CN115401969A - Front film material and photovoltaic module - Google Patents

Front film material and photovoltaic module Download PDF

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Publication number
CN115401969A
CN115401969A CN202210966366.9A CN202210966366A CN115401969A CN 115401969 A CN115401969 A CN 115401969A CN 202210966366 A CN202210966366 A CN 202210966366A CN 115401969 A CN115401969 A CN 115401969A
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China
Prior art keywords
ultraviolet absorbent
liquid
light stabilizer
film material
transparent film
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CN202210966366.9A
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Chinese (zh)
Inventor
许先华
陈汝建
孙楠楠
孙晨洋
康春香
薛群山
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Zhongtian Photovoltaic Materials Co ltd
Jiangsu Zhongtian Technology Co Ltd
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Zhongtian Photovoltaic Materials Co ltd
Jiangsu Zhongtian Technology Co Ltd
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Priority to CN202210966366.9A priority Critical patent/CN115401969A/en
Publication of CN115401969A publication Critical patent/CN115401969A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/166—Magnesium halide, e.g. magnesium chloride
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    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

The invention provides a front film material and a photovoltaic module. The front film material comprises a fluorine-containing plastic transparent film and a water-blocking film, wherein a weather-resistant adhesive layer for connecting the fluorine-containing plastic transparent film and the water-blocking film is arranged between the fluorine-containing plastic transparent film and the water-blocking film, and a hydrophobic anti-reflection layer is arranged on the surface of one side of the fluorine-containing plastic transparent film, which is far away from the water-blocking film; the raw materials of the hydrophobic antireflection layer comprise magnesium fluoride, titanium dioxide and polydimethylsiloxane; the raw materials of the fluorine-containing plastic transparent film comprise fluorine-containing plastic, an antioxidant, a composite ultraviolet absorbent and a light stabilizer, wherein the composite ultraviolet absorbent comprises an organic ultraviolet absorbent and an inorganic ultraviolet absorbent. The invention also provides a photovoltaic module containing the front film material. The front film material provided by the invention has the characteristics of high light transmittance, high hydrophobicity, aging resistance and the like, and can be applied to the manufacturing of light and flexible photovoltaic modules.

Description

Front film material and photovoltaic module
Technical Field
The invention relates to the technical field of solar photovoltaic manufacturing, in particular to a front film material and a photovoltaic module.
Background
With the continuous development of the solar photovoltaic industry, the dual-glass assembly has a wide application prospect in the aspects of high-efficiency batteries, photovoltaic building integration and the like, however, due to double-sided glass packaging, the dual-glass assembly has the problems of large weight, high fragment rate of battery pieces, difficulty in installation, glass burst and the like, and is limited by the bearing requirements of part of industrial and commercial roofs and civil roofs.
Due to the crystal structure characteristic of PVDF, the light transmittance of PVDF is not high, basically about 90%, and cannot reach the light transmittance (94%) of glass, so that the PVDF cannot be used in batches. Moreover, although the PVDF surface itself has a certain hydrophobicity, the surface is prone to accumulate dust after being placed outdoors for a long time, thereby affecting the overall light transmission effect.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a front film material and a photovoltaic module. The front film material is light, high in light transmission, high in barrier property and strong in weather resistance, and can be applied to manufacturing of light and flexible photovoltaic modules.
In order to achieve the purpose, the invention provides a front film material which comprises a fluorine-containing plastic transparent film and a water-blocking film, wherein a weather-resistant adhesive layer for connecting the fluorine-containing plastic transparent film and the water-blocking film is arranged between the fluorine-containing plastic transparent film and the water-blocking film, and a hydrophobic antireflection layer is arranged on the surface of one side of the fluorine-containing plastic transparent film, which is far away from the water-blocking film; wherein the hydrophobic anti-reflection layer comprises the following raw materials in mass ratio of 1; the raw materials of the fluorine-containing plastic transparent film comprise, by mass, 85-100 parts of fluorine-containing plastic, 1-5 parts of an antioxidant, 1-5 parts of a composite ultraviolet absorbent and 1-5 parts of a light stabilizer, wherein the composite ultraviolet absorbent comprises an organic ultraviolet absorbent and an inorganic ultraviolet absorbent, and the mass ratio of the organic ultraviolet absorbent to the inorganic ultraviolet absorbent is more than 1; the inorganic ultraviolet absorbent comprises inorganic nano particles with the particle size of 5nm-50nm, and the organic ultraviolet absorbent comprises benzotriazole ultraviolet absorbent and/or triazine ultraviolet absorbent.
In the specific embodiment of the invention, the light transmittance of the fluorine-containing plastic such as PVDF and the like is about 90 percent and is lower than that of glass; in addition, although the fluoroplastic has certain hydrophobicity, after long-term outdoor use, the fluoroplastic can affect the overall light transmission effect due to dust accumulated on the surface. The hydrophobic anti-reflection layer is additionally arranged on the surface of the fluorine-containing plastic transparent film, so that the light transmittance of the fluorine-containing plastic transparent film can be improved to be more than 94 percent, and the degree equivalent to that of glass is achieved; and the hydrophobic antireflection layer can endow the surface of the fluorine-containing plastic transparent film with a self-cleaning effect, so that the photovoltaic module containing the front film material can generate electricity efficiently for a long time.
The hydrophobic antireflection layer provided by the invention is simple in raw material composition, and obtains a good antireflection hydrophobic effect through the synergistic effect between titanium dioxide and magnesium fluoride.
In the hydrophobic antireflection layer, the particle size of the magnesium fluoride is generally 1nm-1000nm, and the particle size of the titanium dioxide is generally 1nm-1000nm. By controlling the particle sizes of the magnesium fluoride and the titanium dioxide within a specific range, the method is favorable for obtaining lower surface energy and higher light transmittance, so that an excellent hydrophobic anti-reflection effect is obtained.
In the hydrophobic antireflection layer, the particle size of the polydimethylsiloxane may be 1 μm to 1000 μm.
According to a specific embodiment of the present invention, the thickness of the hydrophobic antireflection layer may be controlled to be 1 μm to 5 μm, and the contact angle of the hydrophobic antireflection layer with water may be 120 ° to 150 °, for example, 137 °.
