CN113881104B - Weather-resistant agent, weather-resistant polyester film, preparation method and application thereof - Google Patents

Weather-resistant agent, weather-resistant polyester film, preparation method and application thereof Download PDF

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Publication number
CN113881104B
CN113881104B CN202010619636.XA CN202010619636A CN113881104B CN 113881104 B CN113881104 B CN 113881104B CN 202010619636 A CN202010619636 A CN 202010619636A CN 113881104 B CN113881104 B CN 113881104B
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weather
polyester film
tert
resistant
agent
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CN113881104A (en
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钱振超
王睿
况军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
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    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

The invention relates to a weather-proof agent, a weather-proof polyester film, a preparation method and application thereof. The weather-resistant agent comprises a carrier and an auxiliary agent, wherein the carrier is a porous material, and the auxiliary agent is at least one of an antioxidant, a light stabilizer and an anti-hydrolysis agent. The porous material has pores with a pore diameter of 2 nm-10 mu m, and the porosity is more than 70%. The carrier is at least one selected from fumed silica, fumed titanium dioxide and fumed aluminum oxide. And (3) melting, blending and extruding the weather-resistant agent and thermoplastic polyester to form a film, so as to obtain the weather-resistant polyester film. The weather-resistant polyester film has hydrolysis resistance and ultraviolet resistance, and can be used for a solar cell backboard.

Description

Weather-resistant agent, weather-resistant polyester film, preparation method and application thereof
Technical Field
The invention relates to the field of films, in particular to a weather-proof agent, a hydrolysis-resistant ultraviolet-resistant weather-proof polyester film, a preparation method and application thereof.
Background
In the photovoltaic cell, the photovoltaic backboard is positioned on the back of the photovoltaic cell, plays a role in protecting and supporting the cell, is a photovoltaic packaging material which is directly contacted with the surrounding environment in a large area, and has the performances of ageing resistance (damp heat, dry heat, ultraviolet), electric insulation, water vapor blocking and the like. The photovoltaic backboard is classified according to chemical composition and mainly comprises a fluorine-containing backboard and a fluorine-free backboard. The fluorine-containing backboard is a backboard with a fluorine film or a fluorine coating as a weather-resistant protective layer, has excellent ultraviolet resistance, corrosion resistance, heat resistance and other performances, is suitable for being used as a backboard protective layer material, but has the defects of high price, high recovery technical requirement, easiness in generating environmental pollution and the like. Compared with fluorine-containing backboard, the fluorine-free backboard has the advantage of environmental protection, and the development of the fluorine-free backboard is mainly limited by poor weather resistance at present.
The prior art can reduce the content of carboxyl end groups to improve the hydrolysis resistance of the polyester by adding end capping agents such as carbodiimide, glycidyl ether/ester and isocyanate compounds to the polyester.
The patent CN101878251a blends polyester with modified polyolefin to improve the water resistance of the polyester film.
Patent CN101733925a discloses the addition of ultraviolet light absorbers and antioxidants to polyesters to improve the ultraviolet resistance of the polyesters.
Although the ultraviolet resistance and the hydrolysis resistance of the polyester can be improved to a certain extent in the prior art, the problems that the additive is easy to separate out and is easy to lose efficacy in the long-term service process exist, the content of the additive is limited, and the mechanical property and the processing property of the polyester can be influenced by excessive additives.
Disclosure of Invention
The invention provides a weather-proof agent and a weather-proof polyester film for a photovoltaic backboard, which is ultraviolet resistant and hydrolysis resistant. The weather-resistant polyester film contains a weather-resistant agent, the weather-resistant agent comprises a porous material loaded with an anti-aging auxiliary agent, an anti-aging function is realized in the service process of the weather-resistant polyester film, and continuous anti-ultraviolet and hydrolysis resistance is provided for the material.
The invention aims at providing a weather-proof agent which comprises a carrier and an auxiliary agent, wherein the carrier is a porous material, and the auxiliary agent is at least one of an antioxidant, a light stabilizer and an anti-hydrolysis agent.
In the weather-resistant agent, the porous material has pores with the pore diameter of 2 nm-10 mu m, and the porosity of the porous material is more than 70%;
further, the pore diameter of the porous material is 20-100nm, and the porosity is more than 75%.
In the weathering agent of the present invention, the pore volume of the porous material is preferably 0.5 to 5cm 3 Preferably 0.5 to 3cm 3 /g；
In the weathering agent of the present invention, the specific surface area of the porous material is preferably 100 to 500m 2 Preferably 150 to 300m 2 /g。
In the weathering agent of the present invention, the mass ratio of the auxiliary agent to the carrier is preferably (1 to 20): 1, more preferably (1 to 10): 1.
