CN114806460A - Low-acid type white EVA photovoltaic packaging adhesive film and preparation method thereof - Google Patents
Low-acid type white EVA photovoltaic packaging adhesive film and preparation method thereof Download PDFInfo
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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
- 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
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- 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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- 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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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- 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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- C08L2203/00—Applications
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- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- 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
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Abstract
The invention belongs to the technical field of photovoltaic modules, and particularly relates to a low-acid type white EVA photovoltaic packaging adhesive film and a preparation method thereof, wherein the preparation method comprises the following steps: 100 parts of EVA resin, 5-10 parts of titanium dioxide, 1-5 parts of composite acid inhibitor, 0.5-1.0 part of peroxide crosslinking agent, 0.3-1.0 part of auxiliary crosslinking agent, 0.2-0.6 part of coupling agent, 0.1-0.5 part of antioxidant and 0-0.5 part of ultraviolet absorbent, wherein the composite acid inhibitor comprises amphiphilic polymer, alkali metal compound, carbodiimide compound and macromolecular coupling agent, and is prepared by mixing and granulating according to a proportion. According to the low-acid white EVA photovoltaic packaging adhesive film, the composite acid inhibitor is added, so that the power loss of the assembly caused by water vapor erosion can be solved, free acetic acid generated in the long-term aging process of EVA can be effectively neutralized, the corrosion of the packaging adhesive film to a battery piece, a bus bar and a metal frame can be effectively relieved, and the service life of the assembly can be prolonged.
Description
Technical Field
The invention belongs to the technical field of photovoltaic modules, and particularly relates to a low-acid type white EVA photovoltaic packaging adhesive film and a preparation method thereof.
Background
The white high-reflection packaging adhesive film is one of packaging materials commonly used for photovoltaic modules, and has higher light utilization efficiency, so the white high-reflection packaging adhesive film always has higher proportion in the technical field of photovoltaic packaging. Compared with POE, EVA resin has better compatibility with white filler, the dispersion of inorganic filler is more uniform, and the advantages of easy irradiation pre-crosslinking, faster lamination curing rate and the like are achieved, and the phenomena of flanging, white overflow and the like are almost avoided, so that the EVA resin is widely applied to the industrial production of white adhesive films. However, the EVA resin containing a large amount of vinyl acetate comonomer has a high polarity, which also causes a high water vapor transmission rate, and is very susceptible to the influence of environmental factors such as light, heat, water, etc. to cause hydrolysis reaction as follows:
the generated free acetic acid not only aggravates the aging of the adhesive film and promotes the PID attenuation of the assembly caused by ion transmission, but also corrodes the grid lines, bus bars and the like of the battery, and the service life of the assembly is greatly reduced.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a low-acid type white EVA photovoltaic packaging adhesive film.
In order to achieve the purpose, the enhanced composite acid inhibitor provided by the invention is prepared by mixing an amphiphilic polymer, an alkaline metal compound, a carbodiimide compound, a macromolecular coupling agent and the like according to a certain proportion and carrying out twin-screw granulation, and a glue film prepared from the enhanced composite acid inhibitor has the advantages of excellent hydrolysis resistance, low acid content, aging resistance, PID resistance and the like.
On one hand, the carbodiimide compound can react with moisture contained in the adhesive film, moisture decomposed by peroxide and moisture invaded from the edge in the aging process of the assembly, the hydrolysis of vinyl acetate in EVA is inhibited from the source, urea substances which have little influence on the performance of the adhesive film are generated, and the reaction formula of water generated by the decomposition of the peroxide and imine and water is as follows:
on the other hand, free acid generated in the aging process or acid invading in the environment can also react with the added alkaline metal compound, so that the content of the free acid generated in the long-term aging process of the adhesive film is further reduced, the corrosion to grid lines, bus bars and the like of the battery piece is avoided, the service life of the assembly is prolonged, and the reaction formula of the alkaline metal compound and acetic acid is as follows:
most importantly, the enhanced compound acid inhibitor provided by the invention, carbodiimide and an alkaline metal compound can play a good synergistic effect. The carbodiimide can not only well absorb the moisture in the adhesive film and the moisture generated by peroxide, but also effectively absorb the moisture generated by the reaction of free acetic acid and an alkaline metal compound, thereby playing the roles of reducing and inhibiting the hydrolysis of EVA; meanwhile, free acetic acid generated by hydrolysis can be consumed by alkaline metal oxide in time, so that the content of acid is reduced, and the power loss of the component caused by corrosion is avoided.