According to the specific embodiment of the invention, compared with the case that the organic ultraviolet absorbent or the inorganic ultraviolet absorbent is added alone, the composite ultraviolet absorbent formed by adding the organic ultraviolet absorbent and the inorganic ultraviolet absorbent in a certain proportion into the fluoroplastic can not only improve the weather resistance, the ultraviolet insulation degree (especially the ultraviolet absorption in the wave band of 300-400 nm) and the long-term ultraviolet insulation property of the fluoroplastic transparent film formed by the fluoroplastic, thereby effectively protecting the water-blocking film positioned at the lower layer of the fluoroplastic transparent film from being damaged; the compatibility among all components of the fluorine-containing plastic transparent film can be improved, and the fluorine-containing plastic transparent film is prevented from being separated out under the condition of damp heat aging. The fluorine-containing plastic transparent film can keep high light transmission for a long time through the synergistic effect of the composite ultraviolet absorbent and the hydrophobic anti-reflection layer.
According to a specific embodiment of the present invention, the raw material of the fluoroplastic transparent film may further include 0 to 50 parts by mass of modified polymethyl methacrylate. The modified polymethyl methacrylate can improve the transverse toughness of the fluoroplastic transparent film, and simultaneously enhance the processability of the fluoroplastic, especially the processability of the fluoroplastic in a blow molding process.
In the above fluoroplastic transparent film, the fluoroplastic may include PVDF or the like.
In the above fluoroplastic transparent film, the inorganic ultraviolet absorber comprises zinc oxide, or a combination of zinc oxide and titanium dioxide. By adding zinc oxide, diffuse reflection can be reduced, the integral transparency of the fluorine-containing plastic transparent film is improved, and the light transmittance is increased, so that more light rays can be received by a photovoltaic module cell where the front film material is positioned, and the integral power generation power of the photovoltaic module is improved. In addition, the zinc oxide can also improve the absorption effect of ultraviolet rays of the fluorine-containing plastic transparent film in 350nm-400nm (UVA wave band), and improve the overall weather resistance of the front film material. By adding a small amount of titanium dioxide, the self-cleaning performance of the fluorine-containing plastic transparent film can be further improved, and the super-hydrophobicity of the hydrophobic anti-reflection layer can be kept in the long-term outdoor use process.
In the above fluoroplastic transparent film, when the inorganic ultraviolet absorber comprises a combination of zinc oxide and titanium dioxide, the mass ratio of the zinc oxide to the titanium dioxide is generally controlled to be 1.
The research of the invention finds that better stability and structural uniformity can be obtained in the production process of the fluorine-containing plastic transparent film by adjusting the particle size of the inorganic nano particles in the inorganic ultraviolet absorbent. When the particle size of the inorganic nano particles is too large, the fluorine-containing plastic transparent film has larger crystal points, and the haze of the product is higher and the transparency is poor; when the particle size of the inorganic nanoparticles is too small, obvious nanoparticle agglomeration appears in the fluorine-containing plastic transparent film, and the appearance of the product is adversely affected. According to the invention, the particle size of the inorganic nanoparticles is controlled within the range of 5-50nm, so that the haze of the product can be controlled within a proper range, the production stability of the product is effectively improved, and the problem of crystal points is avoided.
In some embodiments, the inorganic ultraviolet absorber may employ zinc oxide having a particle size of 5nm to 50nm, titanium dioxide having a particle size of 5nm to 50nm, or the like.
In the fluorine-containing plastic transparent film, the organic ultraviolet absorbent is generally selected from efficient absorbents such as benzotriazole ultraviolet absorbent, triazine ultraviolet absorbent and the like, and has strong absorption in the UVB waveband range of 300-350 nm. Compared with benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers have better durability. Specifically, the benzotriazole-based ultraviolet absorber may include a 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol-based ultraviolet absorber (UV 234 ultraviolet absorber).
According to the specific embodiment of the invention, compared with UVA, UVB has larger influence on the aging process of the water-resisting film, and according to the international standard regulation, the proportion of UVB in the ultraviolet aging box for the laboratory at present needs to reach 3% -10%. The amount of organic uv absorber is therefore generally controlled to be greater than the amount of inorganic uv absorber to achieve better UVB barrier and aging resistance.
The research of the invention finds that in the composite ultraviolet absorbent, the organic ultraviolet absorbent belongs to a consumable material, once the organic ultraviolet absorbent loses efficacy due to consumption, the organic ultraviolet absorbent loses efficacy from local expansion to the whole, and the overall weather resistance and the protective effect on the water-blocking film of the fluorine-containing plastic transparent film are influenced. In addition, if the content of the organic ultraviolet absorber is insufficient, the overall weather resistance of the transparent film is low, and particularly after UV200KWh, the fluorine-containing plastic transparent film becomes brittle and loses toughness, so that the water-blocking film covered by the fluorine-containing plastic transparent film cannot be protected. If the addition amount of the organic ultraviolet absorbent is too large, the fluorine-containing plastic transparent film is easy to have the precipitation problem under the dry heat and wet heat conditions: in some embodiments, the organic uv absorber precipitates after being placed under dry heat conditions (e.g., room temperature) for 2 months, and also precipitates under wet heat conditions (e.g., PCT96 h), which can significantly affect the transmittance of the entire fluoroplastic transparent film, thereby affecting the power generation efficiency of the module. The fluorine-containing plastic transparent film is rough due to the excessively high content of the inorganic ultraviolet absorbent, and the fluorine-containing plastic transparent film is easy to agglomerate due to large specific surface area and large surface energy of the inorganic ultraviolet absorbent such as nano zinc oxide, nano titanium oxide and the like, so that agglomeration is caused in the processing process, the appearance of the fluorine-containing plastic transparent film has obvious raised crystal points and other defects, and the appearance and the reliability of a photovoltaic module are influenced; if the content of the inorganic ultraviolet absorbent is too low, the composite ultraviolet absorbent cannot play an effective blocking role on ultraviolet rays in UVA wave bands, so that the integral fluorine-containing plastic transparent film fails in the UVA wave bands. Therefore, the organic ultraviolet absorbent and the inorganic ultraviolet absorbent are compounded according to a specific proportion, so that the ultraviolet absorption capacity of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent can be effectively exerted, the structural stability and the performance stability of a system can be greatly improved, the front film material still keeps higher ultraviolet isolation performance and light transmission after being placed for a long time or under an aging condition, and the precipitation phenomenon is avoided. In a specific embodiment of the present invention, the mass ratio of the organic uv absorber to the inorganic uv absorber is generally controlled from more than 1, less than 5.
