CN114702919B - Photovoltaic adhesive film and preparation method thereof - Google Patents
Photovoltaic adhesive film and preparation method thereof Download PDFInfo
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- CN114702919B CN114702919B CN202111297930.4A CN202111297930A CN114702919B CN 114702919 B CN114702919 B CN 114702919B CN 202111297930 A CN202111297930 A CN 202111297930A CN 114702919 B CN114702919 B CN 114702919B
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- eva
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- coupling agent
- silane coupling
- foaming
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 282
- 238000005187 foaming Methods 0.000 claims abstract description 99
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 70
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 55
- 238000002156 mixing Methods 0.000 claims description 42
- 239000004611 light stabiliser Substances 0.000 claims description 36
- 239000000155 melt Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000003490 calendering Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 27
- IGWHDMPTQKSDTL-JXOAFFINSA-N TMP Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 16
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 14
- JZEXORLUKMQOFA-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(C)C(CO)(CO)CO JZEXORLUKMQOFA-UHFFFAOYSA-N 0.000 description 13
- 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 description 8
- 229940116351 sebacate Drugs 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 8
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- IXDAOYYROAXYLL-UHFFFAOYSA-N tert-butyl 2-ethylhexoxy carbonate Chemical compound CCCCC(CC)COOC(=O)OC(C)(C)C IXDAOYYROAXYLL-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of photovoltaic modules, belongs to IPC (IPC) classification number of C09J7/00, and particularly relates to a photovoltaic adhesive film and a preparation method thereof. The preparation raw materials of the photovoltaic adhesive film comprise EVA foaming particles, EVA particles B, a cross-linking agent, a crosslinking assistant agent, a coupling agent and EVA particles, and the EVA foaming particles prepared by the preparation method can uniformly and rapidly adsorb the cross-linking agent and the crosslinking assistant agent, so that the production efficiency is improved, and meanwhile, the adhesive film has good mechanical properties and low shrinkage.
Description
Technical Field
The invention relates to the technical field of photovoltaic modules, belongs to IPC (IPC) classification number of C09J7/00, and particularly relates to a photovoltaic adhesive film and a preparation method thereof.
Technical Field
The photovoltaic adhesive film is a hot melt adhesive which mainly plays a role in bonding in a photovoltaic module, EVA is an adhesive film which is used more at present and has good optical performance and electrical performance, but the EVA adhesive film also has the defects of poor hydrolysis and PID (potential induced degradation) resistance effect and has too high shrinkage rate.
In order to increase the PID resistance of the EVA adhesive film, the EVA with the VA content of 20-22% is selected as a main raw material in the patent CN105820764A, and the PID resistance of the adhesive film is increased to a certain extent, but the mechanical property of the prepared EVA adhesive film is poor, and the PID resistance effect and the mechanical property cannot be well balanced.
Disclosure of Invention
In order to solve the technical problem, the first aspect of the invention provides a photovoltaic adhesive film, which is prepared from EVA foaming particles, EVA particles B, a cross-linking agent, a co-cross-linking agent, a coupling agent and EVA particles.
Preferably, the preparation raw materials of the photovoltaic adhesive film comprise 8-20% of EVA foaming particles, 5-15% of EVA particles B, 0.5-2% of cross-linking agent, 0.2-0.8% of auxiliary cross-linking agent, 0.05-0.3% of coupling agent and 100% of EVA particles according to mass fraction.
Further preferably, the preparation raw materials of the photovoltaic adhesive film comprise, by mass, 11-16% of EVA foaming particles, 10-14% of EVA particles B, 0.8-1% of cross-linking agent, 0.3-0.45% of auxiliary cross-linking agent, 0.1-0.18% of coupling agent and 100% of EVA particles.
Still more preferably, the raw materials for preparing the photovoltaic film comprise, by mass, 12.5% of EVA foaming particles, 12% of EVA particles B, 0.9% of cross-linking agent, 0.37% of auxiliary cross-linking agent, 0.15% of coupling agent and 100% of EVA particles.
The EVA foaming particles are prepared from EVA particles A through physical foaming or chemical foaming.
Preferably, the EVA foaming particle is prepared from EVA particles A through physical foaming.
