Packaging adhesive film, preparation method thereof and photovoltaic module

Abstract

The invention discloses a packaging adhesive film, a preparation method thereof and a photovoltaic module, and relates to the technical field of packaging adhesive films. The packaging adhesive film comprises matrix resin, an anti-hydrolysis agent grafted modified acid acceptor and an auxiliary agent, and the auxiliary agent comprises a cross-linking agent and an assistant cross-linking agent; the mass ratio of the anti-hydrolysis agent grafted modified acid acceptor to the matrix resin is (0.1-1): 100; the grafting rate of the hydrolysis-resistant agent grafted modified acid acceptor is 1%-4%. The packaging adhesive film has good long-acting corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of encapsulation adhesive film, in particular to an encapsulation adhesive film, a preparation method thereof and a photovoltaic module. BACKGROUND

[0002] The corrosion resistance of a photovoltaic module is a key technology to ensure its long-term stable operation, and improving the corrosion resistance of the encapsulation adhesive film material is an important direction to improve the corrosion resistance of the photovoltaic module.

[0003] Currently, there are two main methods to improve the corrosion resistance of the encapsulation adhesive film. One is to add inorganic acid absorbents such as alkali metal oxides, alkali metal hydroxides and hydrotalcite to the encapsulation adhesive film to absorb the acetic acid generated by the degradation of ethylene-vinyl acetate copolymer (EVA) or the acidic components remaining in the additives. The other is to add an anti-hydrolysis agent to reduce the probability of degradation of the encapsulation adhesive film due to the penetration of water vapor, so as to improve the water vapor barrier performance.

[0004] Most of the existing solutions directly add acid absorbents and anti-hydrolysis agents to the resin. Although the basic sites of the acid absorbents can help to absorb the acidic substances generated in the encapsulation adhesive film, these basic sites can also catalyze the degradation of ester polymers in high-temperature environments, which can result in a narrow application range of the encapsulation adhesive film and poor long-term corrosion resistance. SUMMARY

[0005] The main purpose of the present application is to provide an encapsulation adhesive film, a preparation method thereof and a photovoltaic module to solve the problem of poor long-term corrosion resistance of the encapsulation adhesive film in the prior art.

[0006] In order to achieve the above-mentioned purpose, according to the first aspect of the present application, an encapsulation adhesive film is provided, which comprises a base resin, an anti-hydrolysis agent grafted modified acid absorbent and an additive, wherein the additive comprises a crosslinking agent and a co-crosslinking agent; the mass ratio of the anti-hydrolysis agent grafted modified acid absorbent to the base resin is (0.1-1):100; and the grafting rate of the anti-hydrolysis agent grafted modified acid absorbent is 1%-4%.

[0007] Further, the raw materials for preparing the anti-hydrolysis agent grafted modified acid absorbent include a first silane coupling agent, an acid absorbent and an anti-hydrolysis agent.

[0008] Further, the first silane coupling agent includes at least one of a carboxyl silane coupling agent, an amino silane coupling agent and a mercapto silane coupling agent.

[0009] Further, the carboxyl silane coupling agent includes at least one of β-(carboxyethyl) silatrane, carboxyethyl silatrane sodium salt and 3-(trimethoxysilyl) propionic acid.

[0010] Further, the aminosilane coupling agent includes at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and phenylaminomethyltrimethoxysilane.

[0011] Further, the mercaptosilane coupling agent includes at least one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and bis-(3-triethoxysilylpropyl)disulfide.

[0012] Further, the acid-adsorbing agent is a basic metal compound, and the basic metal compound includes at least one of a metal oxide, a metal hydroxide, a carbonate, and a phosphate.

[0013] Further, the metal oxide includes at least one of magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, and manganese oxide.

[0014] Further, the metal hydroxide includes at least one of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, and hydrotalcite.

[0015] Further, the carbonate includes at least one of magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and magnesium bicarbonate.

[0016] Further, the phosphate includes at least one of zirconium phosphate, hydrogen zirconium phosphate, ammonium phosphate, ammonium polyphosphate, and hydrogen titanium phosphate.

[0017] Further, the specific surface area of the acid-adsorbing agent is 5 m 2 / g~50 m 2 / g.

[0018] Further, the anti-hydrolysis agent is at least one of a carbodiimide compound, a glycidyl ether compound, and an epoxy compound.

[0019] Further, the carbodiimide compound includes at least one of dicyclohexyl carbodiimide, N,N'-diisopropyl carbodiimide, polydicyclohexylmethane carbodiimide, polyhexamethylene carbodiimide, polyisophorone carbodiimide, poly 4,4'-diphenylmethane carbodiimide, polycumene carbodiimide, polycyclohexane carbodiimide, and (γ-triethoxysilylpropyl)carbodiimide.

[0020] Further, the glycidyl ether compound includes at least one of phenyl glycidyl ether, triglycidyl isocyanurate, trimethoxy[3-(glycidyl ether)propyl]silane, and triethoxy[3-(glycidyl ether)propyl]silane.

[0021] Further, the epoxy compound includes at least one of 4-vinyl epoxy cyclohexane, (3,4-epoxycyclohexyl)methyl acrylate, and β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.

[0022] Further, the mass ratio of the crosslinking agent to the hydrolysis-resistant agent grafted and modified acid absorbent is (0.01-1.5):(0.1-1), and the mass ratio of the co-crosslinking agent to the hydrolysis-resistant agent grafted and modified acid absorbent is (0.5-5):(0.1-1).

[0023] Further, the base resin is selected from at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, polyethylene, polyvinyl butyral, polymethyl methacrylate, polycarbonate, polyolefin plastomer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-maleic anhydride copolymer, and thermoplastic polyurethane. Further preferably, it is at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, and polyvinyl butyral.

[0024] Further, the crosslinking agent is selected from any one or more of dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl peroxyisopropyl carbonate, tert-amyl peroxyacetate, tert-amyl peroxy-(2-ethylhexyl) carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-di-tert-butylperoxy cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-butyl peroxy-tert-amyl benzoate, 1,1-di(tert-amylperoxy)cyclohexane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane.

[0025] Further, the co-crosslinking agent is selected from any one or more of triethylamine, dimethylaminoethanol, methyl ethyl ketone oxime, cyclohexanone oxime, diphenylthiourea, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glyceryl triacrylate, propoxylated glyceryl triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-l,3,5-triazine, tricyclogene diol dimethacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-l,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate.

[0026] Further, the co-agents also include an antioxidant, a second silane coupling agent, and an anti-PID co-agent.

[0027] Further, the mass ratio of the antioxidant to the graft-modified acid-adsorbing agent of the anti-hydrolysis agent is (0.1-0.5):(0.1-1); the mass ratio of the second silane coupling agent to the graft-modified acid-adsorbing agent of the anti-hydrolysis agent is (0.1-5):(0.1-1); and the mass ratio of the anti-PID co-agent to the graft-modified acid-adsorbing agent of the anti-hydrolysis agent is (0.1-0.5):(0.1-1).