In the above-mentioned fluoroplastic transparent film, the antioxidant generally includes one or a combination of two or more of hindered phenol-based antioxidants, phosphorous-based antioxidants and the like. In some embodiments, the antioxidant may also be a complex antioxidant, and specifically may be a complex antioxidant comprising a hindered phenolic antioxidant and a phosphorous antioxidant. For example, the present invention may employ a complex antioxidant in which the primary antioxidant is a hindered phenol 1010 and the secondary antioxidant is a phosphite 168.
In the above fluoroplastic transparent film, the light stabilizer generally includes one or a combination of two or more of a polymeric high molecular weight hindered amine light stabilizer, a low molecular weight Hindered Amine Light Stabilizer (HALS), and a non-polymeric high molecular weight hindered amine light stabilizer. Wherein, the molecular weight of the polymeric high molecular weight hindered amine light stabilizer adopted by the invention can be 2000-4000, such as Tinuvin 622; the molecular weight of the low molecular weight hindered amine light stabilizer adopted by the invention can be 100-1000; the molecular weight of the non-polymeric high molecular weight hindered amine light stabilizer adopted by the invention can be 100-200.
According to the specific embodiment of the invention, the thickness of the fluorine-containing plastic transparent film is generally controlled to be 10-50 μm, and the light transmittance of the fluorine-containing plastic transparent film at 400-1100nm can reach more than or equal to 91%; the barrier rate of the fluorine-containing plastic transparent film to ultraviolet rays with the wavelength of 280nm-380nm can reach more than or equal to 98 percent.
According to a specific embodiment of the present invention, the raw materials of the weather-resistant adhesive layer may include a pressure-sensitive adhesive, a liquid uv absorber combination, and a solid uv absorber combination.
According to the specific embodiment of the present invention, the mass ratio of the liquid ultraviolet absorbent combination to the solid ultraviolet absorbent combination can be controlled to be 3. According to the research of the invention, when the mass ratio of the liquid ultraviolet absorbent combination to the solid ultraviolet absorbent combination is 3. In some embodiments, the liquid uv absorber combination and the solid uv absorber combination have a uv blocking capability of 4.
In the above weather-resistant adhesive layer, the pressure-sensitive adhesive may include one or a combination of two or more of an acrylate-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a polyurethane-based pressure-sensitive adhesive. In some embodiments, the pressure sensitive adhesive is preferably an acrylate pressure sensitive adhesive, which has better long-lasting properties than polyester pressure sensitive adhesives and polyurethane pressure sensitive adhesives, and requires less solvent and is more environmentally friendly.
In the weather-resistant adhesive layer, the acrylate pressure-sensitive adhesive is generally a one-component solvent-based pressure-sensitive adhesive, and for example, a one-component solvent-based pressure-sensitive adhesive whose main component is a polyisocyanate resin may be used. In some embodiments, the one-component solvent-based pressure-sensitive adhesive may have a solid content of 30% to 50%, and a viscosity of 3500 to 5500 mPa-s at 25 ℃ at room temperature. In a specific embodiment, when the solvent-based acrylate pressure-sensitive adhesive is used, the total mass of the raw materials of the weather-resistant adhesive layer is calculated by taking the solution mass of the solvent-based acrylate pressure-sensitive adhesive as the mass of the pressure-sensitive adhesive.
In the weather-resistant adhesive layer, the liquid ultraviolet absorbent combination and the solid ultraviolet absorbent combination are added into the pressure-sensitive adhesive, so that the weather resistance of the pressure-sensitive adhesive can be improved, and the whole weather resistance and the service life of the weather-resistant adhesive layer can be prolonged.
In the above weatherable adhesive layer, the liquid uv absorber combination may include a liquid uv absorber, a liquid light stabilizer, and a liquid antioxidant.
In the above liquid ultraviolet absorber combination, the liquid ultraviolet absorber may include a liquid benzotriazole-based ultraviolet absorber UV-571 and/or a liquid triazine-based ultraviolet absorber UV-400MPA, and the like.
In the above liquid ultraviolet absorber combination, the liquid antioxidant includes liquid hindered phenol antioxidant AO-1135, etc.
In the above liquid ultraviolet absorber combination, the liquid light stabilizer is generally a liquid-like composite light stabilizer. The composite light stabilizer comprises a synergistic mixture of IRGANOX 1135, TINUVIN 571 and TINUVIN 765. In some embodiments, the composite light stabilizer may be a composite light stabilizer B75 manufactured by basf corporation.
In the above liquid ultraviolet absorber combination, the mass ratio of the liquid ultraviolet absorber, the liquid light stabilizer and the liquid antioxidant is preferably 1.
In the above weatherable adhesive layer, the solid uv absorber combination may include a solid uv absorber and a solid light stabilizer.
In the above solid ultraviolet absorber combination, the solid ultraviolet absorber may include one or a combination of two or more of a powdered benzotriazole-based ultraviolet absorber UV-234, a powdered triazine-based ultraviolet absorber UV-1577, a powdered BETTERSOL UV-1697, and the like.
In the above-mentioned solid UV absorber combinations, the solid light stabilizer is preferably selected from neutral solid light stabilizers, for example, hindered Amine Light Stabilizers (HALS) may be used. The Hindered Amine Light Stabilizer (HALS) includes HALS-292, HALS-123, and the like.
In the above solid ultraviolet absorber combination, the mass ratio of the solid ultraviolet absorber to the solid light stabilizer is preferably 1.
According to the specific embodiment of the invention, the thickness of the weather-resistant adhesive layer can be controlled to be 20-100 μm, the light transmittance of the weather-resistant adhesive layer in the range of 400-1100nm can be more than or equal to 90%, and the ultraviolet blocking rate in the range of 280-380nm can be more than or equal to 97%.
In the foregoing film material, the water blocking film may include a material having water blocking performance, or may include a material having no water blocking performance. For example, the material of the water-blocking film may specifically include film materials such as PET and polyester (e.g., polycarbonate).
According to the specific embodiment of the invention, the light transmittance of the front film material in the range of 400nm-1100nm can reach more than 93%; the blocking rate of the front film material to ultraviolet rays of 280-380nm can reach more than 98%, and the whole thickness of the front film material is 50-300 mu m.