Experiments show that the adhesive film prepared by adopting physical foaming in the invention has better flatness compared with the adhesive film prepared by adopting chemical foaming, probably because the foam holes of EVA foaming particles formed by physical foaming are smaller and uniform, and the flatness of the adhesive film in use can be improved.
In the prior art, the crosslinking degree of the EVA adhesive film is lower, so that the mechanical property of the product is lower, the crosslinking agent and the auxiliary crosslinking agent can be well adsorbed through the porous structure in the EVA foaming particles in the EVA adhesive film, then the EVA foaming particles and the EVA master batches B, EVA particles can be heated to generate crosslinking reaction under the action of the coupling agent to form, and components such as the crosslinking agent and the like can be fully adsorbed during mixing, so that the adsorption speed is effectively accelerated, and the efficiency is improved. The inventor finds that the addition amount of the EVA foaming particles in the system is not as large as possible, and the addition amount of the EVA foaming particles is likely to cause defects in the product as the addition amount of the EVA foaming particles is increased, so that the mechanical property of the product is reduced, the tensile property of the product can be better increased by adding a specific amount of the EVA foaming particles in the system, and the addition of the weight part of the EVA foaming particles can play a supporting and reinforcing role in the system, so that the system can be crosslinked well.
The mass percentage of VA in the EVA particles A is 12-30%; preferably, the mass percentage of VA in the EVA particles A is 20-28%; further preferably, the EVA particles A have a VA content of 22% by mass.
The melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 1.5-3 g/min; preferably, the EVA particles A have a melt index of 2g/min at 190℃and 2.16 kg.
In some embodiments EVA particle A is sold under the trade designation HANWHA EVA 1317.
In the prior art, in order to increase the elasticity and flexibility of the adhesive film, the mass percentage of VA is always EVA particles with the mass percentage of more than 28% when the EVA adhesive film is prepared, but the applicant finds that the flexibility of the adhesive film is not only reduced when the EVA particles A are used, but also has good PID resistance when the EVA particles A are especially used, and the number of ions generated by dissociation is probably less at the moment, so that the current carriers in the adhesive film are reduced, the volume resistivity of the adhesive film is increased, the phenomena of leakage and the like are better relieved when the volume resistivity is increased, and the PID resistance of the adhesive film is better increased. Meanwhile, the EVA particles A are prepared into EVA foaming particles through a specific process, so that the EVA foaming particles have good toughness, and the toughness of the adhesive film is improved.
Wherein the physical foaming is supercritical CO 2 The preparation steps of the EVA foaming particles comprise: EVA particles A are added into a single screw extruder to be melted, and simultaneously CO is injected into the single screw extruder 2 And (3) extruding the supercritical fluid to obtain EVA foaming particles.
Using supercritical CO 2 Continuously foaming, and obtaining the foaming particles with controllable structures through controlling the foaming process.
Preferably, the preparation steps of the EVA foaming particle comprise: the temperature of each section of the single screw extruder is regulated to 70-90 ℃ for preheating, after the preheating temperature is reached, the temperature of each section of the machine barrel is set to 75-95 ℃, the temperature of 78-98 ℃ and the temperature of the die head is set to 75-95 ℃, EVA particles A are added into the single screw extruder for melting, and simultaneously CO is injected into the machine barrel of the second section 2 And (3) extruding the supercritical fluid to obtain EVA foaming particles.
Further preferably, the preparation steps of the EVA foam particles include: the temperature of each section of the single screw extruder is regulated to 75-85 ℃, preheating is carried out, after the preheating temperature is reached, the temperature of each section of the machine barrel is set to 82-88 ℃, 85-93 ℃ and the temperature of a die head are set to 82-88 ℃, EVA particles A are added into the single screw extruder for melting, and simultaneously CO is injected into the machine barrel of the second section 2 And (3) extruding the supercritical fluid to obtain EVA foaming particles.
Still more preferably, the preparation step of the EVA foam particles includes: the temperature of each section of the single screw extruder is regulated to 80 ℃ for preheating,after the preheating temperature is reached, the temperature of each section of the machine barrel is set to be 85 ℃, 90 ℃ and 85 ℃ and the temperature of a die head is set to be 85 ℃, EVA particles A are added into a single screw extruder to be melted, and simultaneously CO is injected into the machine barrel of the second section 2 And (3) extruding the supercritical fluid to obtain EVA foaming particles.