[0028] Further, the antioxidant is selected from any one or more of 2,6-di-tert-butyl-4-methylphenol, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, dilauryl thiodipropionate, tris(1,2,2,6,6-pentamethyl-4-piperidyl) phosphite, bis-2,2,6,6-tetramethylpiperidinol decanoate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and 2,4-dichloro-6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine, a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine, a polymer of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,6-hexanediamine and morpholine-2,4,6-trichloro-1,3,5-triazine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate / methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate complex, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione / bis(2,4-dicumylphenyl) pentaerythritol diphosphite complex.

[0029] Further, the second silane coupling agent is selected from any one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(tert-butylperoxy)silane, vinyltriacetoxysilane, vinyltris(β-methoxyethoxy)silane, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3-aminopropyltrimethylsilane.

[0030] Further, the anti-PID additive is selected from any one or more of zirconium hydrogen phosphate, zinc phosphate, lithium triisopropylphosphonate, and lithium trimethylphosphonate.

[0031] According to a second aspect of the present application, a preparation method of a packaging adhesive film is provided, comprising the following steps:

[0032] S1, dispersing an acid-adsorbing agent in a first solvent to obtain a suspension;

[0033] S2, adding the suspension into a first silane coupling agent to perform a first reaction, to obtain a silanized acid-adsorbing agent;

[0034] S3, mixing the silanized acid-adsorbing agent with an anti-hydrolysis agent in a second solvent to perform a second reaction, to obtain an anti-hydrolysis agent grafted and modified acid-adsorbing agent;

[0035] S4, the hydrolysis-resistant agent graft-modified acid-adsorbing agent is mixed with the first base resin, granulated, to obtain a hydrolysis-resistant agent graft-modified acid-adsorbing agent master batch;

[0036] S5, the hydrolysis-resistant agent graft-modified acid-adsorbing agent master batch is mixed with the second base resin and the auxiliary agent, and is cast into a film to obtain the encapsulation adhesive film.

[0037] According to a third aspect of the present application, a photovoltaic module is provided, which comprises the encapsulation adhesive film of the first aspect of the present application or the encapsulation adhesive film prepared by the preparation method of the second aspect of the present application.

[0038] By adding the hydrolysis-resistant agent graft-modified acid-adsorbing agent to the base resin, controlling the amount of addition and the grafting rate, the active sites of the basic groups in the acid-adsorbing agent are chemically shielded, and the catalytic hydrolysis reaction is avoided. In addition, when water or acidic substances appear in the encapsulation adhesive film, the acid-adsorbing agent component in the hydrolysis-resistant agent graft-modified acid-adsorbing agent can neutralize the hydrogen ions in the acidic substances, and the hydrolysis-resistant agent component can capture carboxylic acid and water molecules to terminate the hydrolysis chain reaction, thereby realizing the synergistic effect of the acid-adsorbing agent and the hydrolysis-resistant agent, and improving the corrosion resistance of the encapsulation adhesive film. In addition, the interfacial compatibility of the acid-adsorbing agent and the encapsulation adhesive film is improved, which is conducive to ensuring the long-term stable and efficient operation of the photovoltaic module. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme of the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0040] As described in the background of the present application, the existing technology has the problem of poor long-term corrosion resistance of the encapsulation adhesive film. In order to solve the above problem, in a typical embodiment of the present application, an encapsulation adhesive film is provided, which comprises a base resin, a hydrolysis-resistant agent graft-modified acid-adsorbing agent and an auxiliary agent, wherein the auxiliary agent comprises a crosslinking agent and a co-crosslinking agent; the mass ratio of the hydrolysis-resistant agent graft-modified acid-adsorbing agent to the base resin is (0.1-1):100; and the grafting rate of the hydrolysis-resistant agent graft-modified acid-adsorbing agent is 1%-4%.

[0041] In the above-mentioned embodiments of the present application, by adding the anti-hydrolysis agent grafting modified acid absorbent in the resin, and controlling the addition amount and grafting rate of the anti-hydrolysis agent grafting modified acid absorbent, the basic group active sites in the acid absorbent are chemically shielded, avoiding catalyzing the hydrolysis reaction. In addition, when water or acidic substances appear in the encapsulation adhesive film, the acid absorbent component in the anti-hydrolysis agent grafting modified acid absorbent can neutralize the hydrogen ions in the acidic substances, and the anti-hydrolysis agent component can capture carboxylic acid and water molecules to terminate the hydrolysis chain reaction, thereby realizing the synergistic effect of the acid absorbent and the anti-hydrolysis agent, and improving the corrosion resistance of the encapsulation adhesive film. In addition, the interfacial compatibility of the acid absorbent and the encapsulation adhesive film is improved, which is conducive to ensuring the long-term stable and efficient operation of the photovoltaic module. When the grafting rate of the anti-hydrolysis agent grafting modified acid absorbent is less than 1%, part of the acid absorbent component in the anti-hydrolysis agent grafting modified acid absorbent is still exposed, which is easy to catalyze the degradation of ester polymer, thereby reducing the corrosion resistance of the encapsulation adhesive film. When the grafting rate of the anti-hydrolysis agent grafting modified acid absorbent is higher than 4%, the acid absorbent component is excessively coated, which hinders the neutralization reaction with the acidic component, and also reduces the corrosion resistance of the encapsulation adhesive film. In addition, when the content of the anti-hydrolysis agent grafting modified acid absorbent is less than 0.1%, its improvement effect on the corrosion resistance of the resin is effective, and when the content of the anti-hydrolysis agent grafting modified acid absorbent is higher than 1%, the aging yellowing rate of the encapsulation adhesive film is high.

[0042] In some embodiments, the encapsulation adhesive film comprises a second base resin, an anti-hydrolysis agent grafting modified acid absorbent master batch and an additive; the anti-hydrolysis agent grafting modified acid absorbent master batch comprises an anti-hydrolysis agent grafting modified acid absorbent and a first base resin, the mass ratio of the anti-hydrolysis agent grafting modified acid absorbent to the first base resin is (2-10):100; the total mass ratio of the anti-hydrolysis agent grafting modified acid absorbent to the first base resin and the second base resin is (0.1-1):100; and the grafting rate of the anti-hydrolysis agent grafting modified acid absorbent is 1%-4%.

[0043] By preparing the anti-hydrolysis agent grafting modified acid absorbent and the first base resin into a master batch, the dispersion uniformity of the anti-hydrolysis agent grafting modified acid absorbent in the encapsulation adhesive film is improved, and the performance consistency of the encapsulation adhesive film is improved.