According to a specific embodiment of the present invention, the method for preparing the front film material may comprise:
s1, uniformly stirring a liquid ultraviolet absorbent, a liquid light stabilizer, a liquid antioxidant, a solid ultraviolet absorbent, a solid light stabilizer and a solid antioxidant in proportion, then mixing the obtained mixture with a pressure-sensitive adhesive to obtain a raw material of a weather-resistant adhesive layer, and preferably stirring and dissolving at the temperature of about 50 ℃ to facilitate the rapid dissolution of the solid ultraviolet absorbent, the solid light stabilizer and the solid antioxidant; after the materials are completely dissolved, coating the raw materials of the weather-resistant adhesive layer on the surface of the water-blocking film, controlling the thickness of the weather-resistant adhesive layer to be 20-100 mu m (preferably 50 mu m), standing at room temperature for 24h, and curing at 60 ℃ for 24h to form the weather-resistant adhesive layer;
s2, mixing the fluorine-containing plastic, the composite ultraviolet absorbent, the light stabilizer, the antioxidant and the modified polymethyl methacrylate, and obtaining the fluorine-containing plastic transparent film in a double-layer extrusion film blowing mode;
s3, stirring and mixing magnesium fluoride, titanium dioxide and a polydimethylsiloxane solution (generally taking ethyl acetate as a solvent) at normal temperature, stirring to form a raw material of a hydrophobic anti-reflection layer, and putting the raw material into a spraying device for later use;
s4, compounding the fluorine-containing plastic transparent film with the surface of the weather-resistant adhesive layer; and then spraying a raw material of the hydrophobic anti-reflection layer on the surface of the fluorine-containing plastic transparent film on the side far away from the water-resistant film, standing at room temperature for 24h, and curing at 55 ℃ for 48h to obtain the front film material.
The invention also provides a photovoltaic module which comprises the front film material. The front film material can be used as a transparent back plate to be applied to packaging of double-sided components, and plays excellent packaging and protection roles.
The invention has the beneficial effects that: the front film material provided by the invention is a novel packaging material with high light transmission, high barrier, strong weather resistance and light weight, can replace the existing front cover plate glass, effectively solves the problems of heaviness, difficult installation, easy burst, high fragment rate and the like faced by the glass packaging material, and can meet the outdoor use of a solar photovoltaic module.
Drawings
Fig. 1 is a schematic structural view of a front film material of example 1.
Fig. 2 is a water contact angle test chart of sample 2 of test example 1.
Fig. 3 is a water contact angle test chart of sample 3 of test example 1.
Fig. 4 is an SEM image of the crystal dot region in sample 7 of test example 2.
Fig. 5 is the EDS analysis result of the crystal spot region in sample 7 of test example 2.
Fig. 6 is a photomicrograph of the surface precipitated region of the sample in test example 3 in which the mass ratio of the organic ultraviolet absorber to the inorganic ultraviolet absorber is 6.
Fig. 7 is a photomicrograph of the surface area of the sample in test example 3 with a mass ratio of organic uv absorber to inorganic uv absorber of 4.
Fig. 8 is a result of an experiment performed on the PVDF transparent film of test example 3 in which the mass ratio of the organic ultraviolet absorber to the inorganic ultraviolet absorber is 4.
Description of the symbols
A hydrophobic antireflection layer 1, a PVDF transparent film 2, a weather-resistant adhesive layer 3 and a water-blocking film 4.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention should not be construed as limiting the implementable scope of the present invention.
Example 1
This embodiment provides a front film material having the structure shown in fig. 1. The front film material comprises a hydrophobic antireflection layer 1, a PVDF transparent film 2, a weather-resistant adhesive layer 3 and a water-blocking film 4 which are sequentially laminated. The weather-resistant adhesive layer 3 is used for connecting the PVDF transparent film 2 and the water-blocking film 4, and the weather-resistant adhesive layer 3 can prevent the water-blocking film 4 from aging by isolating most ultraviolet rays, so that the service life of the front film material is prolonged; the hydrophobic anti-reflection layer 1 is arranged on the surface of the PVDF transparent film 2 and used for providing self-cleaning and anti-reflection effects and enabling the PVDF transparent film 2 to keep high light transmittance for a long time. The thickness of the hydrophobic antireflection layer 1 is 5 micrometers, the thickness of the PVDF transparent film 2 is 25 micrometers, and the thickness of the weather-resistant adhesive layer 3 is 50 micrometers.
The preparation method of the front membrane material comprises the following steps:
1. weighing 2g of magnesium fluoride, 1g of titanium dioxide, 9g of polydimethylsiloxane and 100mL of ethyl acetate, dissolving the polydimethylsiloxane in the ethyl acetate, stirring at normal temperature until the polydimethylsiloxane is dissolved, then adding the magnesium fluoride and the titanium dioxide, and stirring and dissolving to form a raw material of a hydrophobic anti-reflection layer 1;
wherein the particle size of the magnesium fluoride is 200nm, the particle size of the titanium dioxide is 50nm, and the particle size of the polydimethylsiloxane is 500 mu m.
2. Stirring 100 parts of polyvinylidene fluoride, 30 parts of modified polymethyl methacrylate, 5 parts of composite ultraviolet absorbent, 5 parts of antioxidant and 5 parts of light stabilizer in parts by mass to form a raw material of a PVDF transparent film; the composite ultraviolet absorbent consists of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent in a mass ratio of 4 to 1, wherein the organic ultraviolet absorbent is a 2- (2H-benzotriazole-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol ultraviolet absorbent, the inorganic ultraviolet absorbent consists of zinc oxide and titanium dioxide in a mass ratio of 2 to 1, the particle sizes of the zinc oxide and the titanium dioxide are both 50nm, the antioxidant is a composite antioxidant, the main antioxidant of the composite antioxidant is hindered phenol 1010, and the auxiliary antioxidant is phosphite 168; the light stabilizer is Tinuvin 622.
3. Weighing 2g of liquid ultraviolet absorbent, 1g of liquid light stabilizer and 1g of liquid antioxidant as a liquid ultraviolet absorbent combination, weighing 64g of solid ultraviolet absorbent and 32g of solid light stabilizer as a solid ultraviolet absorbent combination, and simultaneously weighing 3400g of solvent type acrylate pressure-sensitive adhesive. Mixing the liquid ultraviolet absorbent combination and the solid ultraviolet absorbent combination, then mixing the mixture with the solvent type acrylate pressure-sensitive agent, and stirring and dissolving the mixture uniformly at 50 ℃ to form a raw material of the weather-resistant adhesive layer;
the liquid ultraviolet absorbent is a liquid triazine ultraviolet absorbent UV-400MPA, the liquid light stabilizer is a liquid composite light stabilizer B75, the liquid antioxidant is a liquid hindered phenol antioxidant AO-1135, the solid ultraviolet absorbent is a benzotriazole ultraviolet absorbent UV-234, the solid light stabilizer is a hindered amine light stabilizer HALS-292, and the solvent type acrylate pressure sensitive adhesive manufacturer is Shanghai WeikI new photoelectric material Co., ltd, and is of the model number XA640.