The average particle diameter of the EVA particles A is 2-7 mm; preferably, the EVA particles A have an average particle diameter of 3-5 mm; still more preferably, the EVA particles A have an average particle diameter of 4mm.
The water content of the EVA particles A is 0.5-1.5 wt%; preferably, the water content of the EVA particles A is 0.8-1.2 wt%; further preferably, the EVA particles A have a water content of 1wt%.
The control method of the water content of the EVA particles A comprises the following steps: if the water content of the purchased EVA particles A is lower than the required water content, water can be added to mix with the EVA particles A to increase the water content to the required water content; if the water content of the EVA particles A obtained by purchase is higher than the required water content, the water content of the EVA particles A can be controlled by adopting a conventional drying method, and the control method of the water content of the EVA particles A is a conventional method in the field and is not described in detail.
The average grain diameter of the EVA foaming particles is 0.4-1 cm; preferably, the EVA foaming particles have an average particle size of 0.5-0.8 cm; further preferably, the EVA foam particles have an average particle diameter of 0.6cm.
In the prior art, some particles are often dried and then foamed, but in the system of the invention, if the EVA particles A are dried and then foamed, bridging phenomenon easily occurs in the process of preparing the adhesive film, so that the adhesive film cannot be well formed, and the applicant finds that when the water content of the EVA particles A is controlled to be 0.8-1.2 and wwt%, the particle size of the EVA foamed particles can be well controlled, so that the subsequent processing performance of production is not affected, and probably because the expansion rate of the EVA particles A is reduced to a certain extent due to the existence of water.
Wherein the rotating speed of the single screw extruder is 30-50 r/min; preferably, the rotational speed of the single screw extruder is 40r/min.
CO 2 The air injection amount of the supercritical fluid is 0.005-0.01 mL/min; preferably, CO 2 The air injection amount of the supercritical fluid is 0.006-0.009 mL/min; further preferably, CO 2 The gas injection amount of the supercritical fluid was 0.008mL/min.
In the prior art, the existence of water possibly degrades EVA particles A so as to influence the mechanical property of the adhesive film, but the applicant finds that the adhesive film still has better tensile strength in the system of the invention in experiments, and the experimental regulation and control finds that the adhesive film is likely to be beneficial to CO in the presence of trace water 2 Can effectively increase the porosity of the running holes when the gas injection amount in the system is 0.006-0.009 mL/min, and simultaneously, the CO is injected into the barrel of the second section in the system 2 Supercritical fluid, at which time EVA particles A have softened or melted such that CO 2 The EVA foaming particle can be better uniformly diffused in the system, the nucleation rate of the foam holes is increased during the gas injection, the void ratio of the EVA foaming particles can be better increased, and the CO is generated when the rotating speed of the single screw extruder is 30-50 r/min 2 The EVA foaming particles can better control the shrinkage rate of the adhesive film, and the prepared adhesive film can bear the tensile strength of energy consumption when being stretched, and can be uniformly crosslinked better when being laminated, so that the adhesive film is smoother.
The coupling agent is a silane coupling agent; the silane coupling agent is at least one selected from silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172, silane coupling agent A-1100, silane coupling agent A-187, silane coupling agent A-174, silane coupling agent A-1120, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent KH-792, silane coupling agent HR-63, silane coupling agent HR-64, silane coupling agent HR-65 and silane coupling agent KBM-602.
Preferably, the silane coupling agent is a silane coupling agent KH-570.
According to the invention, a specific KH-570 is selected, so that the adhesive film has good hydrophobic performance, the inventor finds that the adhesive film can be better increased in overall performance and peel strength between the adhesive film and glass by adding the coupling agent in specific time through repeated experiments, the possible silane coupling agent KH-570 can be adsorbed into cells on one hand, EVA foaming particles can be better coated on the other hand, a capsule-shaped liquid structure is formed, meanwhile, unsaturated double bonds contained in the KH-570 are subjected to grafting reaction with EVA molecular chains, so that polar side chains of EVA molecules can be formed, and the connection strength of the EVA molecules can be increased through covalent bonding with the glass or the substrate surface in the lamination process.
The VA of the EVA particles B accounts for 25-33% by mass; preferably, the VA content of the EVA particles B is 27 to 29% by mass.
The melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 15-35 g/min; preferably, the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 22-29 g/min; further preferably, the EVA particles B have a melt index of 25g/min at 190℃and 2.16 kg.