[0044] In some embodiments, the raw materials for preparing the anti-hydrolysis agent grafting modified acid absorbent comprise a first silane coupling agent, an acid absorbent and an anti-hydrolysis agent; specifically but not limitedly, the first silane coupling agent comprises at least one of a carboxyl silane coupling agent, an amino silane coupling agent and a mercapto silane coupling agent.

[0045] In the above-mentioned embodiments of the present application, the first silane coupling agent, as an intermediate, can react with the hydroxyl groups on the surface of the acid absorbent to form a stable silanized acid absorbent, and the organic functional group at the other end of the silane coupling agent can graft with the hydrolysis-resistant agent, so that the hydrolysis-resistant agent component is coated on the surface of the acid absorbent component, avoiding direct contact between the acid absorbent component and the esterified polymer, and reducing the negative impact of the acid absorbent component on the encapsulation adhesive film. Exemplarily, the grafting mechanism is as follows: ① R-OH (hydroxyl group on the surface of the inorganic acid absorbent) + HOOC-R1-Si(OH)3 (carboxyl silane: one end containing siloxane (hydrolyzed to silanol), and one end containing carboxyl or anhydride group) → R-O-Si(OH)2-R1-COOH (carboxylated modified basic metal compound); ② R-O-Si(OH)2-R1-COOH + R'-N=C=N-R'' → R-O-Si(OH)2-R1-C(O)-N(R')-CH=N-R''.

[0046] Specifically but not limitedly, the carboxyl silane coupling agent includes at least one of β-(carboxyethyl)silicic triol, sodium carboxyethylsilicic triol, and 3-(trimethoxysilyl)propionic acid; the amino silane coupling agent includes at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and phenylaminomethyltrimethoxysilane; and the mercapto silane coupling agent includes at least one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and bis-(3-triethoxysilylpropyl)disulfide.

[0047] The first silane coupling agent described above can react with the acid absorbent to form a stable silanized acid absorbent, which is helpful to improve the compatibility of the acid absorbent with the base resin; and the first silane coupling agent has good stability, which is further helpful to improve the stability of the encapsulation adhesive film and prevent the encapsulation adhesive film from being decomposed at high temperature, thereby improving the long-term corrosion resistance of the encapsulation adhesive film.

[0048] In some embodiments, the acid absorbent is a basic metal compound, and the basic metal compound includes at least one of a metal oxide, a metal hydroxide, a carbonate, and a phosphate. Specifically but not limitedly, the metal oxide includes at least one of magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, and manganese oxide; the metal hydroxide includes at least one of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, and hydrotalcite; the carbonate includes at least one of magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and magnesium bicarbonate; and the phosphate includes at least one of zirconium phosphate, hydrogen zirconium phosphate, ammonium phosphate, polyammonium phosphate, and hydrogen titanium phosphate.

[0049] The acid absorbent described above can remain stable during the high-temperature processing and long-term use of the packaging adhesive film and is not prone to decomposition, thereby ensuring the long-term corrosion resistance of the packaging adhesive film. In addition, the acid absorbent described above helps to neutralize the acid generated by the degradation of the base resin and the acidic particles invading from the external environment, thereby protecting the packaging adhesive film from corrosion. In addition, the carbonates and phosphates described above have good dispersibility in the base resin after surface modification, which helps to improve the transparency and mechanical properties of the packaging adhesive film.

[0050] In some embodiments, the specific surface area of the acid absorbent is 5 m 2 / g~50 m 2 / g.

[0051] In the above embodiments of the present application, controlling the specific surface area of the acid absorbent within the above range helps to balance the corrosion resistance and light transmittance of the packaging adhesive film, thereby improving the overall performance of the packaging adhesive film. Specifically, controlling the specific surface area of the acid absorbent within the above range helps to increase the contact area between the acid absorbent and the silane coupling agent and the hydrolysis-resistant agent, thereby improving the chemical reaction efficiency during the graft modification process. In turn, this helps to better shield the active sites of the basic groups in the acid absorbent, thereby enhancing the chemical stability of the packaging adhesive film and improving its corrosion resistance in a high-temperature environment. In addition, the appropriate specific surface area of the acid absorbent helps to increase the amount of active sites of the acid absorbent, thereby helping to improve the corrosion resistance of the packaging adhesive film.

[0052] In some embodiments, the hydrolysis-resistant agent is at least one of a carbodiimide compound, a glycidyl ether compound, and an epoxy compound. Specifically, but not limited to, the carbodiimide compound includes at least one of dicyclohexyl carbodiimide, N,N'-diisopropyl carbodiimide, polydicyclohexylmethane carbodiimide, polyhexamethylene carbodiimide, polyisophorone carbodiimide, poly 4,4'-diphenyl methane carbodiimide, polytoluene carbodiimide, poly-p-phenyl carbodiimide, polycyclohexane carbodiimide, and (γ-triethoxysilyl propyl) carbodiimide; the glycidyl ether compound includes at least one of phenyl glycidyl ether, triglycidyl isocyanurate, trimethoxy[3-(glycidyl ether)propyl]silane, and triethoxy[3-(glycidyl ether)propyl]silane; and the epoxy compound includes at least one of 4-vinyl epoxy cyclohexane, (3,4-epoxycyclohexyl)methyl acrylate, and β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.

[0053] The anti-hydrolysis agent can quickly respond when the encapsulation adhesive film starts to hydrolyze, and prevent the hydrolysis reaction from proceeding. It can form a hydrophobic network through reaction, and enhance the barrier ability of the encapsulation adhesive film to water vapor, which helps to prevent moisture from penetrating from the external environment. It also has good chemical stability in the encapsulation adhesive film, which is conducive to improving the long-acting corrosion resistance of the encapsulation adhesive film. In addition, grafting the acid absorbent with the above anti-hydrolysis agent can achieve a synergistic effect of acid absorption and hydrolysis inhibition, maximizing the corrosion resistance of the encapsulation adhesive film. Furthermore, the anti-hydrolysis agent has good dispersibility in the resin, which helps to ensure the light transmittance and mechanical properties of the encapsulation adhesive film, and improves the comprehensive performance of the encapsulation adhesive film.

[0054] In some embodiments, the mass ratio of the crosslinking agent to the acid absorbent grafted and modified by the anti-hydrolysis agent is (0.01-1.5):(0.1-1); and the mass ratio of the co-crosslinking agent to the acid absorbent grafted and modified by the anti-hydrolysis agent is (0.5-5):(0.1-1).

[0055] Controlling the mass ratio of the crosslinking agent, the co-crosslinking agent, and the acid absorbent grafted and modified by the anti-hydrolysis agent within the above range helps to ensure that the encapsulation adhesive film has good flexibility and impact resistance, and helps to improve the bonding effect between the encapsulation adhesive film and the photovoltaic module.