The carrier in the weather-resistant agent is preferably one or a combination of more of fumed silica, fumed titanium dioxide and fumed aluminum oxide.
In the weather resistant agent of the present invention, the antioxidant may be selected from one or more of antioxidants commonly used in the art, preferably N, N ' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 2, 6-di-tert-butyl-p-cresol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene, N ' -bis (2-naphthyl) p-phenylenediamine, tris (2, 4-di-tert-butylphenyl) phosphite, 4' - [1,1' -biphenyl ] diphosphonite-tetrakis [2, 4-di-tert-butylphenyl ] phosphite, tris (4-nonylphenyl) phosphite, triphenyl phosphite; more preferably one or more of N, N '-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, tris (nonylphenol) phosphite, pentaerythritol tetrakis [3- (3', 5 '-di-tert-butyl-4' -hydroxyphenyl) propionate ], tris (4-nonylphenyl) phosphite.
In the weather resistant agent, the light stabilizer can be selected from one or more of light stabilizers common in the art, preferably 2-hydroxy-4-n-octoxybenzophenones, 2-hydroxy-4-methoxybenzophenone, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, polymers of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol, and 2, 2-thiobis (4-tert-octylphenol) n-butylamine nickel salt; more preferably one or more of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, 2-hydroxy-4-n-octoxybenzophenone.
In the weather-resistant agent, the weather-resistant agent can be selected from one or more of carbodiimide, polycarbodiimide, epoxidized polyolefin, epoxidized fatty acid ester, maleic anhydride grafted polyolefin and glycidyl methacrylate grafted polyolefin which are common in the art; more preferably one or more combinations of carbodiimide, maleic anhydride grafted polyolefin.
Various common assistants in the field, such as processing aids, chain extenders and the like, can be added into the weather-resistant agent according to the need, and the dosage of the weather-resistant agent is conventional or is adjusted according to the actual condition.
The second purpose of the invention is to provide a preparation method of the weather-resistant agent, which comprises the following steps: mixing the components including the carrier and the auxiliary agent with a solvent, and drying to obtain the weather-resistant agent.
According to a preferred embodiment of the present invention, the mass ratio of the auxiliary agent to the porous material is preferably (1 to 20): 1, and more preferably (1 to 10): 1.
According to a preferred embodiment of the present invention,
the solvent is not particularly limited, but is preferably one or more of ethanol, N-propanol, isopropanol, dioxane, phenol, acetic acid, acetone, acetonitrile, toluene, xylene, 1, 2-dichloroethane, trichloroethylene, pentane, cyclohexane, N-hexane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, ethyl acetate, diethyl ether, methyl butyl ether, and dimethyl sulfoxide.
The amount of the solvent is not particularly limited, and is mainly for the purpose of sufficiently mixing the components, and the mass ratio of the porous material to the solvent is preferably 1 (4 to 100), more preferably 1 (10 to 50).
The mixing is not particularly limited, and various mixing methods generally used in the art may be employed.
The drying treatment is not particularly limited, and may be a drying treatment method generally used in the art, and preferably one or a combination of more of supercritical drying, freeze drying, reduced pressure drying, normal pressure drying, spray drying, microwave drying, and infrared drying.
It is a further object of the present invention to provide a weatherable polyester film comprising a thermoplastic polyester and the weatherable agent described above.
In the weather-resistant polyester film, the mass fraction of the weather-resistant agent in the weather-resistant polyester film is 1-20%, preferably 1-10%.
The thermoplastic polyester is not particularly limited, and is preferably one or a combination of more of polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polypropylene terephthalate, polycyclohexane dimethanol terephthalate, and polyethylene naphthalate.
Among the thermoplastic polyesters described above, the thermoplastic polyesters may be homopolymers, copolymers, or a mixture of polymers.
According to the invention, the elongation at break of the polyester film is maintained at more than 30% after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH.
According to the invention, the polyester film is subjected to ultraviolet radiation with the wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the polyester film is lower than 3.
The fourth object of the invention is to provide a preparation method of the weather-resistant polyester film, which comprises the following steps: and (3) melting, blending and extruding the weather-resistant agent and thermoplastic polyester to form a film, so as to obtain the weather-resistant polyester film.
In the preparation method of the weather-resistant polyester film, the extrusion film forming process is one or a combination of a plurality of casting process, calendaring process and two-way stretching process.