In addition, in order to realize the synergistic effect, the amphiphilic polymer is used as a carrier, the carbodiimide and the alkali metal compound are well compounded by utilizing the macromolecular silane coupling agent, and the water absorption property of the silane is skillfully utilized, so that the enhanced composite acid inhibitor can better capture the moisture in the adhesive film, and the hydrolysis resistance of the adhesive film is greatly improved.
The preparation of the composite acid inhibitor is carried out by adopting a double-screw granulation mode, and the temperature is 70-120 ℃; wherein the amphiphilic polymer, the alkaline metal compound, the carbodiimide compound and the macromolecular coupling agent are respectively 1: 0.02-0.1: 0.01-0.05: 0.02 to 0.06, preferably 1: 0.05-0.1: 0.02-0.04: 0.04-0.06.
The amphiphilic polymer includes, but is not limited to, one or more of ethylene-vinyl acetate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-methacrylate copolymer, and ethylene-acrylate-glycidyl methacrylate terpolymer.
Furthermore, in order to ensure the compatibility with the matrix resin, the ethylene-vinyl acetate binary copolymer is preferred, the VA content is 20-30%, the melt flow rate is 2-30g/10min, and the melting point is 55-110 ℃.
Furthermore, the ethylene-vinyl acetate binary copolymer has the preferable VA content of 25-30%, the melt flow rate of 15-30g/10min and the melting point of 65-90 ℃.
The basic metal compound includes, but is not limited to, one or more of magnesium hydroxide, aluminum hydroxide, zinc oxide, zinc stearate, basic magnesium carbonate, basic aluminum carbonate, and zirconium hydrogen phosphate.
Further, in order to prevent the influence of the addition of the alkali metal compound on the reflectance and the volume resistivity and the defects such as decomposition and bubbles due to high-temperature lamination, it is preferable that the purity be 99.9% or more, for example, high-temperature magnesium hydroxide or indirect zinc oxide.
The carbodiimide-based compound includes, but is not limited to, one or more of N, N ' -bis (2, 6-diisopropylphenyl) carbodiimide, dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N ' -diisohexylcarbodiimide, 1, 3-bis (2, 2-dimethyl-1, 3-dioxolan-4-ylmethyl) carbodiimide, poly (2, 6-diisopropylphenyl) carbodiimide, and di-t-butylcarbodiimide.
Further, in order to prevent a defect such as yellowing due to aging of the imine, the carbodiimide-based compound is preferably one or two of non-aromatic imines N, N '-diisopropylcarbodiimide, N' -diisohexylcarbodiimide, 1, 3-bis (2, 2-dimethyl-1, 3-dioxolan-4-ylmethyl) carbodiimide and di-t-butylcarbodiimide.
The macromolecular coupling agent is prepared by carrying out free radical polymerization on vinyl acetate and styrene serving as main monomers and gamma-methacryloxypropyltrimethoxysilane serving as a functional monomer.
Further, in order to ensure the compatibility and dispersibility of the inorganic filler, the polymer and the polar monomer in the composite acid inhibitor, the proportion of the functional monomer in the macromolecular coupling agent is 1-10%, preferably 4-6%.
In the invention, the low-acid white EVA photovoltaic packaging adhesive film prepared from the enhanced composite acid inhibitor comprises the following components in parts by weight: 100 parts of vinyl acetate-vinyl acetate copolymer (EVA), 5-10 parts of titanium dioxide, 1-5 parts of composite acid inhibitor, 0.5-1.0 part of peroxide crosslinking agent, 0.3-1.0 part of auxiliary crosslinking agent, 0.2-0.6 part of coupling agent, 0.1-0.5 part of antioxidant and 0-0.5 part of ultraviolet absorbent.
The ethylene-vinyl acetate binary copolymer is commercial photovoltaic EVA resin, the VA content is 28-30%, and the melt flow rate is 20-28g/10 min.
The titanium dioxide is selected from high rutile TiO sold in the market 2 The particle size range is 100-500nm, and the purity is more than 99%.