[0056] Specific, but not limiting, crosslinking agents are selected from any one or more of dicumyl peroxide, t-butyl peroxy 2-ethylhexanoate, di-t-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, t-amyl peroxybenzoate, t-butyl peroxybenzoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl peroxy isopropylcarbonate, t-amyl peroxyacetate, t-amyl peroxy (2-ethylhexyl) carbonate, t-butyl peroxy 3,5,5-trimethylhexanoate, 1,1-di-t-butylperoxy cyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl peroxy t-amylate, 1,1-di(t-amylperoxy)cyclohexane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane. Co-crosslinking agents are selected from any one or more of triethylamine, dimethylaminoethanol, methyl ethyl ketoxime, cyclohexanone oxime, diphenylthiourea, tris(2-hydroxyethyl)isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glyceryl triacrylate, propoxylated glyceryl triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclohexanedimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate.

[0057] In some embodiments, the base resin is selected from at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, polyethylene, polyvinyl butyral, polymethyl methacrylate, polycarbonate, polyolefin plastomer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-maleic anhydride copolymer, and thermoplastic polyurethane. Further preferred are at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, and polyvinyl butyral.

[0058] The base resin described above is a commonly used base resin for preparing encapsulation adhesive films, has good light transmittance, and has certain weather resistance and mechanical properties, and is suitable for application to encapsulating photovoltaic modules.

[0059] In some embodiments, the adjuvant further comprises an antioxidant, a second silane coupling agent, and a PID resistance adjuvant.

[0060] The addition of the antioxidant helps to improve the aging resistance of the encapsulation film and improve its service life; the addition of the second silane coupling agent helps to improve the dispersibility of the various additives in the encapsulation film, thereby helping to ensure the long-term corrosion resistance and light transmittance of the encapsulation film; the addition of the anti-PID additive helps to improve the anti-PID performance, light transmittance, and weather resistance of the encapsulation film.

[0061] In some embodiments, the mass ratio of the antioxidant to the hydrolysis-resistant agent grafted and modified acid absorbent is (0.1-0.5):(0.1-1); the mass ratio of the second silane coupling agent to the hydrolysis-resistant agent grafted and modified acid absorbent is (0.1-5):(0.1-1); and the mass ratio of the anti-PID additive to the hydrolysis-resistant agent grafted and modified acid absorbent is (0.1-0.5):(0.1-1).

[0062] Controlling the mass ratio of the antioxidant to the hydrolysis-resistant agent grafted and modified acid absorbent within the above range helps to improve the aging resistance of the encapsulation film and improve the service life of the encapsulation film. Controlling the mass ratio of the second silane coupling agent to the hydrolysis-resistant agent grafted and modified acid absorbent within the above range helps to improve the performance consistency of the encapsulation film, thereby helping to improve the corrosion resistance and light transmittance of the encapsulation film. Controlling the mass ratio of the anti-PID additive to the hydrolysis-resistant agent grafted and modified acid absorbent within the above range helps to further improve the anti-PID performance, corrosion resistance, and light transmittance of the encapsulation film.

[0063] Specifically but not limitedly, the antioxidant is selected from any one or more of 2,6-di-tert-butyl-4-methylphenol, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, dilauryl thiodipropionate, tris(1,2,2,6,6-pentamethyl-4-piperidyl) phosphite, bis-2,2,6,6-tetramethylpiperidinyl sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and 2,4-dichloro-6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine, a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine, a polymer of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,6-hexanediamine and morpholine-2,4,6-trichloro-1,3,5-triazine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate / methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate complex, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione / bis(2,4-dicumylphenyl) pentaerythritol diphosphite complex.

[0064] Specifically but not limitedly, the second silane coupling agent is selected from any one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(tert-butylperoxy)silane, vinyltriacetoxysilane, vinyltris(β-methoxyethoxy)silane, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3-aminopropyltrimethylsilane.

[0065] Specifically but not limitedly, the anti-PID additive is selected from any one or more of zirconium hydrogen phosphate, zinc phosphate, lithium triisopropylphosphonate, and lithium trimethylphosphonate.

[0066] In another exemplary embodiment of the present application, a method for preparing the encapsulation adhesive film in the above-mentioned embodiments is provided, comprising the following steps:

[0067] S1, dispersing the acid-adsorbing agent in a first solvent to obtain a suspension;

[0068] S2, adding the suspension into a first silane coupling agent to perform a first reaction, thereby obtaining a silanized acid-adsorbing agent;

[0069] S3, mixing the silanized acid-adsorbing agent with the hydrolysis-resistant agent in a second solvent to perform a second reaction, thereby obtaining a hydrolysis-resistant agent grafted and modified acid-adsorbing agent.

[0070] S4, mixing the hydrolysis-resistant agent graft-modified acid absorbent with the first base resin, granulating to obtain a hydrolysis-resistant agent graft-modified acid absorbent master batch;

[0071] S5, mixing the hydrolysis-resistant agent graft-modified acid absorbent master batch with the second base resin and the auxiliary agent, and casting into a film to obtain the encapsulation adhesive film.

[0072] In the above-mentioned embodiments of the present application, S2 helps to improve the interfacial compatibility of the acid absorbent and the base resin, and the dispersibility is good, which ensures the high transparency of the encapsulation adhesive film. S3 helps to achieve a synergistic effect between the acid absorbent and the hydrolysis-resistant agent. The grafted hydrolysis-resistant agent not only effectively prevents the occurrence of hydrolysis reaction, but also avoids the decomposition of the resin matrix catalyzed by the acid absorbent, and the acid absorbent can fully play its advantage of absorbing acidic substances, and the hydrolysis-resistant agent can improve the long-term corrosion resistance of the encapsulation adhesive film.

[0073] In some embodiments, before dispersing the acid absorbent in the solvent in S1, the acid absorbent is first dried. In S1, by drying the acid absorbent, the hydroxyl groups on the surface of the acid absorbent are activated, which makes it easy to form chemical bonds with the carboxyl silane coupling agent, improves the grafting rate, and thus improves the long-term corrosion resistance of the encapsulation adhesive film.

[0074] Specifically but not limitedly, the above-mentioned first solvent and the second solvent each independently include at least one of toluene, acetone, and butanone. The first silane coupling agent can fully react with the acid absorbent in the above-mentioned solvent to form a stable silanized acid absorbent.

[0075] In some embodiments, the first reaction temperature is 50°C to 110°C, and the reaction time is 1h to 6h, and the second reaction temperature is 80°C to 140°C, and the reaction time is 0.5h to 8h.

[0076] In some embodiments, the molar ratio of the carboxyl, amino, or mercapto groups in the acid absorbent to the silane coupling agent is 100: (0.3-5).