In some embodiments, EVA particle B is sold under the trademark28-25。
The VA of the EVA particles accounts for 25-33% by mass; preferably, the VA content of the EVA particles is 28% by mass.
The melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 3-10 g/min; preferably, the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 5-6 g/min; further preferably, the EVA particles have a melt index of 6g/min at 190℃and 2.16 kg.
In some embodiments, the EVA particles are sold under the brand name Braskem EVA HM728F.
Meanwhile, the EVA particles B with specific melt index and the EVA foaming particles are selected to be in synergistic effect with each other in the system, so that the adhesive strength of the adhesive film can be further improved, probably because the adhesive film has better wettability when the melt index is 22-29 g/min, the adhesive film can be better uniformly coated with the light stabilizer and the antioxidant, the spreadability of the adhesive film in the laminating process is improved, and under the action of the EVA particles with the melt index of 5-6 g/min and the EVA foaming master batch, the cohesive strength and the flowability can be better balanced, and the contact area of the adhesive film and the substrate can be increased, and meanwhile, the better strength can be kept.
In order to further increase the light stability and heat stability of the film, in some embodiments, the photovoltaic film is prepared from a raw material further comprising 0.1 to 0.15wt% of a light stabilizer and 0.1 to 0.15wt% of an antioxidant.
The light stabilizer is hindered amine light stabilizer and/or diphenyl ketone light stabilizer; preferably, the light stabilizer is a hindered amine light stabilizer; as the hindered amine light stabilizer, there may be mentioned poly (4-hydroxy-2, 6-tetramethyl-1-piperidylethanol) succinate poly { [6- [ (1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4-bis [ (2, 6), -tetramethyl-piperidinyl) imino ] -1, 6-hexamethylenediyl [ (2, 6-tetramethyl-4-piperidinyl) imino ] }, poly (4-hydroxy-2, 6-tetramethyl-1-piperidylethanol) succinate or bis (1-octyloxy-2, 6-tetramethyl-4-piperidyl) sebacate, and the like. The hindered amine light stabilizer used in the invention is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770.
The antioxidant is at least one selected from antioxidant BHT, antioxidant 168, antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant 1222, antioxidant 1035 and antioxidant 168; antioxidant 1076 is preferred.
The cross-linking agent is selected from one of tert-butyl peroxycarbonate-2-ethylhexyl ester (TBEC), dicumyl peroxide (DCP) and 2, 5-di-tert-butyl peroxy2, 5-methyl hexane (DHBP); preferably, the cross-linking agent is TBEC.
The co-crosslinking agent comprises a monomer containing two or three identical polymerizable groups; the polymerizable group comprises one of allyl, acrylate and methacrylate; mention may be made of the polymerizable compoundsAmong the monomers having a group are triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA), and the like, preferably TAIC and TMP (EO) 3 Combination of TAs.
The TAIC and TMP (EO) 3 TA is (1-5): (0.8-3); preferably, the TAIC is combined with TMP (EO) 3 TA is (2-3): (1-1.5); further preferably, the TAIC is combined with TMP (EO) 3 TA weight ratio of 2.5:1.2.
in order to increase the ageing resistance of the system, antioxidants and light stabilizers are added into the adhesive film, but the antioxidants and the light stabilizers capture free radicals generated by the crosslinking agent, so that the reduction of the utilization rate of the crosslinking agent can inhibit the action of the crosslinking agent in the adhesive film, and in the invention, the specific TMP (EO )3 The synergistic effect of TA, TAIC and a cross-linking agent can better increase the cross-linking of the system, and on the other hand, the mechanical property of the adhesive film can be further increased through the EVA foaming particles prepared.
Applicants have unexpectedly found that TAIC and TMP (EO) are selected for use in the present system 3 TA also increases film shrinkage and film flatness during lamination, probably because the longer molecular chains of triallyl isocyanurate and 3 (ethoxy) trimethylolpropane triacrylate reduce film torque during crosslinking, improve flexibility, and also probably because 3 (ethoxy) trimethylolpropane triacrylate can slightly reduce the average molecular weight between EVA crosslinking points, making the system more flexible, but applicants have found that in the present system it is not 3 (ethoxy) trimethylolpropane triacrylate that is more preferable, when 3 (ethoxy) trimethylolpropane triacrylate is too much, it can have some effect on film tensile strength, probably because a specific amount of 3 (ethoxy) trimethylolpropane triacrylate can increase EVA chemical crosslinking density, so that tensile strength increases, but when 3 (ethoxy) trimethylolpropane triacrylate is too much, it can increase EVA physical crosslinking density, and when the adhesive is too much, it can increase EVA physical crosslinking densityThe physical crosslink density is easily compromised when the film is subjected to tensile stress.