In the preparation process of the polyester film, the blending and extrusion processes of the raw material components can adopt the common polyester film processing process in the prior art.
The equipment used in the invention is also equipment in the polyester film processing in the prior art, such as a screw extruder, a casting machine, a calender, a film biaxial stretching machine and the like.
According to a preferred embodiment of the invention, the dried weathering agent is mixed with the thermoplastic polyester and blended in a screw extruder; the weather-proof polyester film is prepared by an extrusion film forming process.
The fifth purpose of the invention is to provide the application of the weather-proof polyester film in a solar cell backboard.
The weather-resistant polyester film has hydrolysis resistance and ultraviolet resistance, and can be used for a solar cell backboard.
The beneficial effects of the invention are as follows:
the invention prepares the weather-proof agent by embedding the auxiliary agent into the porous material in advance, and obtains the weather-proof polyester film by blending and extruding the weather-proof agent and the polyester through the existing polymer processing technology. In the service process of the weather-proof polyester film, the anti-aging function is realized, and durable protection is provided for the resin. Compared with the traditional weather-resistant polyester film obtained by directly blending the anti-aging agent with the resin, the polyester film prepared by the invention has more excellent weather resistance and longer service life.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are all disclosed in the prior art, if not particularly limited, and may be obtained, for example, directly or prepared according to the preparation method disclosed in the prior art.
Example 1
100g of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 50g of tris (4-nonylphenyl) phosphite, 50g of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 50g of carbodiimide, 200g of fumed silica (pore volume 0.8 cm) 3 Per g, pore diameter of 20-90nm, specific surface area of 200m 2 And/g, the porosity is 92%) and 2kg of ethyl acetate, and uniformly mixing the materials, drying the materials under reduced pressure, uniformly mixing the materials with 10kg of polyethylene terephthalate in a screw extruder, and obtaining the weather-resistant polyester film by a tape casting process.
The prepared polyester film has elongation at break after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RHThe holding rate was 45%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 1.5.
Example 2
20g of pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid were taken]60g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester, 80g of maleic anhydride-grafted polyolefin, 30g of fumed titanium dioxide (pore volume 1.3 cm) 3 Per g, pore diameter of 30-100nm, specific surface area of 150m 2 And (3) uniformly mixing/g with 300g of toluene, freeze-drying, uniformly mixing with 12kg of polyethylene naphthalate in a screw extruder, and calendaring to obtain the weather-resistant polyester film.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 50%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the film is 1.2.
Example 3
120g of 2, 6-di-tert-butyl-p-cresol, 80g of tris (nonylphenol) phosphite, 50g of 2-hydroxy-4-n-octoxybenzophenone, 50g of polycarbodiimide, 30g of gaseous aluminum oxide (pore volume 1.1 cm) 3 Per g, pore diameter of 20-90nm, specific surface area of 250m 2 And (3) uniformly mixing/g with 600g of isopropanol, performing supercritical drying, uniformly mixing with 16kg of polybutylene terephthalate in a screw extruder, and preparing the weather-resistant polyester film by using a tape casting process and a biaxial stretching process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 46%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 0.8.
Example 4
50g of stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 50g of triphenyl phosphite, 50g of 2-hydroxy-4-methoxybenzophenone, 50g of epoxidized polyolefin, 50g of fumed silica (pore volume 0.5 cm) 3 Per g, pore diameter of 20-80nm, specific surface area of 100m 2 And (3) uniformly mixing per gram, 75% of porosity) and 2kg of N, N-dimethylformamide, uniformly mixing with 7kg of polytrimethylene terephthalate in a screw extruder after freeze drying, and preparing the weather-resistant polyester film by a calendaring process and a biaxial stretching process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 52%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the film is 1.0.
Example 5
90g of 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene, 60g of tris (4-nonylphenyl) phosphite, 40g of 2, 2-thiobis (4-tert-octylphenol) n-butylamine nickel salt, 50g of epoxidized fatty acid ester, 60g of gaseous titanium dioxide (pore volume 1.5cm 3 Per g, pore diameter of 20-100nm, specific surface area of 300m 2 And (3) uniformly mixing the polyester film with 3kg of tetrahydrofuran, drying the mixture under reduced pressure, uniformly mixing the dried mixture with 3kg of poly (cyclohexanedimethanol terephthalate) in a screw extruder, and preparing the weather-resistant polyester film by a biaxial stretching process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 48%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the film is 1.4.