[0077] By controlling the molar ratio of the active groups in the acid absorbent to the silane coupling agent within the above-mentioned range, the acid absorbent can be moderately surface-modified, and thus the stability of the silanized acid absorbent is ensured. The appropriate molar ratio helps to improve the dispersibility of the acid absorbent in the encapsulation adhesive film and the compatibility with the base resin, which helps to improve the chemical stability of the encapsulation adhesive film on the one hand, and ensures that the acid absorbent can fully play its role on the other hand.

[0078] In some embodiments, the molar ratio of the silanized acid absorbent to the hydrolysis-resistant agent is 100: (0.5-6).

[0079] Controlling the molar ratio of the silanized acid-adsorbing agent and the hydrolysis-resistant agent within the above range helps to achieve the desired synergistic effect between the acid-adsorbing agent and the hydrolysis-resistant agent, on the one hand, helps to prevent the acid-adsorbing agent component from directly contacting the ester polymer and catalyzing the decomposition of the ester polymer at high temperatures, and on the other hand, helps to sufficiently prevent the hydrolysis reaction from proceeding, improves the acid-adsorbing efficiency, and improves the long-term corrosion resistance of the encapsulation adhesive film.

[0080] In another typical embodiment of the present application, a photovoltaic module is provided, which comprises the corrosion-resistant encapsulation adhesive film in the above-mentioned embodiments of the present application or the corrosion-resistant encapsulation adhesive film prepared by the preparation method in the above-mentioned embodiments of the present application. Since the above-mentioned corrosion-resistant encapsulation adhesive film has good long-term corrosion resistance, the above-mentioned photovoltaic module has good corrosion resistance and stability, and has a wide range of applications.

[0081] The present application will be further described in detail below in conjunction with specific examples, which should not be construed as limiting the scope of the present application.

[0082] The information of the supplementary materials in the examples and comparative examples is as follows:

[0083] Magnesium hydroxide A: Japan Synergy, Kisuma 5A, specific surface area 5 m 2 / g;

[0084] Magnesium hydroxide B: Qinghai Western Magnesium Industry, XDM-10, specific surface area 25 m 2 / g;

[0085] Magnesium hydroxide C: Xuancheng Jingrui New Material, JR-MH02, specific surface area 50 m 2 / g;

[0086] Magnesium hydroxide D: Yantai Haoyu Magnesium Industry, HY-90, specific surface area 3 m 2 / g;

[0087] Magnesium hydroxide E: Xuancheng Jingrui New Material, JR-MH03, specific surface area 60 m 2 / g;

[0088] Calcium oxide: Shanxi Changxiang New Material Technology Co., Ltd., CX-CaO-01, specific surface area 30 m 2 / g;

[0089] Magnesium carbonate: Hebei Magnesium God, MS-MC, specific surface area 20 m 2 / g;

[0090] Zirconium phosphate: Xuancheng Jingrui New Material, JR-ZrP01, specific surface area 40 m 2 / g;

[0091] Ethylene-vinyl acetate copolymer: HANWA VF024, HANWA E280PV;

[0092] Polyolefin elastomer: Dow 38669, Exxon Mobil 38668;

[0093] Polyvinyl butyral: Teijin SG10, Sekisui Chemical BX-11.

[0094] Example 1

[0095] An embodiment of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film described in this embodiment is as follows:

[0096] S1, dry the acid absorber magnesium hydroxide A, the drying temperature is 100℃, the drying time is 3h, dissolve the dried magnesium hydroxide in anhydrous toluene to obtain a suspension; In the suspension, the concentration of magnesium hydroxide is 10% by mass fraction;

[0097] S2, drop the silane coupling agent 3-(trimethoxysilyl) propionic acid into the suspension, carry out the first reaction, the reaction temperature is 80℃, the time is 3h, then filter, wash and dry, the drying temperature is 100℃, the drying time is 3h, to obtain the silanized acid absorber; The molar ratio of magnesium hydroxide in the suspension to carboxyl in the silane coupling agent is 100:2;

[0098] S3, mix the silanized acid absorber and the hydrolysis-resistant agent N,N'-diisopropyl carbodiimide in anhydrous toluene, carry out the second reaction, the reaction temperature is 110℃, the time is 5h, then wash and dry, the drying temperature is 100℃, the drying time is 3h, to obtain the hydrolysis-resistant agent grafted and modified acid absorber; The molar ratio of the silanized acid absorber to the hydrolysis-resistant agent is 100:3;

[0099] S4, add the hydrolysis-resistant agent grafted and modified acid absorber and the ethylene-vinyl acetate copolymer into the granulator according to the mass ratio of 2:100, melt at 100℃, and granulate to obtain the hydrolysis-resistant agent grafted and modified acid absorber masterbatch;

[0100] S5, mix the hydrolysis-resistant agent grafted and modified acid absorber masterbatch, the ethylene-vinyl acetate copolymer, the dicumyl peroxide, the triethylamine, the 2,6-di-tert-butyl-4-methyl phenol, the vinyl trimethoxysilane and the lithium triisopropyl phosphonate according to the mass ratio of 5.4:100:1.06:2.12:0.318:2.12:0.212, melt at 90℃, and form a film by extrusion casting to obtain the packaging adhesive film.

[0101] Example 2

[0102] An embodiment of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film described in this embodiment is as follows:

[0103] S1, drying the acid-accepting agent magnesium hydroxide A, the drying temperature is 100℃, the drying time is 3h, dissolving the dried acid-accepting agent in anhydrous toluene to obtain a suspension; in the suspension, the concentration of the acid-accepting agent is 10% by mass fraction;

[0104] S2, dropping the silane coupling agent 3-(trimethoxysilyl) propionic acid into the suspension to perform a first reaction, the reaction temperature is 50℃, the time is 6h, then filtering, washing and drying to obtain a silylated acid-accepting agent; in the suspension, the molar ratio of the acid-accepting agent to the carboxyl in the silane coupling agent is 100:2;

[0105] S3, mixing the silylated acid-accepting agent and the hydrolysis-resistant agent N,N'-diisopropyl carbodiimide in anhydrous toluene to perform a second reaction, the reaction temperature is 140℃, the time is 0.5h, then washing and drying to obtain a hydrolysis-resistant agent grafted and modified acid-accepting agent; the molar ratio of the silylated acid-accepting agent to the hydrolysis-resistant agent is 100:3;

[0106] S4, adding the hydrolysis-resistant agent grafted and modified acid-accepting agent and the ethylene-vinyl acetate copolymer into a granulator according to a mass ratio of 5:100, melting at 100℃, and granulating to obtain a hydrolysis-resistant agent grafted and modified acid-accepting agent master batch;

[0107] S5, mixing the hydrolysis-resistant agent grafted and modified acid-accepting agent master batch, the ethylene-vinyl acetate copolymer, dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methyl phenol, vinyl trimethoxysilane and lithium triisopropyl phosphonate according to a mass ratio of 11.67:100:5.56:11.11:1.67:5.56:1.11, melting at 90℃, and forming a film by extrusion casting to obtain an encapsulation adhesive film.

