CN104178042B - A kind of solar module sealed Cellophane - Google Patents

Abstract

A solar cell component sealant film, the components are calculated in parts by mass: olefin polymer 100; thermal conductive filler 5-30; anti-aging agent 0.05-2; adhesion promoting polymer 1-20; The polymer is composed of a first olefin polymer and a second olefin polymer. The glass transition temperature of the first olefin polymer measured by DSC is in the range of -59°C to -32°C, and the melting peak is in the range of 42°C to 100°C. °C; the melting peak of the second olefin polymer measured by DSC ranges from 111 °C to 130 °C, and the melt flow rate measured at 190 °C under 2.16 kg ranges from 0.5 to 5 g/10 min; the first olefin polymer and the second The mass ratio of the diene polymer is 65:35˜90:10. The adhesive film of the present invention does not permeate into the transparent adhesive film on the glass side, is safe and reliable, has obvious heat conduction effect, can reduce the working temperature of the component, and improves the photoelectric conversion efficiency of the component when it is continuously working. Meanwhile, the manufacturing process is simple and the use is convenient.

Description

A kind of sealing film of solar cell module

technical field

The invention relates to the technical field of solar energy, in particular to a sealant film used for sealing solar battery modules.

Background technique

At present, EVA film is widely used in the sealing of solar cell modules. In recent years, some new sealing materials have emerged, such as silicone materials, polyvinyl butyral, polyurethane materials, polyolefin materials, etc., all of which have good properties. Aging resistance and adhesive properties. However, these materials all have the problem of poor thermal conductivity. The surface temperature of solar cell modules is often as high as 80°C when they are used outdoors. Relevant research shows that every 1°C decrease in module temperature can increase power generation efficiency by 0.4%. Therefore, reducing the operating temperature of modules is an effective means to improve power generation efficiency of modules.

The sealing film of the solar cell module is in direct contact with the cell, and its thermal conductivity is directly related to the heat dissipation of the entire module. Improving the thermal conductivity of the solar cell module sealing film can quickly transfer the heat generated by the cell to the external environment. Transfer, thereby reducing the operating temperature of solar modules.

In order to increase the thermal conductivity of solar cell module sealant film, many scientific research institutions and experts and scholars have made efforts in this area, but most of them are aimed at the improvement of EVA film. Ethylene-vinyl acetate polymer (EVA) can be firmly bonded to polar materials because of the polar vinyl acetate structural unit in its molecule, but it is precisely because of the presence of vinyl acetate polar structural units that the material’s The volume insulation resistivity is generally only 10 ¹³ Ω.cm. Adding inorganic thermally conductive fillers to the system will reduce the insulation performance of the adhesive film, which may cause quality accidents. In addition, the strong fluidity of EVA will cause white EVA on the back panel side. The problem of transparent EVA seeping into the glass side will cause the edge of the cell to turn white, which will affect the amount of light received by the edge of the cell, which in turn will reduce the power generation efficiency of the module. Chinese patent CN201320656697.9 introduces a double-layer photovoltaic module sealant film, which successfully solves the quality problem of the diffusion of the thermally conductive EVA film on the backplane side to the glass side EVA film, and due to the high reflectivity of EVA on the backplane side , It also improves the reuse of light by the battery sheet and increases the power generation efficiency of the module. Because the thermal conductivity of the adhesive film is improved, the heat dissipation performance of the module is also increased, but there are also problems in this solution. On the one hand, the thermal conductivity layer of the sealing adhesive film It needs to be cross-linked, because the presence of fillers will reduce the degree of cross-linking of the thermally conductive layer, thereby affecting the aging resistance of the adhesive film; on the other hand, the double-layer structure is used, and its manufacturing process is more complicated, which increases the cost.

Contents of the invention

In order to solve the above-mentioned problems of poor aging resistance and complex manufacturing process, the present invention provides a solar cell module sealing film.