Example 6
70g of N, N ' -bis (2-naphthyl) p-phenylenediamine and 50g of 4,4' - [1,1' -biphenyl were taken]Subunit bisphosphonic acid-tetrakis [2, 4-di-tert-butylbenzene radical]Ester, polymer of succinic acid 10g with 4-hydroxy-2, 6-tetramethyl-1-piperidinol, maleic anhydride graft Polymer 20gOlefin, 50g of gas phase aluminum oxide (pore volume of 2.1 cm) 3 Per g, pore diameter of 25-90nm, specific surface area of 350m 2 And (3) uniformly mixing/g with 2kg of methyl butyl ether, drying at normal pressure, uniformly mixing with 1.4kg of polyethylene naphthalate in a screw extruder, and preparing the weather-resistant polyester film by a tape casting process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 50%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 1.5.
Example 7
100g of pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid were taken]Esters, 50g of tris (2, 4-di-tert-butylphenyl) phosphite, 50g of 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 11g of fumed silica (pore volume 2.9 cm) 3 Per g, pore diameter of 25-95nm, specific surface area of 400m 2 And (3) uniformly mixing/g, with 90% of porosity) and 60g of ethanol, uniformly mixing with 10kg of polyethylene terephthalate in a screw extruder after spray drying, and obtaining the weather-resistant polyester film by a calendaring process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 35%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 2.2.
Example 8
100g of 2, 6-di-tert-butyl-p-cresol, 50g of tris (4-nonylphenyl) phosphite, 50g of glycidyl methacrylate-grafted polyolefin, 15g of fumed titanium dioxide (pore volume 1.1 cm) 3 Per g, pore diameter of 20-100nm, specific surface area of 250m 2 Per g, porosity 82%) and 1kg dioxane, mixing uniformly, microwave drying, mixing uniformly with 8kg polyethylene naphthalate in a screw extruder, and preparing weather-proof polyester by tape casting and biaxial stretchingA film.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 40%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 2.5.
Example 9
20g of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 50g of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 50g of carbodiimide, 110g of aluminum oxide in the gas phase (pore volume 3.5 cm) 3 Per g, pore diameter of 20-70nm, specific surface area of 280m 2 And/g, porosity 92%) and 1kg of xylene, uniformly mixing, drying under reduced pressure, uniformly mixing with 4.6kg of poly (cyclohexanedimethanol terephthalate) in a screw extruder, and preparing the weather-resistant polyester film by a tape casting process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 50%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the film is 1.1.
Example 10
50g of 2-hydroxy-4-n-octoxybenzophenone, 50g of polycarbodiimide and 50g of fumed silica (pore volume of 4.0cm 3 Per g, pore diameter of 20-60nm, specific surface area of 300m 2 And (3) uniformly mixing/g with 2kg of ethyl acetate, infrared drying, uniformly mixing with 10kg of polyethylene terephthalate in a screw extruder, and preparing the weather-resistant polyester film by a biaxial stretching process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 48%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 0.9.
Comparative example 1
100g of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 50g of tris (4-nonylphenyl) phosphite, 50g of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 50g of carbodiimide and 2kg of ethyl acetate are taken, uniformly mixed, dried under reduced pressure and uniformly mixed with 10kg of polyethylene terephthalate in a screw extruder, and a weather-resistant polyester film is prepared by a tape casting process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 25%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 4.5.
Comparative example 2
20g of pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ], 60g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, 80g of maleic anhydride grafted polyolefin and 300g of toluene are taken, uniformly mixed, and after freeze drying, the mixture is uniformly mixed with 12kg of polyethylene naphthalate in a screw extruder, so that the weather-resistant polyester film is prepared by a calendaring process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 28%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled to be 60+/-5 ℃, the yellowing value of the film is 3.2.
Comparative example 3
100g of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 50g of tris (4-nonylphenyl) phosphite, 50g of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 50g of carbodiimide, 300g of fumed silica (pore volume 0.8 cm) 3 Per g, pore diameter of 20-90nm, specific surface area of 200m 2 Per g, porosity 92%) and 2kg of ethyl acetate, drying under reduced pressure, mixing with 10kg of polyethylene terephthalate in a screw extruderAnd uniformly mixing, and preparing the weather-resistant polyester film by using a tape casting process.