4. Coating the raw material of the weather-resistant adhesive layer on the surface of a water-blocking PET film by using scraper type coating equipment, standing at room temperature for 24h, curing at 60 ℃ for 24h through a drying channel, then compounding the PVDF transparent film with the surface of the weather-resistant adhesive layer, spraying the raw material of the hydrophobic antireflection layer on the surface (the side far away from the water-blocking PET film) of the PVDF transparent film, standing for 24h, and curing at 55 ℃ for 48h to obtain the front film material.
Example 2
This embodiment provides a front film material having the structure shown in fig. 1. The front film material comprises a hydrophobic antireflection layer 1, a PVDF transparent film 2, a weather-resistant adhesive layer 3 and a water-blocking film 4 which are sequentially laminated. The weather-resistant adhesive layer 3 is used for connecting the PVDF transparent film 2 and the water-blocking film 4, and prevents the water-blocking film 4 from aging under the action of isolating most ultraviolet rays, so that the service life of the front film material is prolonged; the hydrophobic anti-reflection layer 1 is arranged on the surface of the PVDF transparent film 2 and is used for providing self-cleaning and anti-reflection effects and enabling the PVDF transparent film to keep high light transmittance for a long time. The thickness of the hydrophobic antireflection layer 1 is 2 micrometers, the thickness of the PVDF transparent film 2 is 25 micrometers, and the thickness of the weather-resistant adhesive layer 3 is 50 micrometers.
The preparation method of the front film material of the embodiment comprises the following steps:
1. the components and the proportion of the raw materials of the hydrophobic anti-reflection layer are the same as those of the raw materials of the embodiment 1; wherein the particle size of the magnesium fluoride is 50nm, the particle size of the titanium dioxide is 50nm, and the particle size of the polydimethylsiloxane is 100 mu m.
2. Stirring 100 parts of polyvinylidene fluoride, 15 parts of modified polymethyl methacrylate, 3 parts of composite ultraviolet absorber, 1 part of antioxidant and 1 part of light stabilizer in parts by mass to form a raw material of the PVDF transparent film; the composite ultraviolet absorbent consists of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent in a mass ratio of 3; the light stabilizer is Tinuvin 622.
3. Weighing 2g of liquid ultraviolet absorbent, 1g of liquid light stabilizer and 1g of liquid antioxidant as a liquid ultraviolet absorbent combination, weighing 64g of solid ultraviolet absorbent and 32g of solid light stabilizer as a solid ultraviolet absorbent combination, and simultaneously weighing 3400g of solvent type acrylate pressure-sensitive adhesive. Mixing the liquid ultraviolet absorbent combination and the solid ultraviolet absorbent combination, then mixing the mixture with the solvent type acrylate pressure-sensitive agent, and stirring and dissolving the mixture evenly at 50 ℃ to form a raw material of the weather-resistant adhesive layer;
the liquid ultraviolet absorbent is a liquid triazine ultraviolet absorbent UV-400MPA, the liquid light stabilizer is a liquid composite light stabilizer B75, the liquid antioxidant is a liquid hindered phenol antioxidant AO-1135, the solid ultraviolet absorbent is a benzotriazole ultraviolet absorbent UV-234, the solid light stabilizer is a hindered amine light stabilizer HALS-292, and the solvent type acrylate pressure sensitive adhesive manufacturer is Shanghai WeikI new photoelectric material Co., ltd, and is of the model number XA640.
4. Coating the raw material of the weather-resistant adhesive layer on the surface of a water-blocking PET film by using a scraper type coating device, standing for 24h at room temperature, curing for 24h at 60 ℃ through a drying channel, then compounding the PVDF transparent film with the surface of the weather-resistant adhesive layer, spraying the raw material of the hydrophobic anti-reflection layer on the surface of the PVDF transparent film (the side far away from the water-blocking PET film), standing for 24h, and curing for 48h at 55 ℃ to obtain the front film material.
Example 3
This embodiment provides a front film material having the structure shown in fig. 1. The front film material comprises a hydrophobic antireflection layer 1, a PVDF transparent film 2, a weather-resistant adhesive layer 3 and a water-blocking film 4 which are sequentially laminated. The weather-resistant adhesive layer 3 is used for connecting the PVDF transparent film 2 and the water-blocking film 4, and prevents the water-blocking film 4 from aging under the action of isolating most ultraviolet rays, so that the service life of the front film material is prolonged; the hydrophobic anti-reflection layer 1 is arranged on the surface of the PVDF transparent film 2 and is used for providing self-cleaning and anti-reflection effects and enabling the PVDF transparent film to keep high light transmittance for a long time. The thickness of the hydrophobic antireflection layer 1 is 5 micrometers, the thickness of the PVDF transparent film 2 is 15 micrometers, and the thickness of the weather-resistant adhesive layer 3 is 50 micrometers.
The preparation method of the front film material comprises the following steps:
1. the components and the proportion of the raw materials of the hydrophobic anti-reflection layer are the same as those of the raw materials of the embodiment 1; wherein the particle size of the magnesium fluoride is 70nm, the particle size of the titanium dioxide is 50nm, and the particle size of the polydimethylsiloxane is 200 mu m.
2. Stirring 100 parts of polyvinylidene fluoride, 10 parts of modified polymethyl methacrylate, 3 parts of composite ultraviolet absorber, 1 part of antioxidant and 1 part of light stabilizer in parts by mass to form a raw material of a PVDF transparent film; the composite ultraviolet absorbent consists of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent in a mass ratio of 3; the light stabilizer is Tinuvin 622.
3. Weighing 2g of liquid ultraviolet absorbent, 1g of liquid light stabilizer and 1g of liquid antioxidant as a liquid ultraviolet absorbent combination, weighing 64g of solid ultraviolet absorbent and 32g of solid light stabilizer as a solid ultraviolet absorbent combination, and simultaneously weighing 3400g of solvent type acrylate pressure-sensitive adhesive. Mixing the liquid ultraviolet absorbent combination and the solid ultraviolet absorbent combination, then mixing the mixture with the solvent type acrylate pressure-sensitive agent, and stirring and dissolving the mixture uniformly at 50 ℃ to form a raw material of the weather-resistant adhesive layer;
the liquid ultraviolet absorbent is a liquid triazine ultraviolet absorbent UV-400MPA, the liquid light stabilizer is a liquid composite light stabilizer B75, the liquid antioxidant is a liquid hindered phenol antioxidant AO-1135, the solid ultraviolet absorbent is a benzotriazole ultraviolet absorbent UV-234, the solid light stabilizer is a hindered amine light stabilizer HALS-292, and the solvent type acrylate pressure sensitive adhesive manufacturer is Shanghai WeikI new photoelectric material Co., ltd, and is of the model number XA640.