The peroxide crosslinking agent is selected from one or a mixture of more of the following components: tert-butyl peroxy-2-ethylhexyl carbonate, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxy-neodecanoic acid and benzoyl peroxide.
The auxiliary crosslinking agent is selected from one or a mixture of more than two of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and the like.
The coupling agent is one or a mixture of more than two of gamma-methacryloxypropyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, vinyl-tri (2-methoxyethoxy) silane, vinyl triacetoxysilane and the like.
The antioxidant is selected from one or a mixture of more than two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 4- [ (4, 6-dioctylthio-1, 3, 5-triazin-2-yl) amino ] -2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tris (2, 4-di-tert-butyl) phenyl phosphite, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionylhydrazine and the like.
The ultraviolet absorbent is selected from one or a mixture of more than two of 4-methoxy-2-hydroxybenzophenone, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-dodecyloxy benzophenone, phenyl salicylate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-benzoyloxy-2, 2,6, 6-tetramethyl piperidine, bis-2, 2,6, 6-tetramethyl piperidine sebacate and the like.
It is worth mentioning that: the low-acid white EVA photovoltaic packaging adhesive film disclosed by the invention can be properly added with other known additives according to the purpose and application under the condition of not influencing the packaging use effect. The additive also comprises whitening agent, sensitizing agent, antistatic agent, flame retardant, antibacterial agent, shrinkage inhibitor, heat stabilizer, light stabilizer, metal deactivator, mildew preventive and tackifier. The above additives may be used alone, or two or more thereof may be used in combination.
The low-acid white EVA photovoltaic packaging adhesive film provided by the invention is prepared by mixing, melting, tape casting, rolling, trimming, rolling and packaging the components in proportion.
Specifically, the preparation method of the low-acid type white EVA photovoltaic packaging adhesive film comprises the following steps:
step 1: preparing a composite acid inhibitor:
weighing 1 part of amphiphilic polymer, 0.02-0.1 part of alkaline metal compound, 0.01-0.05 part of carbodiimide compound and 0.02-0.06 part of macromolecular coupling agent according to parts by weight, and preparing the composite acid inhibitor by adopting a double-screw granulation mode;
step 2: preparing a low-acid type white EVA photovoltaic packaging adhesive film:
weighing 100 parts of EVA resin, 5-10 parts of titanium dioxide, 1-5 parts of composite acid inhibitor, 0.5-1.0 part of peroxide crosslinking agent, 0.3-1.0 part of auxiliary crosslinking agent, 0.2-0.6 part of coupling agent, 0.1-0.5 part of antioxidant and 0-0.5 part of ultraviolet absorbent according to parts by weight, mixing, putting the mixture into an extruder for mixing and plasticizing, and carrying out embossing shaping, cooling, traction and coiling on the extrudate to obtain the low-acid type white EVA (ethylene-vinyl acetate) photovoltaic packaging adhesive film.
Compared with the prior art, the invention has the beneficial effects that:
compared with the existing white EVA adhesive film, the low-acid type white EVA photovoltaic packaging adhesive film has the advantages of more excellent hydrolysis resistance, lower acid content, higher PID (proportion integration differentiation) resistance and the like, and the reflectivity, yellowing resistance and the like are hardly influenced.
The invention provides a preparation strategy of an enhanced composite acid inhibitor for the first time, and the adopted imine substances not only can well absorb the water in the adhesive film and the water generated by peroxide, but also play a role in reducing and inhibiting the hydrolysis of EVA; meanwhile, free acetic acid generated by hydrolysis can be consumed by alkaline metal oxide in time, so that the content of acid is reduced, and the power loss of the component caused by corrosion is avoided.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a flow chart of a preparation method of a low-acid type white EVA photovoltaic packaging adhesive film of the invention.