The elongation at break retention rate of the prepared polyester film after 48 hours under the environment of the temperature of 121 ℃ and the humidity of 100%RH is 31%. The obtained polyester film is subjected to ultraviolet radiation with a wavelength of 280-385nm of 15kWh/m 2 Ultraviolet radiation with a wavelength of 280-320nm of 5kWh/m 2 When the temperature is controlled at 60+/-5 ℃, the yellowing value of the film is 2.8.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (11)

1. The weather-resistant polyester film comprises thermoplastic polyester and a weather-resistant agent, wherein the weather-resistant agent comprises a carrier and an auxiliary agent, the carrier is a porous material, and the auxiliary agent is at least one of an antioxidant, a light stabilizer and an anti-hydrolysis agent; the porous material is provided with pores with the pore diameter of 2 nm-10 mu m, and the porosity of the porous material is more than 70 percent; the pore volume of the porous material is 0.5-5 cm 3 /g; the specific surface area of the porous material is 100-500 m 2 /g; the carrier is at least one of fumed silica, fumed titanium dioxide and fumed aluminum oxide; the mass ratio of the auxiliary agent to the carrier is (1-20): 1; the preparation method of the weather-resistant agent comprises the following steps: mixing the components including the carrier and the auxiliary agent with a solvent, and drying.
2. The weatherable polyester film according to claim 1, characterized in that:
the mass fraction of the weather-proof agent in the weather-proof polyester film is 1-20%.
3. The weather-resistant polyester film according to claim 2, wherein:
the mass fraction of the weather-proof agent in the weather-proof polyester film is 1-10%.
4. The weatherable polyester film according to claim 1, characterized in that:
the thermoplastic polyester is at least one selected from polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polypropylene terephthalate, polycyclohexane dimethanol terephthalate and polyethylene naphthalate.
5. The weatherable polyester film according to claim 1, characterized in that:
the pore diameter of the porous material is 20-100nm, and the porosity of the porous material is more than 75%; and/or the number of the groups of groups,
the pore volume of the porous material is 0.5-3 cm 3 /g; and/or the number of the groups of groups,
the specific surface area of the porous material is 150-300 m 2 /g; and/or the number of the groups of groups,
the mass ratio of the auxiliary agent to the carrier is (1-10): 1.
6. The weatherable polyester film according to claim 1, characterized in that:
at least one antioxidant selected from N, N ' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 2, 6-di-tert-butyl-p-cresol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene, N ' -bis (2-naphthyl) p-phenylenediamine, tris (2, 4-di-tert-butylphenyl) phosphite, 4' - [1,1' -biphenyl ] phosphinate-tetrakis [2, 4-di-tert-butylphenyl ] phosphite, tris (nonylphenol) phosphite, tris (4-nonylphenyl) phosphite, triphenyl phosphite; and/or;
the light stabilizer is at least one selected from 2-hydroxy-4-n-octoxybenzophenones, 2-hydroxy-4-methoxybenzophenone, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol, and nickel n-butylamine salt of 2, 2-thiobis (4-tert-octylphenol); and/or;
the anti-hydrolysis agent is at least one selected from carbodiimide, polycarbodiimide, epoxidized polyolefin, epoxidized fatty acid ester, maleic anhydride grafted polyolefin and glycidyl methacrylate grafted polyolefin.
7. The weatherable polyester film according to claim 1, characterized in that:
the mass ratio of the auxiliary agent to the carrier is (1-10) 1; and/or the number of the groups of groups,
the mass ratio of the carrier to the solvent is 1 (4-100); and/or the number of the groups of groups,
the solvent is at least one selected from ethanol, N-propanol, isopropanol, dioxane, phenol, acetic acid, acetone, acetonitrile, toluene, xylene, 1, 2-dichloroethane, trichloroethylene, pentane, cyclohexane, N-hexane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, ethyl acetate, diethyl ether, methyl butyl ether and dimethyl sulfoxide; and/or the number of the groups of groups,
the drying treatment is at least one of supercritical drying, freeze drying, reduced pressure drying, normal pressure drying, spray drying, microwave drying and infrared drying.
8. The weatherable polyester film according to claim 7, characterized in that:
the mass ratio of the carrier to the solvent is 1 (10-50).
9. A method for producing the weather-resistant polyester film according to any one of claims 1 to 8, comprising the steps of:
and (3) melting, blending and extruding the weather-resistant agent and thermoplastic polyester to form a film, so as to obtain the weather-resistant polyester film.
10. The method for producing a weather-resistant polyester film according to claim 9, characterized in that:
the extrusion film forming process is one or a combination of more of a casting process, a calendaring process and a biaxial stretching process.
11. Use of the weatherable polyester film according to any one of claims 1 to 8 in a solar cell backsheet.
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