4. Coating the raw material of the weather-resistant adhesive layer on the surface of a water-blocking PET film by using a scraper type coating device, standing for 24h at room temperature, curing for 24h at 60 ℃ through a drying channel, then compounding the PVDF transparent film with the surface of the weather-resistant adhesive layer, spraying the raw material of the hydrophobic anti-reflection layer on the surface of the PVDF transparent film (the side far away from the water-blocking PET film), standing for 24h, and curing for 48h at 55 ℃ to obtain the front film material.
Test example 1
The test example provides a test experiment of the whole ultraviolet blocking effect, the light transmission effect and the hydrophobic effect of the front film before and after the surface of the PVDF transparent film is coated with the hydrophobic anti-reflection layer.
Sample 1 was a pre-film material prepared similarly to example 1, except that: sample 1 does not contain a hydrophobic antireflection layer, and the mass ratio of the organic ultraviolet absorber to the inorganic ultraviolet absorber in the PVDF transparent film of sample 1 is 3.
Sample 2 was a pre-film material prepared similarly to example 1, except that: the mass ratio of the organic ultraviolet absorber to the inorganic ultraviolet absorber in the PVDF transparent film of sample 2 was 3.
The test results are summarized in table 1. The test wave band of the light transmittance is 400nm-1100nm, and the test wave band of the ultraviolet blocking rate is 280nm-380nm.
TABLE 1
UV blocking Rate% Light transmittance% Water contact Angle (°)
Sample No. 1 98.65％ 90.94％ 122
Sample 2 98.76％ 93.27％ 137
As can be seen from Table 1, the overall transmittance (400-1100 nm) of the front film material without surface anti-reflection treatment is less than 91%, and has a certain difference compared with the photovoltaic glass (about 94%). After the PVDF transparent film is subjected to antireflection treatment (a hydrophobic antireflection film is additionally arranged), the light transmittance of the front film material with the hydrophobic antireflection layer is improved to 93 percent, which is close to that of glass, and the ultraviolet blocking capability is not influenced. The above results show that the method of the present invention adds a hydrophobic anti-reflection layer on the surface of the PVDF transparent film, which can greatly improve the overall light transmittance of the PVDF transparent film and the front film material.
Fig. 2 and 3 are water contact angle measurements of sample 1 and sample 2, which measured contact angles of about 122 ° and 137 ° for sample 1 and sample 2, respectively. It can be seen from table 1 that the hydrophobic anti-reflection layer can effectively improve the hydrophobicity of the surface of the front film material.
Test example 2
This test example provides a product stability test on PVDF transparent films containing inorganic uv absorbers of different particle sizes.
And respectively taking inorganic nano-particles with the particle sizes of more than 50nm, 5-50nm and less than 5nm as inorganic ultraviolet absorbers to prepare PVDF transparent films, and marking the PVDF transparent films as a sample 3, a sample 4 and a sample 5. Other component parameters and preparation methods of PVDF transparent film raw materials of sample 3, sample 4 and sample 5 are the same as those of example 1. The results of the haze test and the production stability results for each PVDF transparent film sample are summarized in table 2.
TABLE 2
Haze%) Production stability
Sample 3 (particle size > 50 nm) 19.7 Large crystal point problem
Sample 4 (particle size 5-50 nm) 8.42 Problem of non-crystal point
Sample 5 (particle size < 5 nm) 6.32 Large crystal point problem caused by agglomeration
Note: the large crystal point refers to a black point with the diameter of more than or equal to 1.3mm presented on the PVDF transparent film under a backlight lamp; the problem of large crystal points means that large crystal points exist on the film surface, and the number of the large crystal points is more than 2 per square meter;
the number of the film crystal points is inspected in the production process of the samples 4 and 5 by using a defect inspection machine, and the inspection result is as follows: in the production process of the sample 4, no black spots or transparent spots with the diameter of more than or equal to 1.3mm are generated, the diameter of most of the black spots or transparent spots is between 0.5mm and 1.3mm (not containing 1.3 mm), the number of the black spots or transparent spots is averagely 1 to 2 per square meter, and the appearance of the PVDF transparent film is excellent; in the batch production process of the sample 5, large crystal points (the diameter is more than or equal to 1.3 mm) on the surface are dense, and the average number of the large crystal points is 8-10 per square meter, so that the appearance of the PVDF transparent film surface is seriously influenced, the integral material of the front film is poor, and the service life of a photovoltaic module is shortened.
Fig. 4 is an SEM image of the crystal dot region in sample 5, and fig. 5 is the EDS analysis result of the crystal dot region in sample 5.
As can be seen from Table 2, when the particle size of the inorganic UV absorber is too large or too small, the PVDF transparent film has the crystal point problem, which affects the structural uniformity of the film, and the haze of the film material is increased by too large particle size of the inorganic UV absorber, which further affects the light transmittance (400 nm-1100 nm) of the PVDF transparent film. As can be seen from fig. 4 and 5, the inorganic uv absorber having an excessively small particle size causes agglomeration of inorganic particles, mainly zinc oxide, to form a crystalline region.
Test example 3
The test example provides the test of light transmittance, ultraviolet isolation and stability of PVDF transparent films containing inorganic ultraviolet absorbers and organic ultraviolet absorbers in different proportions. The other composition parameters and preparation method of the PVDF transparent film in this test example are the same as those in example 1, except for the mass ratio of the inorganic uv absorber to the organic uv absorber. The test results are shown in Table 3. In the table 3, 280nm-380nm is a test wave band for testing the ultraviolet blocking rate of the PVDF transparent film, and the test result is the blocking rate; 400nm-1100nm is the wave band for testing the light transmittance of the PVDF transparent film, and the test result is the light transmittance. The aging conditions of UV300KWh are the requirements of ultraviolet aging tests specified in section 6.26 of transparent protective film for packaging double-sided battery pack of the T/CPIA 0031-2021 standard, and the aging conditions of DH2000h are as follows: aging at 85 deg.C and 85RH% relative humidity for 2000 hr.