Detailed Description
In order to better explain the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments, but those skilled in the art will understand that the following described embodiments are a part of the embodiments of the present invention, rather than the whole embodiments, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
As shown in fig. 1, the flow chart of the preparation method of the low-acid type white EVA photovoltaic encapsulation adhesive film of the invention is shown, and the preparation method of the low-acid type white EVA photovoltaic encapsulation adhesive film of the invention comprises the following steps:
step 1: preparing a composite acid inhibitor:
weighing 1 part of amphiphilic polymer, 0.02-0.1 part of alkaline metal compound, 0.01-0.05 part of carbodiimide compound and 0.02-0.06 part of macromolecular coupling agent according to parts by weight, and preparing the composite acid inhibitor by adopting a double-screw granulation mode;
step 2: preparing a low-acid type white EVA photovoltaic packaging adhesive film:
weighing 100 parts of EVA resin, 5-10 parts of titanium dioxide, 1-5 parts of composite acid inhibitor, 0.5-1.0 part of peroxide crosslinking agent, 0.3-1.0 part of auxiliary crosslinking agent, 0.2-0.6 part of coupling agent, 0.1-0.5 part of antioxidant and 0-0.5 part of ultraviolet absorbent according to parts by weight, mixing, putting the mixture into an extruder for mixing and plasticizing, and carrying out embossing shaping, cooling, traction and coiling on the extrudate to obtain the low-acid type white EVA (ethylene-vinyl acetate) photovoltaic packaging adhesive film.
Example 1
Preparing a composite acid inhibitor: the preparation is carried out by adopting a double-screw granulation mode, and the temperature range of each temperature zone is 70-120 ℃; wherein the ethylene-vinyl acetate binary copolymer, the magnesium hydroxide, the N, N' -diisopropylcarbodiimide and the macromolecular coupling agent are respectively 1: 0.05: 0.02: 0.04, wherein the content of the functional monomer in the macromolecular coupling agent is 5 percent.
Preparation of low-acid type white EVA adhesive film A1: according to the weight portion, 100 portions of EVA raw material with 28 percent of vinyl acetate content and 25g/10min of melt index value are added with: 7 parts of titanium dioxide, 3 parts of composite acid inhibitor, 0.6 part of tert-butyl peroxy-2-ethylhexyl carbonate, 0.4 part of triallyl isocyanurate, 0.3 part of gamma-methacryloxypropyl trimethoxy silane, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.2 part of 4-methoxy-2-hydroxybenzophenone, mixing for 30min, feeding the mixture into an extruder for mixing and plasticizing, and controlling the temperature of the extruder at 85 ℃. And embossing and shaping, cooling, drawing, coiling and the like to obtain the EVA adhesive film A1 with the thickness of 0.5 mm.
Example 2
Under the same other conditions as in example 1, the amount of N, N '-diisopropylcarbodiimide added was increased by 0.07, that is, the ethylene-vinyl acetate copolymer, magnesium hydroxide, N' -diisopropylcarbodiimide and macromolecular coupling agent were 1: 0.07: 0.02: 0.04, example EVA adhesive film A2 was prepared.
Example 3
The other conditions are the same as the example 2, the N, N ' -diisopropylcarbodiimide is changed to N, N ' -diisohexylcarbodiimide, namely, the ethylene-vinyl acetate binary copolymer, the magnesium hydroxide, the N, N ' -diisohexylcarbodiimide and the macromolecular coupling agent are respectively 1: 0.07: 0.02: 0.04, example EVA adhesive film A3 was prepared.
Example 4
The other conditions are the same as the example 3, the magnesium hydroxide is replaced by indirect zinc oxide, namely, ethylene-vinyl acetate binary copolymer, indirect zinc oxide, N' -diisohexylcarbodiimide and macromolecular coupling agent, and the weight ratio is 1: 0.07: 0.02: 0.04 example EVA film A4 was prepared.
Example 5
The other conditions are the same as the example 4, and the proportion of the N, N '-diisohexylcarbodiimide is increased to 0.04, namely the ethylene-vinyl acetate binary copolymer, the indirect method zinc oxide, the N, N' -diisohexylcarbodiimide and the macromolecular coupling agent are respectively 1: 0.07: 0.04: 0.04, example EVA adhesive film A5 was prepared.
Example 6
Preparing a composite acid inhibitor: the preparation method is the same as example 5.
Preparation of low-acid type white EVA adhesive film A6: according to the weight portion, 100 portions of EVA raw material with 28 percent of vinyl acetate content and 25g/10min of melt index value are added with: 7 parts of titanium dioxide, 3 parts of composite acid inhibitor, 0.6 part of di-tert-butyl peroxide, 0.5 part of triallyl cyanurate, 0.3 part of vinyl triacetoxysilane, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.2 part of 4-methoxy-2-hydroxybenzophenone, mixing for 30min, and then putting the mixture into an extruder for mixing and plasticizing, wherein the temperature of the extruder is controlled at 85 ℃. And embossing and shaping, cooling, drawing, coiling and the like to obtain the EVA adhesive film A6 with the thickness of 0.5 mm.