The technical scheme that solves the above problems is:

A solar cell module sealant film, each component is calculated as follows in parts by mass:

100 parts by mass of olefin polymer;

Thermally conductive filler 5-30 parts by mass;

0.05 to 2 parts by mass of anti-aging agent;

1-20 parts by mass of adhesion-promoting polymer;

Wherein, the olefin polymer is composed of a first olefin polymer and a second olefin polymer, and the glass transition temperature range of the first olefin polymer measured by DSC is between -59°C and -32°C, and the melting peak range is 42°C. ℃～100℃; the melting peak range of the second olefin polymer measured by DSC is 111℃～130℃, and the melt flow rate measured under the condition of 190℃2.16kg is 0.5～5g/10min; the first olefin polymer The mass ratio of the polymer to the second olefin polymer is 65:35-90:10.

In the solar cell module sealant film, the thermally conductive filler is at least one of metal oxide, metal nitride, silicon dioxide, silicon nitride, and silicon carbide.

In the solar cell component sealant film, the thermally conductive filler is pretreated by one of silane coupling agent, stearic acid, hyperbranched polymer and peroxide.

In the solar cell module sealant film, the first olefin polymer is one or more of ethylene-α-olefin random copolymer and propylene-α-olefin random copolymer.

In the above solar cell module sealant film, the second olefin polymer is high-density polyethylene, low-density polyethylene, linear low-density polyethylene, propylene-alpha olefin copolymer, ethylene-alpha olefin block copolymer one or more.

In the above solar cell module sealant film, the adhesion promoting polymer contains Branched chain structure (n=1~10, m=1~4), the main chain is one of olefin copolymer or olefin homopolymer.

The above solar cell module sealant film, the main chain of the adhesion promoting polymer is ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer , ethylene-1-octene copolymer, ethylene-propylene-hexene copolymer, ethylene-pentene-hexene copolymer, ethylene-propylene-1,6-hexadiene copolymer, ethylene homopolymer, propylene homopolymer One of polymers, isoprene homopolymers, and 4-methyl-1-pentene homopolymers.

In the solar cell module sealing film, the anti-aging agent is composed of an ultraviolet light absorber, a light stabilizer, and an antioxidant.

Beneficial effect

Compared with the prior art, the adhesive film of the present invention does not penetrate into the transparent adhesive film on the glass side, is safe and reliable, and has an obvious heat conduction effect. When used on the back plate side of a solar cell module, it can reduce the working temperature of the module and improve the stability of the module when it continues to work. Photoelectric conversion efficiency.

The adhesive film of the invention has simple manufacturing process, single-layer structure, convenient use and low cost.

The present invention mixes the heat-conducting filler with the olefin polymer to prepare the solar energy sealant film, which solves the heat conduction problem of the sealant film and at the same time ensures the insulation performance; the main resin of the high-performance solar cell module sealant film in the present invention is two The composition of olefin-like polymers can endow the adhesive film with better low temperature resistance and high temperature creep resistance; due to the appropriate melt fluidity, it can ensure that the adhesive film and the cell are fully infiltrated to obtain better bonding performance .

By adding pretreated thermally conductive fillers to olefin polymers, a chemical link is established between thermally conductive fillers and polyolefins, which solves the problem of thermally conductive filler dispersion, improves melt strength during production, and reduces production difficulty. The migration of fillers during lamination is suppressed, and the thermal conductivity of the film is improved; the pretreatment of thermal conductive fillers can also solve the problem of lower melt strength of polyolefin materials caused by ordinary high filler content, ensuring the polyolefin film. Normal production; the improvement of melt strength also solves the problem of migration of thermally conductive fillers in the adhesive film to the upper layer during lamination.

The thermally conductive filler added is white powder, which can reflect light when added to the sealant film of the solar cell module, and can improve the reflectivity of the packaging material on the rear side of the module cell, thereby effectively improving the photoelectric conversion efficiency of the cell.