The second aspect of the invention provides a preparation method of a photovoltaic adhesive film, which comprises the following steps:
(1) Mixing EVA foaming particles with a cross-linking agent and a secondary cross-linking agent in a mixer for 0.8-1.2 h, adding a coupling agent, and mixing for 0.8-1.2 h to obtain EVA master batch A for later use;
(2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 30-50 min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use;
(3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture;
(4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a film to obtain the photovoltaic film.
The rotating speed of the mixer during mixing in the step (1) is 120-200 r/min; preferably, the rotating speed of the mixer during mixing in the step (1) is 150-180 r/min; it is further preferable that the rotational speed of the mixer at the time of mixing in the step (1) is 160r/min.
In the step (2), the stirring speed is 500-600 r/min.
The barrel temperature during extrusion in step (4) was 80-90 ℃.
Wherein, calendaring into a film is a conventional process in the art, and the description is not repeated here.
The thickness of the photovoltaic adhesive film is 0.1-1.5mm.
The third aspect of the invention provides application of a photovoltaic adhesive film, wherein the photovoltaic adhesive film is used for an upper adhesive film in a photovoltaic module.
The beneficial effects are that:
1. compared with the prior art, the EVA foaming particle prepared by the method has better adsorptivity to the crosslinking agent and the auxiliary crosslinking agent, can shorten the adsorption time of EVA and crosslinking auxiliary agents in a system, improves the production rate, and simultaneously selects the specific EVA particle A to prepare the EVA foaming particle, and better relieves the phenomena of electric leakage and the like by increasing the volume resistivity of the adhesive film, so that the PID resistance of the adhesive film is improved;
2. according to the invention, the EVA foaming particles can play a supporting and reinforcing role in the system by controlling the preparation process conditions of the EVA foaming particles, and uniform micro-cells can be formed by controlling the foaming process, so that the cross-linking agent and the auxiliary cross-linking agent can be more uniformly dispersed in the system, the phenomenon of fish eyes of the adhesive film in the lamination process is reduced, and meanwhile, the system can be crosslinked better, and the tensile strength of the adhesive film is increased;
3. according to the invention, the EVA foaming particles uniformly adsorb the specific cross-linking agent and the auxiliary cross-linking agent, and the selection of the specific adsorbent is combined, so that the chemical cross-linking of the cross-linking system is increased, the physical cross-linking of the system is reduced, the torque of the adhesive film is reduced, the flexibility is improved, and the adhesive film has good flatness.
Detailed Description
Example 1
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 11-16% of EVA foaming particles, 10% of EVA particles B, 0.8% of cross-linking agent, 0.3% of auxiliary cross-linking agent, 0.1% of coupling agent, 0.1% of light stabilizer, 0.1% of antioxidant and 100% of EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming; the mass percentage of VA in the EVA particles A is 22%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 2g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A sold under the trade name HANWHA EVA 1317; physical foaming to supercritical CO 2 The preparation steps of the EVA foaming particles comprise: the temperature of each section of the single screw extruder is regulated to 75 ℃ for preheating, after the preheating temperature is reached, the temperature of each section of the machine barrel is set to 82 ℃, 85 ℃, the temperature of a die head is set to 82 ℃, EVA particles A are added into the single screw extruder for melting, and simultaneously CO is injected into the machine barrel of the second section 2 Extruding supercritical fluid to obtain EVA foaming particles; the water content of the EVA particles A is 0.8wt%; the average particle size of the EVA foaming particles is 0.8cm; the rotation speed of the single screw extruder is30r/min; preferably; CO 2 The air injection amount of the supercritical fluid is 0.006mL/min;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 27% in mass percent; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 The weight ratio of TA is 2:1, a step of;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA foaming particles with a cross-linking agent and a co-cross-linking agent in a mixer for 0.8h, adding the coupling agent, and mixing for 0.8h to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 30min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a film to obtain the photovoltaic film.