Example 7
Preparing a composite acid inhibitor: the preparation method is the same as example 5.
Preparation of low-acid type white EVA adhesive film A7: according to the weight portion, 100 portions of EVA raw material with 28 percent of vinyl acetate content and 25g/10min of melt index value are added with: 7 parts of titanium dioxide, 3 parts of a composite acid inhibitor, 0.6 part of di-tert-butyl peroxide, 0.4 part of trimethylolpropane trimethacrylate, 0.3 part of vinyl triacetoxysilane, 0.2 part of 2, 6-di-tert-butyl-p-cresol and 0.2 part of 2, 4-dihydroxy benzophenone, mixing for 30min, feeding the mixture into an extruder, mixing and plasticizing, and controlling the temperature of the extruder at 85 ℃. And embossing and shaping, cooling, drawing, coiling and the like to obtain the EVA adhesive film A7 with the thickness of 0.5 mm.
Comparative example 1
Unlike examples 1-5, the complex acid inhibitor added was removed, wherein examples 1-5 differ in the compounding ratio of the complex acid inhibitor to produce comparative example B1;
comparative example 2
Comparative example B2 was prepared by replacing 3 parts of the complex acid inhibitor in example 1 with 1 part of magnesium hydroxide under the same conditions.
Comparative example 3
Comparative example B3 was prepared by substituting 3 parts of the complex acid inhibitor of example 1 for 0.1 part of N, N' -diisohexylcarbodiimide under the same conditions.
Comprehensive performance evaluation and validation was performed on the above example sample A1-7 and comparative example sample B1-3:
(1) determination of acetic acid content in adhesive film
Sample preparation: respectively cutting 2 EVA adhesive films with specification of 20cm by 20 cm; cutting the back plate and the glass into proper specifications; stacking the glass/EVA/EVA/back plate, and connecting the two EVA pattern surfaces; after lamination, hydrolysis resistant agent containing test samples were obtained.
And (3) testing conditions are as follows: the ten samples are respectively subjected to a damp-heat aging test according to the GB/T2423.3 test method, the temperature is 85 ℃, the relative humidity is 85%, and the time is 1000H.
And (3) testing the content of acetic acid: and (4) taking the glue film in the middle part of the laminating part after the aging is finished, and detecting the content of acetic acid in the aged glue film by adopting a headspace-gas chromatography.
(2) Basic Performance test of adhesive films
1) Measurement of reflectance, degree of crosslinking, volume resistivity
Sample preparation: reference is made to the standard "GB/T29848-2018 ethylene vinyl acetate copolymer (EVA) glue film for photovoltaic module encapsulation". Taking an EVA adhesive film with the size of 50mm multiplied by 50mm, laminating the EVA adhesive film, the non-adhesive film and the back plate material for 15min at 140 ℃ after sequentially laminating the EVA adhesive film, the non-adhesive film and the back plate material from bottom to top. The samples taken from the non-mucosa are required to be flat in upper and lower surfaces and uniform in thickness, after being cooled to room temperature, each group of samples is not less than 3 points, and the average value is taken.
The reflectivity test method comprises the following steps: the test specimens were tested according to the spectrophotometer method of ASTM E424-71 (2015). The wavelength range of the spectrophotometer is set to be 400 nm-700 nm. At least 3 samples were tested and the test results averaged.
The crosslinking degree test method comprises the following steps: weighing 0.50g +/-0.01 g, cutting into small particles with the size of less than 3mm multiplied by 3mm, wrapping with a 120-mesh wire gauze, refluxing and steaming with dimethylbenzene at 140 ℃ for 5 hours, taking out a sample, drying in a vacuum drying oven at 140 ℃ to constant weight, calculating the gel content (crosslinking degree) of the sample, and preparing 3 samples in each group.
The volume resistivity test method comprises the following steps: and (3) taking an uncured adhesive film with the size of 100mm multiplied by 100mm, laminating according to the sample preparation method, testing the volume resistivity of the sample according to the specification of GB/T1410-2006, and taking an average value of the results.