[0108] Example 3

[0109] An embodiment of the anti-corrosion encapsulation adhesive film of the present application, the preparation method of the anti-corrosion encapsulation adhesive film is as follows:

[0110] S1, drying the acid-accepting agent magnesium hydroxide A, the drying temperature is 100℃, the drying time is 2h, dissolving the dried acid-accepting agent in anhydrous toluene to obtain a suspension; in the suspension, the concentration of the acid-accepting agent is 10% by mass fraction;

[0111] S2, dropping the silane coupling agent 3-(trimethoxysilyl) propionic acid into the suspension to perform a first reaction, the reaction temperature is 110℃, the time is 1h, then filtering, washing and drying to obtain a silylated acid-accepting agent; in the suspension, the molar ratio of the acid-accepting agent to the carboxyl in the silane coupling agent is 100:2;

[0112] S3, the silanized acid absorbent and the hydrolysis-resistant agent N,N'-diisopropyl carbodiimide are mixed in anhydrous toluene, a second reaction is carried out, the reaction temperature is 80 DEG C, the time is 8h, then washing, drying, the hydrolysis-resistant agent grafted modified acid absorbent is obtained; the molar ratio of the silanized acid absorbent and the hydrolysis-resistant agent is 100:3;

[0113] S4, the hydrolysis-resistant agent grafted modified acid absorbent and the ethylene-vinyl acetate copolymer are added into granulation according to the mass ratio of 10:100, melt at 100 DEG C, granulation, the hydrolysis-resistant agent grafted modified acid absorbent master batch is obtained;

[0114] S5, the hydrolysis-resistant agent grafted modified acid absorbent master batch, ethylene-vinyl acetate copolymer, dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methyl phenol, vinyl trimethoxysilane, lithium triisopropyl phosphonate are mixed according to the mass ratio of 12.23:100:11.12:22.24:3.36:22.24:2.224, melt at 90 DEG C, film is formed by extrusion casting, the encapsulation adhesive film is obtained.

[0115] Example 4

[0116] An embodiment of the anti-corrosion encapsulation adhesive film of the application, the preparation method of the anti-corrosion encapsulation adhesive film described in this embodiment is different from that of example 2 as follows:

[0117] In S3, the molar ratio of the silanized acid absorbent and the hydrolysis-resistant agent is 100:0.5.

[0118] Example 5

[0119] An embodiment of the anti-corrosion encapsulation adhesive film of the application, the preparation method of the anti-corrosion encapsulation adhesive film described in this embodiment is different from that of example 2 as follows:

[0120] In S3, the molar ratio of the silanized acid absorbent and the hydrolysis-resistant agent is 100:6.

[0121] Example 6

[0122] An embodiment of the anti-corrosion encapsulation adhesive film of the application, the preparation method of the anti-corrosion encapsulation adhesive film described in this embodiment is different from that of example 1 as follows:

[0123] In S1, the acid absorbent is calcium oxide;

[0124] In S3, the hydrolysis-resistant agent is triisocyanate, the molar ratio of the silanized acid absorbent and the hydrolysis-resistant agent is 100:0.5.

[0125] Example 7

[0126] An embodiment of the anti-corrosion encapsulation adhesive film of the application, the preparation method of the anti-corrosion encapsulation adhesive film described in this embodiment is different from that of example 1 as follows:

[0127] S5, the hydrolysis resistant agent graft modification acid absorbent masterbatch, ethylene-vinyl acetate copolymer, dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methyl phenol, vinyl trimethoxysilane, lithium triisopropyl phosphonate are mixed according to the mass ratio of 5.4:100:1.06:2.12:0.318:2.12:0.212 to obtain the upper and lower EVA film premix raw materials;

[0128] S6, the polyolefin elastomer (POE), dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methyl phenol, vinyl trimethoxysilane, lithium triisopropyl phosphonate are mixed according to the mass ratio of 100:1.06:2.12:0.318:2.12:0.212 to obtain the middle layer POE film premix raw material;

[0129] S7, the EVA film premix raw material, the middle layer POE film premix raw material and the EVA film premix raw material are sequentially stacked and arranged, melted at 90℃, co-extruded, cast into a film to form a 3-layer co-extruded film.

[0130] Example 8

[0131] An embodiment of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film described in this embodiment is different from that of example 1 as follows:

[0132] In S1, the acid absorbent is magnesium carbonate;

[0133] In S2, the silane coupling agent is 3-aminopropyl triethoxysilane;

[0134] In S3, the hydrolysis resistant agent is 4-vinyl epoxy cyclohexane;

[0135] In S5, the antioxidant is bis(2,4-di-tert-butylphenyl) pentaerythritol dithiophosphate;

[0136] In addition, in this embodiment, the first base resin raw material and the second base resin raw material are both replaced by polyolefin elastomer instead of ethylene-vinyl acetate copolymer in example 1.

[0137] Example 9

[0138] An embodiment of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film described in this embodiment is different from that of example 1 as follows:

[0139] In S1, the acid absorbent is zirconium phosphate;

[0140] In S2, the silane coupling agent is 3-mercapto propyl trimethoxysilane;

[0141] In S3, the hydrolysis resistant agent is 4-vinyl epoxy cyclohexane;

[0142] In S5, the antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine;

[0143] In addition, in the present embodiment, the first base resin raw material and the second base resin raw material are both replaced with polyvinyl butyral instead of the ethylene-vinyl acetate copolymer in Embodiment 1.

[0144] Embodiment 10

[0145] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0146] In S2, triisopropylsilane is used instead of 3-(trimethoxysilyl)propionic acid.

[0147] Embodiment 11

[0148] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0149] In S1, the acid absorbent is magnesium hydroxide B.

[0150] Embodiment 12

[0151] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0152] In S1, the acid absorbent is magnesium hydroxide C.

[0153] Embodiment 13

[0154] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0155] In S1, the acid absorbent is magnesium hydroxide D.

[0156] Embodiment 14

[0157] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0158] In S1, the acid absorbent is magnesium hydroxide E.