The rotating speed of the mixer during mixing in the step (1) is 150r/min; in the step (2), the stirring speed is 500r/min; in the extrusion in the step (4), the temperature of the machine barrel is 80 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Example 2
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 12.5% of EVA foaming particles, 12% of EVA particles B, 0.9% of cross-linking agent, 0.37% of auxiliary cross-linking agent, 0.15% of coupling agent, 0.12% of light stabilizer, 0.12% of antioxidant and 100% of EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming; the mass percentage of VA in the EVA particles A is 22%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 2g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A sold under the trade name HANWHA EVA 1317; physical foaming to supercritical CO 2 The preparation steps of the EVA foaming particles comprise: regulating the temperature of each section of a single screw extruder to 80 ℃, preheating, setting the temperature of each section of a machine barrel to 85 ℃, 90 ℃ and 85 ℃ after the preheating temperature is reached, adding EVA particles A into the single screw extruder to melt through a die head, and simultaneously injecting CO into a machine barrel of a second section 2 Extruding supercritical fluid to obtain EVA foaming particles; the water content of the EVA particles A is 1wt%; the average particle size of the EVA foaming particles is 0.6cm; the rotating speed of the single screw extruder is 40r/min; CO 2 The air injection amount of the supercritical fluid is 0.008mL/min;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 28% in mass percent; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 TA weight ratio of 2.5:1.2;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA foaming particles with a cross-linking agent and a secondary cross-linking agent in a mixer for 1h, adding the coupling agent, and mixing for 1h to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 40min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a glue film to obtain light Fu Jiaomo; the rotating speed of the mixer during mixing in the step (1) is 160r/min; in the step (2), the stirring speed is 550r/min; in the extrusion in the step (4), the temperature of the machine barrel is 85 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Example 3
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 116% of EVA foaming particles, 14% of EVA particles B, 1% of cross-linking agent, 0.45% of auxiliary cross-linking agent, 0.18% of coupling agent, 0.15% of light stabilizer, 0.15% of antioxidant and 100% of EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming; the mass percentage of VA in the EVA particles A is 22%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 2g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A sold under the trade name HANWHA EVA 1317; physical foaming to supercritical CO 2 The preparation steps of the EVA foaming particles comprise: the temperature of each section of the single screw extruder is regulated to 85 ℃ for preheating, and after the preheating temperature is reached, the temperature of each section of the machine barrel is set to 88 ℃, 93℃,The EVA particles A are added into a single screw extruder to be melted at 93 ℃ and 88 ℃ through a die head temperature, and simultaneously CO is injected into a second section of machine barrel 2 Extruding supercritical fluid to obtain EVA foaming particles; the water content of the EVA particles A is 1.2wt%; the average particle size of the EVA foaming particles is 0.5cm; the rotating speed of the single screw extruder is 50r/min; CO 2 The air injection amount of the supercritical fluid is 0.009mL/min;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 29% by mass; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 TA weight ratio is 3:1.5;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA foaming particles with a cross-linking agent and a co-cross-linking agent in a mixer for 1.2 hours, adding the coupling agent, and mixing for 1.2 hours to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 50min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a glue film to obtain light Fu Jiaomo; the rotating speed of the mixer during mixing in the step (1) is 180r/min; in the step (2), the stirring speed is 600r/min; in the extrusion in the step (4), the temperature of the machine barrel is 90 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Example 4
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 12.5% of EVA foaming particles, 12% of EVA particles B, 0.9% of cross-linking agent, 0.37% of auxiliary cross-linking agent, 0.15% of coupling agent, 0.12% of light stabilizer, 0.12% of antioxidant and 100% of EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming; the mass percentage of VA in the EVA particles A is 40%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 50g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A with a sales number of40-55; physical foaming to supercritical CO 2 The preparation steps of the EVA foaming particles comprise: regulating the temperature of each section of a single screw extruder to 80 ℃, preheating, setting the temperature of each section of a machine barrel to 85 ℃, 90 ℃ and 85 ℃ after the preheating temperature is reached, adding EVA particles A into the single screw extruder to melt through a die head, and simultaneously injecting CO into a machine barrel of a second section 2 Extruding supercritical fluid to