2) Peel Strength test
Sample preparation: preparing two uncured EVA (ethylene vinyl acetate) adhesive films, one glass film and one flexible back plate, wherein the sizes of the two uncured EVA adhesive films, the glass film and the flexible back plate are 300mm multiplied by 150mm, sequentially stacking the two uncured EVA adhesive films and the flexible back plate, laminating the two uncured EVA adhesive films and the flexible back plate at the temperature of 140 ℃ for 15min, wherein the EVA adhesive films in cured samples have no bubbles, and each group is used for preparing 3 samples; then, the flexible backsheet/EVA film layer was cut every 5mm in the width direction just into test pieces having a width of 10mm ± 0.5mm for the test of peel strength.
The test method comprises the following steps: the peel strength between the glass and the adhesive film was tested on a tensile tester at a tensile speed of 100 mm/min. + -. 10mm/min according to the test method of GB/T2790-1995, and the peel strength was averaged for each set of tests.
3) UV aging test
Sample preparation: two EVA adhesive films with the sizes of 300mm multiplied by 150mm are taken, and after the two EVA adhesive films are sequentially laminated according to the glass, the transparent EVA adhesive film, the white EVA adhesive film and the back plate material from bottom to top, the lamination is carried out for 15min at the temperature of 140 ℃ to prepare the lamination piece sample with no defect in appearance. The crosslinking degree of the EVA adhesive film reaches over 75 percent, and 3 laminated piece samples are prepared in each group.
The test method comprises the following steps: according to IEC 61215-2: 2016, and cumulatively irradiating at 60 ℃. + -. 5 ℃ at 120kWh/m 2 . The yellowness index Y1 was measured according to ASTM E313-2010 for each of the laminated samples before and after the test at not less than 3 points and the average was taken. Recording the absolute value of the difference between the yellowness index Y1 after aging and the yellowness index Y2 before aging, namely the yellowness index UV (120 kWh/m) 2 )- 
Y。
4) DH aging test
Sample preparation: two EVA adhesive films with the size of 300mm multiplied by 300mm are taken, and 3 laminated piece samples are prepared in each group according to the requirement of UV aging preparation samples.
The test method comprises the following steps: all the samples were placed in a high temperature and high humidity aging test box, test conditions: temperature 85 ℃ +/-2 ℃ and relative humidity 85% +/-5%, test for 1000 h; the yellowness index Y1 was then measured according to ASTM E313-2010 for each of the laminated samples before and after the test at not less than 3 points and averaged. Recording the absolute value of the difference between the yellowness index Y1 after aging and the yellowness index Y2 before aging, namely the yellowness index DH (1000 h) -
Y。
(3) PID testing
Preparing a component: by adopting a conventional Zhongwei 163 double-sided P-type PERC battery, sequentially preparing an example component A1-A7 and a comparative example component B1-B3 by series welding of battery pieces, laminating of glass-high-transmittance EVA (ethylene vinyl acetate) adhesive film-battery piece-white EVA adhesive film-KPF (Kernel Per fluoride) back plate and laminating (laminating at 140 ℃, vacuumizing for 6min and maintaining pressure for 10 min); the high-permeability EVA adhesive film is a commercially available EVA adhesive film (manufacturer: Lushan, brand: EV1050G 2).
And (3) PID test: the power attenuation test is carried out on the prepared component by referring to the standard IEC61215 and IEC61370, the power change of the example component and the comparative example component before and after the comparison test is carried out for 192h at the temperature of 85 ℃ and the humidity of 85 percent and with the voltage of-1500V, and the specific data are shown in the following table:
compared with comparative examples 1-3, the adhesive film added with the reinforced composite acid inhibitor has the free acetic acid content of no more than 30ppm and is far lower than that of the adhesive film of the comparative examples, and the reflectivity, the crosslinking degree, the volume resistivity, the peel strength, the UV aging property, the DH aging property and the like of the adhesive film are hardly influenced, which fully shows the good inhibition effect of the composite acid inhibitor on the hydrolysis of the white EVA and the feasibility of the scheme. Meanwhile, a PID-192h experiment further proves that the addition of the composite acid inhibitor has a positive effect on the PID resistance of the component.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The utility model provides a low acid type white EVA photovoltaic encapsulation glued membrane which characterized in that: the low-acid white EVA photovoltaic packaging adhesive film comprises, by weight, 100 parts of EVA resin, 5-10 parts of titanium dioxide, 1-5 parts of a complex acid inhibitor, 0.5-1.0 part of a peroxide crosslinking agent, 0.3-1.0 part of an auxiliary crosslinking agent, 0.2-0.6 part of a coupling agent, 0.1-0.5 part of an antioxidant and 0-0.5 part of an ultraviolet absorbent.
