer, so that gas can be effectively prevented from leaking in the foaming process of the core layer, and the core layer can form uniform cells. Meanwhile, the invention also contains assistant cross-linking agent and photosensitizer in the upper and lower surface layers, and the cross-linking density of the upper and lower surface layers is enhanced after irradiation, thus further improving the gas barrier property of the upper and lower surface layers. In addition, a cross-linking structure can be formed between adjacent layers after irradiation, and the interlayer bonding force can be effectively improved.
(4) The invention forms the three layers of materials at one time through melt coextrusion, compared with the traditional processing mode (laminating adhesion or sheet extending-laminating lamination and the like), the invention has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
Drawings
FIG. 1 is a schematic view of the layered structure of the multi-layer foamed photovoltaic adhesive film of the present invention;
FIG. 2 is a sectional SEM image of a multilayer foamed photovoltaic adhesive film prepared in example 1 of the present invention;
FIG. 3 is a sectional SEM image of a multilayer foamed photovoltaic film prepared in example 5 of the present invention;
FIG. 4 is a sectional SEM image of a multilayer foamed photovoltaic adhesive film prepared in comparative example 1 of the present invention;
FIG. 5 is a sectional SEM image of a multilayer foamed photovoltaic adhesive film prepared in comparative example 3 of the present invention;
FIG. 6 is a sectional SEM image of a multilayer foamed photovoltaic adhesive film prepared in comparative example 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A multi-layer foamed photovoltaic adhesive film is shown in figure 1 and comprises an upper surface layer, a foamed buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper surface layer and the lower surface layer comprise the following raw materials in parts by weight: 100 parts of POE colloidal particles and/or EVA colloidal particles, 1-5 parts of gas barrier agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent;
the foaming buffer core layer comprises the following raw materials in parts by weight: 100 parts of POE colloidal particles or EVA colloidal particles, 1-5 parts of foaming agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.1-3 parts of modified porous inorganic nanoparticles, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent.
The gas barrier agent is one or a mixture of montmorillonite, boron nitride and molybdenum disulfide.
The auxiliary crosslinking agent is one or a mixture of more of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate.
The photosensitizer is one or a mixture of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
The antioxidant comprises a hindered phenol antioxidant and a thioester antioxidant/phosphite antioxidant, wherein the hindered phenol antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and 2, 2' -thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The ultraviolet absorbent is benzophenone and/or benzotriazole. More preferably, the ultraviolet light absorber includes but is not limited to one or more of 2-hydroxy-4-n-octoxybenzophenone, 2-tetramethylene bis (3, 1-benzoxazine-4-one), 2- (2 ' -hydroxy-5-methylphenyl) benzotriazole, 2' -dihydroxy-4, 4 ' -dimethoxybenzophenone and the like or a mixture of several thereof.
The foaming agent is an azo foaming agent and/or a sulfonyl hydrazine foaming agent. Preferably, the blowing agent comprises azodicarbonamide and/or 4, 4-oxybis-benzenesulfonylhydrazide.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (one or a mixture of gamma-methacryloxypropyltrimethoxysilane, triacetoxyvinylsilane and vinyltriethoxysilane) and 2, 2' -methylene-bis (4, 6-di-n-butylphenol) sodium phosphate (selectively added) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinyl silane coupling agent is 2-5wt%, and the concentration of the sodium 2, 2' -methylene-bis (4, 6-di-n-butylphenol) phosphate is 2-5 wt%.
(2) Dispersing porous inorganic nanoparticles (one or more of clay, hydrotalcite and mesoporous silica) in a mixed solution, stirring for reaction for 5-6h, taking the precipitate, and drying at the temperature of 110 ℃ under the action of 100-.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 5-40kGy, the foaming temperature is 200-300 ℃, and the traction speed in the foaming process is 5-15 m/min.
Example 1
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 3 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinylsilane coupling agent was 2% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
The sectional morphology of the multilayer foamed photovoltaic adhesive film prepared in example 1 is subjected to SEM characterization, and the result is shown in FIG. 2, and as can be seen from FIG. 2, the material prepared by the method disclosed by the invention has uniform cells, good substrate compatibility and no obvious phase separation.