obtain EVA foaming particles; the water content of the EVA particles A is 1wt%; the average particle size of the EVA foaming particles is 0.6cm; the rotating speed of the single screw extruder is 40r/min; CO 2 The air injection amount of the supercritical fluid is 0.008mL/min;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 28% in mass percent; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 TA weight ratio of 2.5:1.2;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA foaming particles with a cross-linking agent and a secondary cross-linking agent in a mixer for 1h, adding the coupling agent, and mixing for 1h to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 40min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a glue film to obtain light Fu Jiaomo; the rotating speed of the mixer during mixing in the step (1) is 160r/min; in the step (2), the stirring speed is 550r/min; in the extrusion in the step (4), the temperature of the machine barrel is 85 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Example 5
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 12.5% of EVA foaming particles, 12% of EVA particles B, 0.9% of cross-linking agent, 0.37% of auxiliary cross-linking agent, 0.15% of coupling agent, 0.12% of light stabilizer, 0.12% of antioxidant and 100% of EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming; the mass percentage of VA in the EVA particles A is 22%; the EVA particles AThe melt index at 190℃and 2.16kg was 2g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A sold under the trade name HANWHA EVA 1317; physical foaming to supercritical CO 2 The preparation steps of the EVA foaming particles comprise: regulating the temperature of each section of a single screw extruder to 80 ℃, preheating, setting the temperature of each section of a machine barrel to 85 ℃, 90 ℃ and 85 ℃ after the preheating temperature is reached, adding EVA particles A into the single screw extruder to melt through a die head, and simultaneously injecting CO into a machine barrel of a second section 2 Extruding supercritical fluid to obtain EVA foaming particles; the water content of the EVA particles A is 1wt%; the average particle size of the EVA foaming particles is 0.6cm; the rotating speed of the single screw extruder is 10r/min; CO 2 The air injection amount of the supercritical fluid is 0.004mL/min;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 28% in mass percent; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 TA weight ratio of 2.5:5, a step of;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA foaming particles with a cross-linking agent and a secondary cross-linking agent in a mixer for 1h, adding the coupling agent, and mixing for 1h to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 40min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a glue film to obtain light Fu Jiaomo; the rotating speed of the mixer during mixing in the step (1) is 160r/min; in the step (2), the stirring speed is 550r/min; in the extrusion in the step (4), the temperature of the machine barrel is 85 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Example 6
The preparation raw materials of the photovoltaic adhesive film comprise, by mass, 12.5% of EVA particles A, 12% of EVA particles B, 0.9% of cross-linking agent, 0.37% of auxiliary cross-linking agent, 0.15% of coupling agent, 0.12% of light stabilizer, 0.12% of antioxidant and 100% of EVA particles;
the mass percentage of VA in the EVA particles A is 22%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 2g/min; the average particle diameter of the EVA particles A is 4mm; EVA particle A sold under the trade name HANWHA EVA 1317;
the coupling agent is a silane coupling agent; the silane coupling agent is a silane coupling agent KH-570;
the VA of the EVA particles B is 28% in mass percent; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 25g/min; EVA particle B with a sales number of28-25；
The VA of the EVA particles is 28% in mass percent; the melt index of the EVA particles under the conditions of 190 ℃ and 2.16kg is 6g/min; the EVA particles are sold under the brand name of Braskem EVA HM728F;
the light stabilizer is a hindered amine light stabilizer; the hindered amine light stabilizer is bis (2, 6-tetramethyl-4-piperidyl) sebacate, and the sold trademark Tinuvin770;
the antioxidant is antioxidant 1076;
the cross-linking agent is tert-butyl peroxy-2-ethyl hexyl carbonate (TBEC);
the auxiliary crosslinking agent is triallyl isocyanurate (TAIC) and 3 (ethoxy) trimethylolpropane triacrylate (TMP (EO) 3 TA); the TAIC and TMP (EO) 3 TA weight ratio of 2.5:1.2;
the preparation method of the photovoltaic adhesive film comprises the following steps: (1) Mixing EVA particles A with a cross-linking agent and a co-cross-linking agent in a mixer for 3 hours, adding the coupling agent, and mixing for 3 hours to obtain EVA master batch A for later use; (2) Stirring and mixing the residual raw materials except the EVA particles of the EVA particles B for 40min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use; (3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture; (4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a glue film to obtain light Fu Jiaomo; the rotating speed of the mixer during mixing in the step (1) is 160r/min; in the step (2), the stirring speed is 550r/min; in the extrusion in the step (4), the temperature of the machine barrel is 85 ℃; the thickness of the photovoltaic adhesive film is 0.5mm.