In a word, the high-performance solar cell module sealant film in the present invention has high thermal conductivity, high insulation, high reflectivity, low cost and low production process requirements, and the product has strong lamination adaptability, high temperature creep resistance Good denaturation performance.

detailed description

The main resin of the present invention contains two kinds of olefin polymers, and the olefin polymers have the characteristics of good insulation performance and stable molecular structure.

The first olefin polymer in the host resin may be one or more of ethylene-alpha olefin random copolymer and propylene-alpha olefin random copolymer. The first olefin polymer can guarantee the low temperature resistance of the sealant film, even in extremely cold places, it can still protect the cells in the module from being broken by the impact of external forces.

Examples of the ethylene-α-olefin random copolymer include, but are not limited to, the following materials: ethylene-propylene random copolymer, ethylene-1-butene random copolymer, ethylene-isobutylene random copolymer, Ethylene-1-pentene random copolymer, ethylene-2-methyl-1-butene random copolymer, ethylene-3-methyl-1-butene random copolymer, ethylene-1-hexene Regular copolymers, ethylene-1-heptene random copolymers, ethylene-1-octene random copolymers, ethylene-1-nonene random copolymers, ethylene-1-decene random copolymers; as propylene - The α-olefin random copolymers include, but are not limited to, the following materials: propylene-ethylene random copolymers, propylene-butene random copolymers.

An ethylene-1-butene random copolymer is preferably used as the first olefin polymer.

As the first olefin polymer, the glass transition temperature measured by DSC ranges from -59°C to -32°C. When the glass transition temperature of the first olefin polymer is lower than -59°C, the adhesive film is too soft, which is not conducive to components Evacuation during lamination; and when the glass transition temperature of the first olefin polymer is higher than -32°C, the low temperature resistance of the adhesive film is not good, and the battery sheet is easily damaged if it is impacted in a low temperature environment. The range of the melting peak measured by DSC is 42°C to 100°C. If the melting peak of the first olefin polymer is lower than 42°C, the high temperature creep resistance of the adhesive film is not good, which will cause the problem of cell displacement; if the melting peak is higher than 100°C, it cannot be used for the lamination process of the module. The battery sheet provides sufficient protection, so that the battery sheet is vulnerable to impact, causing cracks.

The second olefin polymer in the main resin of the above-mentioned sealant film can be one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, propylene-α olefin random copolymer, and ethylene-α olefin block copolymer. one or more species. The second olefin polymer can guarantee the heat resistance of the sealant film. When the component works normally, its surface temperature often reaches above 70°C. The second olefin polymer has a higher melting point and lower melt fluidity , which can ensure that the adhesive film will not undergo thermal creep and the cell will not slip under the working temperature of the component.

As the propylene-α-olefin random copolymer, the following materials can be listed, but not limited to the following materials: propylene-ethylene random copolymer, propylene-butene random copolymer; as ethylene-α-olefin block copolymer The following materials can be listed, but not limited to: ethylene-propylene block copolymer, ethylene-1-butene block copolymer, ethylene-isobutylene block copolymer, ethylene-1-pentene block copolymer , Ethylene-2-methyl-1-butene block copolymer, Ethylene-3-methyl-1-butene block copolymer, Ethylene-1-hexene block copolymer, Ethylene-1-heptene Block copolymer, ethylene-1-octene block copolymer, ethylene-1-nonene block copolymer, ethylene-1-decene block copolymer.

Low-density polyethylene is preferably used as the second olefin polymer.