TABLE 3
Figure BDA0003795157020000131
As can be seen from Table 3, the initial ultraviolet blocking capacity (280 nm-380 nm) of the PVDF transparent film only containing a single inorganic ultraviolet absorbent is only 56%, and ultraviolet rays cannot be blocked for a long time, and as a front film integral material, the single inorganic ultraviolet absorbent cannot effectively protect a water blocking film after being aged under Ultraviolet (UV) and Damp Heat (DH) conditions, so that the integral front film becomes brittle and fails; and the PVDF transparent film only containing a single organic ultraviolet absorbent is precipitated after being placed indoors for 2 months at normal temperature, and the transmittance of the transparent PVDF film in the wavelength range of 400nm-1100nm is reduced by 2 percent compared with the initial transmittance. Compared with the prior art, the PVDF transparent film simultaneously added with the inorganic ultraviolet absorbent and the organic ultraviolet absorbent has good ultraviolet blocking capacity and high transparency, and further, when the mass ratio of the organic ultraviolet absorbent to the inorganic ultraviolet absorbent is controlled to be 1-4.
When the mass ratio of the organic ultraviolet absorbent to the inorganic ultraviolet absorbent is 4.
Fig. 6 is a photomicrograph of a surface precipitated region of a sample with a mass ratio of the organic ultraviolet absorbent to the inorganic ultraviolet absorbent of 6. Both fig. 6 and 7 were acquired by a kirschner confocal microscope.
Fig. 8 shows the results of a long-time standing test at room temperature for samples in which the mass ratio of the organic ultraviolet absorber to the inorganic ultraviolet absorber is 4.
As can be seen from table 3, fig. 6, fig. 7, and fig. 8, when the amount of the organic uv absorber is excessive relative to the amount of the inorganic uv absorber, the PVDF transparent film may be precipitated after being left for a long time at normal temperature or after aging. When the inorganic ultraviolet absorbent is excessive, the ultraviolet blocking capability is obviously reduced, which shows that the high light transmission, the high ultraviolet blocking performance and the long-term stability can be achieved only when the mass ratio of the two ultraviolet absorbents is controlled in a proper range. Further comparison shows that the simultaneous addition of two ultraviolet absorbers can ensure that the ultraviolet blocking capability of the transparent PVDF film under various aging conditions is maintained at more than 90 percent, so that the water blocking film is better protected, and the service life of the integral material of the front film is prolonged; on the other hand, the PVDF transparent film can be ensured not to precipitate after being placed indoors and outdoors for a long time, and the transmittance (400-1100 nm) of the PVDF transparent film is continuously ensured, which has the technical effect that the PVDF transparent film is not added with an organic ultraviolet absorbent alone or an inorganic ultraviolet absorbent alone.
Test example 4
The test example provides test experiments on the ultraviolet blocking effect, the light transmittance and the weather resistance of the weather-resistant adhesive layer added with different ultraviolet absorbers.
The aging conditions of UV300KWh were the UV aging test requirements specified in section 6.26 of transparent protective film for packaging double-sided battery pack, standard T/CPIA 0031-2021.
Experimental conditions for DH1000 h: aging is continuously carried out for 1000h under the conditions of 85 ℃ temperature and 85RH percent relative humidity.
Experimental conditions for TC 200: in an environmental test chamber cycling between (-40 deg.C) 2 deg.C to +85 deg.C 2 deg.C, the rate of temperature change between the highest and lowest temperatures should not exceed 100 deg.C/h, should remain stable for at least 10min at each extreme temperature, and one cycle time should not exceed 6h for a total of 200 cycles. Two aging experiments were performed according to the IEC61215 standard.
The test wave band of the light transmittance is 400-1100nm, and the test wave band of the ultraviolet blocking rate is 280-380 nm.
Samples 8 to 10 are pre-film materials and were prepared in a similar or identical manner to example 1. Sample 8 differs from the preparation of example 1 only in that: only the liquid ultraviolet absorber combination and the acrylate pressure-sensitive adhesive, and the solid ultraviolet absorber combination are added to the weather-resistant adhesive layer of the sample 8; sample 9 differed from the preparation of example 1 only in that: the weather-resistant adhesive layer of the sample 9 is only added with the solid ultraviolet absorbent combination, the acrylate pressure-sensitive adhesive and the liquid ultraviolet absorbent combination; sample 10 was prepared exactly the same as example 1, with the addition of a solid uv absorber combination and a liquid uv absorber combination to the weatherable adhesive layer of sample 10. The test results are summarized in table 4.
TABLE 4
Figure BDA0003795157020000151
From the results in table 4, it can be seen that the ultraviolet blocking rate of the weather-resistant adhesive layer using a single liquid ultraviolet absorber as an ultraviolet absorbing component is obviously reduced after aging by UV300KWh, DH1000h and TC200, which indicates that the protective capability of the weather-resistant adhesive layer to the water-blocking film is weakened; the weather-resistant adhesive layer taking a single solid ultraviolet absorbent as an ultraviolet absorption component has obviously reduced ultraviolet blocking capability and light transmittance after aging of DH1000h, because the solid ultraviolet absorbent is separated out. The weather-resistant adhesive layer prepared by compounding the liquid ultraviolet absorbent combination and the solid ultraviolet absorbent combination can ensure that the ultraviolet blocking capability of the material keeps excellent level under various aging conditions, can avoid the problem of precipitation under the damp and hot conditions, and ensures the long-lasting property and durability of the whole front film material.

Claims (16)

1. A front film material comprises a fluorine-containing plastic transparent film and a water-blocking film, wherein a weather-resistant adhesive layer for connecting the fluorine-containing plastic transparent film and the water-blocking film is arranged between the fluorine-containing plastic transparent film and the water-blocking film, and a hydrophobic anti-reflection layer is arranged on the surface of one side of the fluorine-containing plastic transparent film, which is far away from the water-blocking film;
wherein the hydrophobic anti-reflection layer comprises the following raw materials in mass ratio of 1;
the raw materials of the fluorine-containing plastic transparent film comprise, by mass, 85-100 parts of fluorine-containing plastic, 1-5 parts of an antioxidant, 1-5 parts of a composite ultraviolet absorbent and 1-5 parts of a light stabilizer, wherein the composite ultraviolet absorbent comprises an organic ultraviolet absorbent and an inorganic ultraviolet absorbent, and the mass ratio of the organic ultraviolet absorbent to the inorganic ultraviolet absorbent is more than 1;
the inorganic ultraviolet absorbent comprises inorganic nano particles with the particle size of 5nm-50nm, and the organic ultraviolet absorbent comprises benzotriazole ultraviolet absorbent and/or triazine ultraviolet absorbent.