Performance testing
Performance testing was performed on the photovoltaic film in the examples:
test of peel strength, shrinkage, volume resistivity, tensile Strength of photovoltaic films in examples 1 to 6: testing was performed according to GB/T29848-2018 (at 140℃and 0.08MPa for 10min for lamination);
light Fu Jiaomo PID 96h decay rate test in examples 1 to 6: the photovoltaic adhesive films in examples 1 to 6 were used for packaging the same batch and model of battery pieces, and DIN IEC/TS 62804-1-2017 (temperature 85.+ -. 2 ℃ C., humidity 85.+ -. 5% and test 1000 hours) was used.
The test results are shown in table 1:
TABLE 1
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Claims (5)
1. The photovoltaic adhesive film is characterized in that the preparation raw materials comprise EVA foaming particles, EVA particles B, a cross-linking agent, a co-cross-linking agent, a coupling agent and EVA particles;
the EVA foaming particles are prepared from EVA particles A through physical foaming;
the physical foaming is supercritical CO2 continuous foaming;
the preparation method of the EVA foaming particle comprises the following steps: regulating the temperature of each section of the single screw extruder to 70-90 ℃, preheating, setting the temperature of each section of the machine barrel to 75-95 ℃, setting the temperature of each section of the machine barrel to 78-98 ℃ and the temperature of each section of the machine barrel to 78-98 ℃ through a die head to 75-95 ℃, adding EVA particles A into the single screw extruder for melting, simultaneously injecting CO2 supercritical fluid into the machine barrel of the second section, and extruding to obtain EVA foaming particles;
the rotating speed of the single screw extruder is 30-50 r/min;
the gas injection amount of the CO2 supercritical fluid is 0.005-0.01 mL/min;
the preparation raw materials of the photovoltaic adhesive film comprise 8-20% of EVA foaming particles, 5-15% of EVA particles B, 0.5-2% of cross-linking agent, 0.2-0.8% of auxiliary cross-linking agent, 0.05-0.3% of coupling agent and 100% of EVA particles by mass fraction;
the mass percentage content of VA in the EVA particles A is 12-30%; the melt index of the EVA particles A under the conditions of 190 ℃ and 2.16kg is 1.5-3 g/min;
the water content of the EVA particles A is 0.8-1.2 wt%;
the VA of the EVA particles B accounts for 25-33% by mass; the melt index of the EVA particles B under the conditions of 190 ℃ and 2.16kg is 15-35 g/min.
2. The photovoltaic film according to claim 1, wherein the EVA foam particles have an average particle size of 0.5-0.8 cm.
3. The photovoltaic film of claim 1, wherein the coupling agent is a silane coupling agent; the silane coupling agent is at least one selected from silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172, silane coupling agent A-1100, silane coupling agent A-187, silane coupling agent A-174, silane coupling agent A-1120, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, silane coupling agent KH-792, silane coupling agent HR-63, silane coupling agent HR-64, silane coupling agent HR-65 and silane coupling agent KBM-602.
4. The photovoltaic film according to claim 1, wherein the photovoltaic film is prepared from the raw materials comprising 0.1-0.15 wt% of light stabilizer and 0.1-0.15 wt% of antioxidant.
5. A method of producing a photovoltaic film according to any one of claims 1 to 4, comprising the steps of:
(1) Mixing EVA foaming particles with a cross-linking agent and a secondary cross-linking agent in a mixer for 0.8-1.2 h, adding a coupling agent, and mixing for 0.8-1.2 h to obtain EVA master batch A for later use;
(2) Stirring and mixing the EVA particles B with the rest raw materials except the EVA particles for 30-50 min to obtain a mixed material B, and extruding the mixed material B through a double-screw extruder to obtain EVA master batch B for later use;
(3) Uniformly mixing EVA master batches A, EVA master batches B, EVA particles by a mixer to obtain a mixture;
(4) Extruding the mixture obtained in the step (3) through an extruder, and calendaring into a film to obtain the photovoltaic film.
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