2. The low-acid type white EVA photovoltaic packaging adhesive film of claim 1, wherein: the composite acid inhibitor is an enhanced acid inhibitor, and comprises an amphiphilic polymer, an alkaline metal compound, a carbodiimide compound and a macromolecular coupling agent, and is prepared by mixing and granulating the amphiphilic polymer, the alkaline metal compound, the carbodiimide compound and the macromolecular coupling agent in proportion.
3. The low-acid type white EVA photovoltaic packaging adhesive film of claim 2, wherein: in the composite acid inhibitor, the ratio of amphiphilic polymer, alkaline metal compound, carbodiimide compound and macromolecular coupling agent is respectively 1: 0.02-0.1: 0.01-0.05: 0.02-0.06.
4. The low-acid type white EVA photovoltaic packaging adhesive film of claim 2, wherein: the amphiphilic polymer includes, but is not limited to, one or more of ethylene-vinyl acetate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-methacrylate copolymer, and ethylene-acrylate-glycidyl methacrylate terpolymer.
5. The low-acid type white EVA photovoltaic packaging adhesive film of claim 4, wherein: the melt index of the amphiphilic polymer is 2-30g/10min, and the melting point is 55-110 ℃.
6. The low-acid type white EVA photovoltaic packaging adhesive film of claim 2, wherein: the basic metal compound includes, but is not limited to, one or more of magnesium hydroxide, aluminum hydroxide, zinc oxide, zinc stearate, basic magnesium carbonate, basic aluminum carbonate, and zirconium hydrogen phosphate.
7. The low-acid type white EVA photovoltaic packaging adhesive film of claim 2, wherein: the carbodiimide-based compound includes, but is not limited to, one or more of N, N ' -bis (2, 6-diisopropylphenyl) carbodiimide, dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N ' -diisohexylcarbodiimide, 1, 3-bis (2, 2-dimethyl-1, 3-dioxolan-4-ylmethyl) carbodiimide, poly (2, 6-diisopropylphenyl) carbodiimide, and di-t-butylcarbodiimide.
8. The low-acid type white EVA photovoltaic packaging adhesive film of claim 7, wherein: the carbodiimide compound is one or two of non-aromatic imine compounds N, N '-diisopropyl carbodiimide, N' -diisohexylcarbodiimide, 1, 3-bis (2, 2-dimethyl-1, 3-dioxolan-4-ylmethyl) carbodiimide and di-tert-butyl carbodiimide.
9. The low-acid type white EVA photovoltaic packaging adhesive film of claim 2, wherein: the macromolecular coupling agent is prepared by carrying out free radical polymerization on vinyl acetate and styrene serving as main monomers and gamma-methacryloxypropyltrimethoxysilane serving as a functional monomer, wherein the content of the functional monomer is 1-10%.
10. A method for preparing a low-acid white EVA photovoltaic encapsulant film according to any of claims 1-9, comprising the following steps:
step 1: preparing a composite acid inhibitor:
weighing 1 part of amphiphilic polymer, 0.02-0.1 part of alkaline metal compound, 0.01-0.05 part of carbodiimide compound and 0.02-0.06 part of macromolecular coupling agent according to parts by weight, and preparing the composite acid inhibitor by adopting a double-screw granulation mode;
step 2: preparing a low-acid type white EVA photovoltaic packaging adhesive film:
weighing 100 parts of EVA resin, 5-10 parts of titanium dioxide, 1-5 parts of composite acid inhibitor, 0.5-1.0 part of peroxide crosslinking agent, 0.3-1.0 part of auxiliary crosslinking agent, 0.2-0.6 part of coupling agent, 0.1-0.5 part of antioxidant and 0-0.5 part of ultraviolet absorbent according to parts by weight, mixing, putting the mixture into an extruder for mixing and plasticizing, and carrying out embossing shaping, cooling, traction and coiling on the extrudate to obtain the low-acid type white EVA (ethylene-vinyl acetate) photovoltaic packaging adhesive film.
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