2. The front film material according to claim 1, wherein in the raw material of the hydrophobic antireflection layer, the particle size of the polydimethylsiloxane is 1 μm to 1000 μm; the particle size of the magnesium fluoride is 1nm-1000nm, and the particle size of the titanium dioxide is 1nm-1000nm.
3. The front film material of claim 1 or 2, wherein the hydrophobic antireflective layer has a thickness of 1 μ ι η to 5 μ ι η and a contact angle with water of 120 ° to 150 °.
4. The front film material according to claim 1, wherein the raw material of the fluoroplastic transparent film further comprises 0 to 50 parts by mass of modified polymethyl methacrylate.
5. The pre-film material of claim 1, wherein the fluoroplastic comprises PVDF.
6. The pre-film material of claim 1, wherein the inorganic ultraviolet absorber comprises zinc oxide, or a combination of zinc oxide and titanium dioxide;
the mass ratio of the zinc oxide to the titanium dioxide is 1.
7. The pre-film material of claim 1, wherein the organic ultraviolet absorber comprises 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol.
8. The front film material according to claim 1, wherein in the raw material of the fluorine-containing plastic transparent film, the antioxidant comprises one or a combination of more than two of hindered phenol antioxidants and phosphorous antioxidants;
the light stabilizer comprises one or the combination of more than two of polymeric high molecular weight hindered amine light stabilizer, low molecular weight hindered amine light stabilizer and non-polymeric high molecular weight hindered amine light stabilizer; wherein the molecular weight of the polymeric high molecular weight hindered amine light stabilizer is 2000-4000, the molecular weight of the low molecular weight hindered amine light stabilizer is 100-1000, and the molecular weight of the non-polymeric high molecular weight hindered amine light stabilizer is 100-200.
9. The front film material according to any one of claims 1 and 4 to 8, wherein the thickness of the fluoroplastic transparent film is 10 μm to 50 μm, and the light transmittance of the fluoroplastic transparent film at 400nm to 1100nm is not less than 91%; the barrier rate of the fluorine-containing plastic transparent film to ultraviolet rays of 280-380nm is more than or equal to 98 percent.
10. The front film material of claim 1, wherein the raw materials of the weatherable adhesive layer comprise a pressure sensitive adhesive, a liquid uv absorber combination, and a solid uv absorber combination;
the mass ratio of the liquid ultraviolet absorbent combination to the solid ultraviolet absorbent combination is 3-97-5.
11. The front film material of claim 10, wherein the liquid uv absorber combination comprises a liquid uv absorber, a liquid light stabilizer, and a liquid antioxidant;
the solid ultraviolet absorber combination comprises a solid ultraviolet absorber and a solid light stabilizer;
the pressure-sensitive adhesive comprises one or the combination of more than two of acrylate pressure-sensitive adhesive, polyester pressure-sensitive adhesive and polyurethane pressure-sensitive adhesive.
12. The front film material of claim 11, wherein the liquid ultraviolet absorber comprises a liquid benzotriazole-based ultraviolet absorber UV-571 and/or a liquid triazine-based ultraviolet absorber UV-400MPA;
the liquid antioxidant comprises a liquid hindered phenol antioxidant AO-1135;
the liquid light stabilizer comprises a liquid-like composite light stabilizer comprising a mixture of IRGANOX 1135, TINUVIN 571, and TINUVIN 765;
the solid ultraviolet absorbent comprises one or more of powdery benzotriazole ultraviolet absorbent UV-234, triazine ultraviolet absorbent UV-1577 and BETTERSOL UV-1697;
the solid light stabilizer comprises a hindered amine light stabilizer, and the hindered amine light stabilizer comprises HALS-292 and/or HALS-123.
13. The pre-film material of claim 11, wherein in the liquid uv absorber combination, the liquid uv absorber, the liquid light stabilizer, and the liquid antioxidant are in a mass ratio of 1;
in the solid ultraviolet absorbent combination, the mass ratio of the solid ultraviolet absorbent to the solid light stabilizer is 1.
14. The front film material according to any one of claims 1 and 10-13, wherein the weatherable adhesive layer has a thickness of 20 μm to 100 μm, a light transmittance of the weatherable adhesive layer at 400nm to 1100nm is not less than 90%, and a uv blocking rate at 280nm to 380nm is not less than 97%.
15. The front film material of claim 1, wherein the light transmittance of the front film material at 400-1100nm is greater than or equal to 93%; the blocking rate of the front film material to ultraviolet rays of 280-380nm is more than or equal to 98%, and the whole thickness of the front film material is 50-300 mu m.
16. A photovoltaic module comprising the front film material of any one of claims 1-15.
CN202210966366.9A 2022-08-12 2022-08-12 Front film material and photovoltaic module Pending CN115401969A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000174297A (en) * 1998-12-07 2000-06-23 Bridgestone Corp Solar cell, and cover material and seal film there for
US20110220184A1 (en) * 2008-12-08 2011-09-15 Asahi Glass Company, Limited Fluororesin film and its use
CN106541656A (en) * 2016-09-19 2017-03-29 浙江凯阳新材料股份有限公司 It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof
JP2017098483A (en) * 2015-11-27 2017-06-01 凸版印刷株式会社 Solar cell surface protective sheet, solar cell module using solar cell surface protective sheet, and method for manufacturing the same
CN112635599A (en) * 2020-12-17 2021-04-09 浙江晶科能源有限公司 Composite film for photovoltaic module backboard, photovoltaic module backboard and photovoltaic module

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000174297A (en) * 1998-12-07 2000-06-23 Bridgestone Corp Solar cell, and cover material and seal film there for
US20110220184A1 (en) * 2008-12-08 2011-09-15 Asahi Glass Company, Limited Fluororesin film and its use
JP2017098483A (en) * 2015-11-27 2017-06-01 凸版印刷株式会社 Solar cell surface protective sheet, solar cell module using solar cell surface protective sheet, and method for manufacturing the same
CN106541656A (en) * 2016-09-19 2017-03-29 浙江凯阳新材料股份有限公司 It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof
CN112635599A (en) * 2020-12-17 2021-04-09 浙江晶科能源有限公司 Composite film for photovoltaic module backboard, photovoltaic module backboard and photovoltaic module

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