Example 2
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 1 part of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 5 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinylsilane coupling agent was 2% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
Example 3
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 3 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinylsilane coupling agent was 2% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
Example 4
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 3 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 5 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing KH570 in the ethanol-water mixed solution to prepare a 2 wt% ethylene silane coupling agent solution;
(2) dispersing mesoporous silica in an ethylene silane coupling agent solution, stirring for reacting for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare modified porous inorganic nanoparticles;
a preparation method of a multilayer foaming adhesive film material comprises the following preparation steps:
(1) uniformly mixing the raw materials by a mixer;
(2) the preparation raw material mixture of the surface layer A is put into a first screw extruder, the preparation raw material mixture of the core layer B is put into a second screw extruder, the preparation raw material mixture of the surface layer A is put into a third screw extruder, the mixture is plasticized at 110-140 ℃, and enters a co-extrusion molding machine head through a connector for extrusion, and the mixture respectively passes through a three-roller press polishing unit, a cooling cold roller, a tractor and a shearing machine to form the multilayer coiled material.
(3) And (3) irradiating and crosslinking the coiled material prepared in the step, and foaming at a high temperature to obtain the finished product foam. The irradiation intensity is 20kGy, the irradiated coiled material is foamed by a high-temperature furnace, the temperature of the high-temperature furnace is 250 ℃, and the traction speed is 6 m/min.
Example 5
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 3 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) putting a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) and sodium 2, 2' -methylene-bis (4, 6-di-n-butylphenol) phosphate into a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinyl silane coupling agent was 2% by weight and the concentration of sodium 2, 2' -methylene-bis (4, 6-di-n-butylphenol) phosphate was 3% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
The sectional morphology of the multilayer foamed photovoltaic adhesive film prepared in example 5 is subjected to SEM characterization, and the result is shown in FIG. 3, and as can be seen from FIG. 3, the material prepared by the invention has uniform cells, good substrate compatibility and no obvious phase separation.
Comparative example 1
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 3 parts of common mesoporous silica particles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
The sectional morphology of the multilayer foamed photovoltaic adhesive film prepared in the comparative example 1 is subjected to SEM characterization, and as shown in FIG. 4, the crack exists in the section of the material due to the fact that the nano particles are not modified.
Comparative example 2
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
A preparation method of a multilayer foaming adhesive film material comprises the following preparation steps:
(1) uniformly mixing the raw materials by a mixer;
(2) the preparation raw material mixture of the surface layer A is put into a first screw extruder, the preparation raw material mixture of the core layer B is put into a second screw extruder, the preparation raw material mixture of the surface layer A is put into a third screw extruder, the mixture is plasticized at 110-140 ℃, and enters a co-extrusion molding machine head through a connector for extrusion, and the mixture respectively passes through a three-roller press polishing unit, a cooling cold roller, a tractor and a shearing machine to form the multilayer coiled material.
(3) And (3) irradiating and crosslinking the coiled material prepared in the step, and foaming at a high temperature to obtain the finished product foam. The irradiation intensity is 20kGy, the irradiated coiled material is foamed by a high-temperature furnace, the temperature of the high-temperature furnace is 250 ℃, and the traction speed is 6 m/min.
Comparative example 3
A multilayer foaming photovoltaic adhesive film comprises an upper surface layer, a foaming buffer core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The foaming buffer core layer comprises: 100 parts of POE particles; 5 parts of an AC foaming agent azodicarbonamide; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 5 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinylsilane coupling agent was 2% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer foaming photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, the foaming temperature is 250 ℃, and the traction speed in the foaming process is 6 m/min.
The sectional morphology of the multilayer photovoltaic adhesive film prepared in the comparative example 3 is subjected to SEM characterization, and the result is shown in FIG. 5, and as can be seen from FIG. 5, the material prepared in the comparative example 3 has no foaming agent added, so that the cells are not obvious, and the foaming effect is not achieved basically.
Comparative example 4
A multi-layer photovoltaic adhesive film comprises an upper surface layer, a core layer and a lower surface layer which are sequentially overlapped. Wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the core layer is 0.4 +/-0.01 mm.
The upper/lower surface layers include: 100 parts of POE particles; 3 parts of gas barrier agent montmorillonite; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorber.