[0159] Comparative Example 1

[0160] In one embodiment of the anti-corrosion packaging adhesive film of the present application, the difference between the preparation method of the anti-corrosion packaging adhesive film of the present embodiment and Embodiment 1 is as follows:

[0161] S1, the acid absorbent magnesium hydroxide A and ethylene-vinyl acetate copolymer were added into a granulator at a mass ratio of 5:100, melted at 100℃, and granulated to obtain an acid absorbent master batch;

[0162] S2, the hydrolysis inhibitor N,N'-diisopropyl carbodiimide and ethylene-vinyl acetate copolymer were added into a granulator at a mass ratio of 2:100, melted at 100℃, and granulated to obtain a hydrolysis inhibitor master batch;

[0163] S3, the acid absorbent master batch, the hydrolysis inhibitor master batch, ethylene-vinyl acetate copolymer, dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methylphenol, vinyl trimethoxysilane, and lithium triisopropyl phosphonate were mixed at a mass ratio of 2.23:0.35:100:1.06:2.12:0.318:2.12:0.212, melted at 90℃, and formed into a film by extrusion casting to obtain a packaging adhesive film.

[0164] Comparative Example 2

[0165] The packaging adhesive film of the present application is prepared by the following method:

[0166] S1, the acid absorbent magnesium hydroxide A and ethylene-vinyl acetate copolymer were added into a granulator at a mass ratio of 1.88:100, melted at 100℃, and granulated to obtain an acid absorbent master batch;

[0167] S2, the hydrolysis inhibitor N,N'-diisopropyl carbodiimide and ethylene-vinyl acetate copolymer were added into a granulator at a mass ratio of 0.12:100, melted at 100℃, and granulated to obtain a hydrolysis inhibitor master batch;

[0168] S3, the acid absorbent master batch, the hydrolysis inhibitor master batch, ethylene-vinyl acetate copolymer, dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methylphenol, vinyl trimethoxysilane, and lithium triisopropyl phosphonate were mixed at a mass ratio of 5.4:5.4:100:1.06:2.12:0.318:2.12:0.212, melted and extruded to obtain a premix material for the upper and lower EVA adhesive films;

[0169] S4, polyolefin elastomer (POE), dicumyl peroxide, triethylamine, 2,6-di-tert-butyl-4-methylphenol, vinyl trimethoxysilane, and lithium triisopropyl phosphonate were mixed at a mass ratio of 100:1.06:2.12:0.318:2.12:0.212, melted and extruded to obtain a premix material for the middle POE adhesive film;

[0170] S7, sequentially laminating the EVA adhesive film premix raw material, the intermediate layer POE adhesive film premix raw material and the EVA adhesive film premix raw material, melting at 90℃, co-extruding, casting into a film to form a 3-layer co-extruded adhesive film.

[0171] Comparative Example 3

[0172] A comparative example of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film of the comparative example is different from that of Example 1 as follows:

[0173] In S5, the hydrolysis-resistant agent grafted and modified acid-absorbing agent masterbatch and ethylene-vinyl acetate copolymer are added into the twin-screw extruder at a mass ratio of 4.25:100.

[0174] Comparative Example 4

[0175] A comparative example of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film of the comparative example is different from that of Example 2 as follows:

[0176] In S5, the hydrolysis-resistant agent grafted and modified acid-absorbing agent masterbatch and ethylene-vinyl acetate copolymer are added into the twin-screw extruder at a mass ratio of 70:100.

[0177] Comparative Example 5

[0178] A comparative example of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film of the comparative example is different from that of Example 2 as follows:

[0179] In S3, the molar ratio of silanized acid-absorbing agent to hydrolysis-resistant agent is 100:0.2, and the grafting rate is 0.62%.

[0180] Comparative Example 6

[0181] A comparative example of the anti-corrosion packaging adhesive film of the present application, the preparation method of the anti-corrosion packaging adhesive film of the comparative example is different from that of Example 2 as follows:

[0182] In S3, the molar ratio of silanized acid-absorbing agent to hydrolysis-resistant agent is 100:10, and the grafting rate is 6.15%.

[0183] Performance Test

[0184] The packaging adhesive films prepared in the examples and comparative examples are tested for performance, and the test method is as follows, and the test results are shown in Table 1.

[0185] (1) Grafting rate: the grafting rate is calculated by the formula (mass of hydrolysis-resistant agent grafted and modified acid-absorbing agent (after grafting)-mass of starting silanized acid-absorbing agent) / mass of starting silanized acid-absorbing agent;

[0186] (2) Corrosion resistance: Calculate the power attenuation rate by testing the power data of 32 half-assembly components before and after DH2000h (85℃, 85%RH) aging;

[0187] (3) Light transmittance: Test the light transmittance of the encapsulation adhesive film in the 400-700nm visible light band by an ultraviolet spectrophotometer (PE, Lambda1050+);

[0188] (4) Yellowing: Calculate the yellowing value by testing the yellowing (YI) value of the small laminated parts (3.2mm photovoltaic glass / 2 layers of encapsulation adhesive film / BEC301 CPC backboard) after 105℃-1000h aging by a color difference meter (ColorQuest XE).

[0189] Table 1

[0190]

[0191] As can be seen from Table 1, the corrosion resistance of the encapsulation adhesive film in the embodiments of the present application is obviously better than that of the comparative examples, has long-term corrosion resistance, and still has high visible light transmittance, good yellowing resistance, and has a broader application prospect.

[0192] It can be found from the performance test results of Comparative Examples 1-5 and Comparative Examples 3-4 that when the mass ratio of the acid absorbent to the base resin in the encapsulation adhesive film satisfies (0.1-1):100, the encapsulation adhesive film has obviously better corrosion resistance.

[0193] It can be found from the performance test results of Comparative Examples 1-5 and Comparative Examples 5-6 that when the grafting rate of the hydrolysis-resistant agent grafted modified acid absorbent is 1%-4%, the corrosion resistance of the encapsulation adhesive film is obviously better.

[0194] It can be found from the performance test results of Example 1 and Examples 8-10 in the present application that when the first silane coupling agent includes at least one of a carboxyl silane coupling agent, an amino silane coupling agent and a mercapto silane coupling agent, the corrosion resistance of the obtained encapsulation adhesive film is obviously better.

[0195] It can be found from the performance test results of Example 1 and Examples 11-14 in the present application that when the specific surface area of the acid absorbent is 5m 2 / g-50m 2 / g, the corrosion resistance of the encapsulation adhesive film is obviously better.

[0196] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An encapsulating film, characterized in that, It includes a matrix resin, an anti-hydrolysis agent graft-modified acid scavenger, and additives, wherein the additives include a crosslinking agent and a co-crosslinking agent; the mass ratio of the anti-hydrolysis agent graft-modified acid scavenger to the matrix resin is (0.1~1):100; and the grafting rate of the anti-hydrolysis agent graft-modified acid scavenger is 1%~4%.

2. The encapsulating film according to claim 1, characterized in that, The raw materials for preparing the anti-hydrolysis agent graft-modified acid absorbent include a first silane coupling agent, an acid absorbent, and an anti-hydrolysis agent.