The core layer includes: 100 parts of POE particles; 3 parts of assistant crosslinking agent TAIC; 5 parts of photosensitizer 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; 3 parts of modified porous inorganic nanoparticles; 1680.5 parts of antioxidant; 10760.5 parts of an antioxidant; 0.5 part of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone.
The preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent (gamma-methacryloxypropyltrimethoxysilane) in a mixed solvent of ethanol and water to prepare a mixed solution; the concentration of the vinylsilane coupling agent was 2% by weight.
(2) Dispersing porous inorganic nanoparticles (mesoporous silicon dioxide) in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at 100 ℃ to prepare the modified porous inorganic nanoparticles.
A preparation method of a multilayer photovoltaic adhesive film comprises the following steps,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature treatment on the obtained coiled material to obtain the multilayer photovoltaic adhesive film. Wherein the irradiation intensity is 20kGy, and the high-temperature treatment temperature is 250 ℃.
The sectional morphology of the multilayer photovoltaic adhesive film prepared in the comparative example 4 is subjected to SEM characterization, and the result is shown in FIG. 6, and it can be known from FIG. 6 that the material prepared in the comparative example 4 is not added with the gas blocking agent in the comparative example 3, and the gas is very easy to leak due to the thinner overall material of the adhesive film, so that the core layer cannot form good cells.
The cell data of the materials prepared in the examples and comparative examples were calculated and according to the national standard. The tensile strength, elongation at break and impact resilience were measured in accordance with GB/T528-1998 determination of tensile stress strain Properties of vulcanized rubber or thermoplastic rubber and the peel strength in accordance with the requirements in GB/T2790-1995 test method for 180 ℃ peel strength of adhesive and GB T1681-.
As can be seen from the above table, the difference between example 1 and example 2 and comparative example 3 is in the content of montmorillonite, and it can be seen that different gas barrier effects can be exhibited by adding different contents of montmorillonite, resulting in different ratios of core layer foaming, for example, in comparative example 3, no gas barrier agent is added, since the overall material of the adhesive film is thin, gas is very easy to leak, and good cells cannot be formed in the core layer.
The difference between example 1 and examples 3 and comparative example 2 is the content of the porous modified inorganic nanoparticles in the core layer, and it can be seen that the modified nanoparticles not only can improve the melt strength, but also can contribute to the improvement of the foamed cells.
The difference between example 1 and examples 4 and comparative example 4 is the content of the foaming agent, the foaming ratio and the cell density, and the mechanical properties. In comparative example 4, in which no blowing agent was added, almost no cells were formed as can be seen from FIG. 5.
The difference between the embodiment 5 and the embodiment 1 is that the organic phosphate nucleating agent is compounded in the porous modified inorganic nanoparticles, and the inorganic nanoparticles and the organic nucleating agent particles can be separated and dispersed from each other, so that the melt strength of a glue film is promoted, the nucleation in the polymer matrix is initiated, the narrower pore size distribution is caused, the free energy barrier is reduced due to the introduction of the additive, more nucleation sites are provided, the diameter of the cells is increased, the cell density is reduced, the foaming ratio is increased, and the better buffer performance is achieved.
The difference between the comparative example 1 and the example 1 is that the mesoporous silica particles are directly adopted without modification, the foaming ratio and the cell density are lower, and the mechanical property is reduced to some extent; meanwhile, as shown in fig. 6, the porous inorganic nanoparticles are not modified, so that the porous inorganic nanoparticles are poor in dispersion and poor in combination with the matrix, and therefore, the cross section of the prepared foam material has more gaps and cracking phenomena.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides a multilayer foaming photovoltaic glued membrane, includes superimposed upper epidermis, foaming buffering sandwich layer and lower top layer in proper order, its characterized in that:
the upper surface layer and the lower surface layer comprise the following raw materials in parts by weight: 100 parts of POE colloidal particles and/or EVA colloidal particles, 1-5 parts of gas barrier agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent;
the foaming buffer core layer comprises the following raw materials in parts by weight: 100 parts of POE colloidal particles or EVA colloidal particles, 1-5 parts of foaming agent, 0.1-5 parts of auxiliary crosslinking agent, 1-5 parts of photosensitizer, 0.1-3 parts of modified porous inorganic nanoparticles, 0.01-0.5 part of antioxidant and 0.1-1 part of ultraviolet absorbent.
2. The multilayer foamed photovoltaic film of claim 1, wherein: the thickness of the upper surface layer and/or the lower surface layer is 0.1 +/-0.01 mm; the thickness of the foaming buffer core layer is 0.4 +/-0.01 mm.
3. The multilayer foamed photovoltaic film of claim 1, wherein: the preparation method of the modified porous inorganic nanoparticles comprises the following steps:
(1) placing a vinyl silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) dispersing the porous inorganic nanoparticles in the mixed solution, stirring for reaction, taking the precipitate, and drying to prepare the modified porous inorganic nanoparticles.
4. The multilayer foamed photovoltaic film of claim 3, wherein: in the step (1):
the vinyl silane coupling agent comprises one or a mixture of gamma-methacryloxypropyl trimethoxysilane, triacetoxy vinyl silane and vinyl triethoxysilane;
the concentration of the vinyl silane coupling agent in the mixed solution is 2-5 wt%.
5. The multilayer foamed photovoltaic film of claim 3, wherein: in the step (2):
the porous inorganic nano particles comprise one or more of clay, hydrotalcite and mesoporous silica;
the stirring reaction time is 5-6 h; the drying temperature is 100-110 ℃.
6. The multilayer foamed photovoltaic film of any of claims 3 to 5, wherein: in the step (1): the mixed solution also contains 2-5wt% of organic phosphate.
7. The multilayer foamed photovoltaic film of claim 6, wherein: the organic phosphate is 2, 2' -methylene-bis (4, 6-di-n-butylphenol) sodium phosphate.
8. The multilayer foamed photovoltaic film of claim 1, wherein:
the gas barrier agent is one or a mixture of montmorillonite, boron nitride and molybdenum disulfide;
the auxiliary crosslinking agent is one or a mixture of more of triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate;
the photosensitizer is one or a mixture of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone;
the antioxidant comprises a hindered phenol antioxidant and a thioester antioxidant/phosphite antioxidant, wherein the hindered phenol antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and 2, 2' -thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
the ultraviolet absorbent is benzophenone and/or benzotriazole;
the foaming agent is an azo foaming agent and/or a sulfonyl hydrazine foaming agent.
9. A method for preparing a multilayer foamed photovoltaic film according to any one of claims 1 to 8, comprising the steps of,
(A) respectively and uniformly mixing the raw materials of each layer;
(B) respectively putting the raw materials of the upper surface layer, the foaming buffer core layer and the lower surface layer into three different screw extruders, plasticizing at 110-140 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain a multilayer coiled material;
(C) and sequentially carrying out irradiation crosslinking and high-temperature foaming on the obtained coiled material to obtain the multilayer foaming photovoltaic adhesive film.
10. The method of claim 9, wherein: the irradiation intensity is 5-40kGy, the foaming temperature is 200-300 ℃, and the traction speed in the foaming process is 5-15 m/min.
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| CN114621702A (en) * | 2022-03-31 | 2022-06-14 | 杭州福斯特应用材料股份有限公司 | Packaging adhesive film |
| CN114621702B (en) * | 2022-03-31 | 2024-03-12 | 杭州福斯特应用材料股份有限公司 | Packaging adhesive film |
| CN115011282A (en) * | 2022-05-20 | 2022-09-06 | 杭州福斯特应用材料股份有限公司 | Preparation method of packaging adhesive film |
| CN115320201A (en) * | 2022-06-22 | 2022-11-11 | 平湖市华达塑料制品有限公司 | Multilayer high-barrier and high-strength biodegradable film and preparation method thereof |
| CN115320201B (en) * | 2022-06-22 | 2024-03-15 | 平湖市华达塑料制品有限公司 | Multilayer high-barrier high-strength biodegradable film and preparation method thereof |
| CN115139603A (en) * | 2022-07-04 | 2022-10-04 | 平湖市华达塑料制品有限公司 | Multilayer biodegradable foaming buffer film and preparation method thereof |
| CN117334756A (en) * | 2023-11-29 | 2024-01-02 | 宁波长阳科技股份有限公司 | Foaming type gap film for photovoltaic module and preparation method thereof |
| CN117334756B (en) * | 2023-11-29 | 2024-03-29 | 宁波长阳科技股份有限公司 | Foaming type gap film for photovoltaic module and preparation method thereof |
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