3. The encapsulating film according to claim 2, characterized in that, The first silane coupling agent includes at least one of carboxylsilane coupling agents, aminosilane coupling agents, and mercaptosilane coupling agents; Preferably, the carboxysilane coupling agent comprises at least one of β-(carboxyethyl)silanetriol, sodium carboxyethylsilanetriol, and 3-(trimethoxysilyl)propionic acid; and / or, the aminosilane coupling agent comprises at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and phenylaminomethyltrimethoxysilane; and / or, the mercaptosilane coupling agent comprises at least one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and bis-(3-triethoxysilylpropyl)disulfide.

4. The encapsulating film according to claim 2, characterized in that, The acid absorbent is an alkaline metal compound, which includes at least one of metal oxides, metal hydroxides, carbonates, and phosphates. Preferably, the metal oxide includes at least one of magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, and manganese oxide; and / or, the metal hydroxide includes at least one of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, and hydrotalcite; and / or, the carbonate includes at least one of magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and magnesium bicarbonate; and / or, the phosphate includes at least one of zirconium phosphate, zirconium hydrogen phosphate, ammonium phosphate, ammonium polyphosphate, and titanium hydrogen phosphate.

5. The encapsulating film according to claim 2, characterized in that, The specific surface area of ​​the acid absorbent is 5m². 2 / g~50m 2 / g.

6. The encapsulating film according to claim 2, characterized in that, The anti-hydrolysis agent is at least one of carbodiimide compounds, glycidyl ether compounds, and epoxy compounds; Preferably, the carbodiimide compound comprises at least one selected from dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, polydicyclohexylmethane carbodiimide, polyhexamethylene carbodiimide, polyisophorone carbodiimide, poly4,4'-diphenylmethane carbodiimide, polytoluene carbodiimide, poly(p-phenylene) carbodiimide, polycyclohexane carbodiimide, and (γ-triethoxysilylpropyl)carbodiimide; and / or The glycidyl ether compound includes at least one of phenyl glycidyl ether, triglycidyl isocyanate, trimethoxy[3-(glycidyl ether)propyl]silane, and triethoxy[3-(glycidyl ether)propyl]silane; and / or, the epoxy compound includes at least one of 4-vinylepoxycyclohexane, (3,4-epoxycyclohexyl)methyl acrylate, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

7. The encapsulating film according to any one of claims 1 to 6, characterized in that, The mass ratio of the crosslinking agent to the anti-hydrolysis agent grafted modified acid scavenger is (0.01~1.5):(0.1~1); the mass ratio of the co-crosslinking agent to the anti-hydrolysis agent grafted modified acid scavenger is (0.5~5):(0.1~1). Preferably, The matrix resin is selected from at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, polyethylene, polyvinyl butyral, polymethyl methacrylate, polycarbonate, polyolefin plastisol, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-maleic anhydride copolymer, and thermoplastic polyurethane, more preferably at least one of ethylene-vinyl acetate copolymer, polyolefin elastomer, and polyvinyl butyral; And / or, the crosslinking agent is selected from any one or more of dicumyl peroxide, tert-butyl peroxide-2-ethylhexanoate, di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, tert-amyl peroxide, tert-butyl peroxide, 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane, tert-butyl peroxide-isopropyl carbonate, tert-amyl peroxide acetate, tert-amyl peroxide-(2-ethylhexyl)carbonate, tert-butyl peroxide-3,5,5-trimethylhexanoate, 1,1-di-tert-butylperoxide-cyclohexane, 2,2-bis(tert-butyl peroxide), tert-butyl peroxide-valerate, 1,1-bis(tert-amylperoxy)cyclohexane, and 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane; And / or, the co-crosslinking agent is selected from triethylamine, dimethylaminoethanol, methyl ethyl ketone oxime, cyclohexanone oxime, diphenylthiourea, tri(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ethoxylated trimethylolpropane triacrylate, propionyl glycerol triacrylate, ethoxylated glycerol triacrylate, propionyl glycerol triacrylate, and bis(trimethylolpropane)isocyanate. The following are any one or more of the following: hydroxymethylpropane tetraacrylate, bis(trimethylolpropane)tetramethacrylate, propionyl oxypentaerythritol tetraacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclodecanedimethyl diacrylate, propionyl oxyneopentyl glycol diacrylate, ethoxybisphenol A diacrylate, ethoxybisphenol A dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate.

8. The encapsulating film according to claim 7, characterized in that, The additives further include an antioxidant, a second silane coupling agent, and an anti-PID additive; the mass ratio of the antioxidant to the anti-hydrolysis agent graft-modified acid scavenger is (0.1~0.5):(0.1~1); the mass ratio of the second silane coupling agent to the anti-hydrolysis agent graft-modified acid scavenger is (0.1~5):(0.1~1); the mass ratio of the anti-PID additive to the anti-hydrolysis agent graft-modified acid scavenger is (0.1~0.5):(0.1~1). Preferably, the antioxidant is selected from 2,6-di-tert-butyl-4-methylphenol, bis(2,4-di-tert-butylphenyl)pentaerythritol dithiophosphate, dilauryl thiodipropionate, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite, bis-2,2,6,6-tetramethylpiperidinol sebacate, succinic acid and polymers of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1 Polymers of 6-hexanediamine and 2,4-dichloro-6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine, polymers of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine, polymers of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,6-hexanediamine and morpholin-2,4,6-trichloro-1,3,5-triazine Polymer, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate / methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate complex, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione / di(2,4-dicumylphenyl)pentaerythritol diphosphite complex; the second silane coupling agent is selected from ethylene. The anti-PID additive is selected from any one or more of the following: γ-triethoxysilane, γ-vinyltrimethoxysilane, γ-vinyltriperoxytert-butylsilane, γ-vinyltriacetoxysilane, γ-vinyltri(β-methoxyethoxy)silane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethylsilane, and 3-aminopropyltrimethylsilane; 9. A method for preparing an encapsulating film according to any one of claims 1 to 8, characterized in that, Includes the following steps: S1, the acid absorbent is dispersed in the first solvent to obtain a suspension; S2, the suspension is added to the first silane coupling agent to carry out the first reaction, and a silanized acid scavenger is obtained; S3, the silanized acid absorbent and the anti-hydrolysis agent are mixed in a second solvent to carry out a second reaction, thereby obtaining an anti-hydrolysis agent grafted and modified acid absorbent; S4, the anti-hydrolysis agent grafted modified acid scavenger is mixed with the first matrix resin and granulated to obtain anti-hydrolysis agent grafted modified acid scavenger masterbatch; S5, the anti-hydrolysis agent grafted modified acid absorbent masterbatch is mixed with the second matrix resin and additives, and cast into a film to obtain the encapsulating film.

10. A photovoltaic module, characterized in that, The photovoltaic module includes the encapsulating film according to any one of claims 1 to 8 or the encapsulating film prepared by the preparation method according to claim 9.

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