As the second olefin polymer, its melting peak measured by DSC ranges from 111°C to 130°C. When the melting peak temperature of the second olefin polymer is lower than 111°C, the adhesive film is prone to thermal creep in a high-temperature working environment , leading to the displacement of the battery sheet; and when the melting peak temperature of the second olefin polymer is higher than 130°C, the blending performance of the second olefin polymer with the first olefin polymer is not ideal, and the thermal conduction path is defective. However, the melt flow rate measured at 190°C and 2.16kg ranges from 0.5 to 5g/10min. If the melt flow rate is lower than 0.5g/10min, the adhesive film will have insufficient infiltration with surrounding materials during component production. , affecting the yield of components; if the melt flow rate is higher than 5g/10min, the adhesive film has poor melt strength during high temperature processing and is not easy to form a film.

The mass ratio of the first olefin polymer to the second olefin polymer in the olefin polymer is in the range of 65:35 to 90:10, and when the mass ratio of the first olefin polymer to the second olefin polymer is lower than 65:35, it will The wettability of the sealant film to other materials is reduced, and the bonding performance is reduced; when the mass ratio of the first olefin polymer to the second olefin polymer is higher than 90:10, it will cause thermal creep of the film at the normal working temperature of the component Change, there is a problem of cell displacement.

Polymer materials generally have the problem of poor thermal conductivity, and olefin polymer materials naturally have the same problem. The thermal conductivity of low-density polyethylene is only 0.3W/m·k, and the thermal conductivity of HDPE with high crystallinity is only 0.4 W. /m•k, so to improve the thermal conductivity of polyolefin materials, it is generally necessary to add thermal conductive fillers. Insulation is a basic requirement of solar cell sealant film, so there will be certain restrictions when selecting thermally conductive fillers. As commonly used thermally conductive insulating fillers, metal oxides, metal nitrides, silicon dioxide, silicon nitride, One or a mixture of silicon carbide, specifically beryllium oxide, aluminum oxide, magnesium oxide, boron oxide, zinc oxide, calcium oxide, silicon dioxide, silicon nitride, silicon carbide, aluminum nitride, boron nitride, etc. Inorganic filler.

In order to obtain better thermal conductivity and price balance, metal oxides, metal nitrides, silicon dioxide, silicon nitride, silicon carbide whiskers and mixtures of their powders are generally used. Preference is given to using a mixture of filler whiskers of 1 to 100 μm and filler powder of 10 to 100 nm. Micron-level fillers can achieve overlapping between particles and form thermal conduction paths with a small amount of use; nano-level filler powders can repair defects in overlapping parts and improve the heat conduction efficiency of the entire heat conduction path.

The above-mentioned thermally conductive filler needs to be interface treated before being mixed with polyolefin resin. The polarity difference between inorganic particles such as thermally conductive filler and polyolefin resin is large, and the interface compatibility is poor, and the filler particles are easy to agglomerate in the matrix resin. , which affects the bridging efficiency of the thermal conduction path; in addition, due to the compatibility of the thermally conductive filler and the polyolefin resin, the polyolefin resin is difficult to infiltrate the surface of the inorganic filler, and voids are often formed at the interface between the two, which increases the polyolefin composite material. interface thermal resistance. Silane coupling agents, stearic acid and hyperbranched polymers can be used to treat the surface of thermally conductive fillers. One end of these modifiers will combine with the hydroxyl groups on the surface of thermally conductive fillers, and the other end will be compatible with the polyolefin matrix resin. One end of the silane coupling agent can condense with the hydroxyl groups on the surface of the filler, and the other end can form a bridge with the polyolefin material. Compared with other modified materials, it can provide more reliable compatibility improvements for thermally conductive fillers and polyolefin materials.

Only using the above-mentioned thermally conductive fillers for interface modification is not enough to obtain ideal performance. It is very necessary to use peroxides to treat them. On the one hand, peroxides can stimulate one end of the silane coupling agent to graft with polyolefin materials. Reaction, enhance the modification effect of silane coupling agent, ensure that the thermally conductive particles are uniformly dispersed in the polyolefin film, and improve the overall thermal conductivity of the film; on the other hand, the processing temperature of the polyolefin film is high, and the melt strength is not good High, the addition of thermally conductive fillers further reduces its melt strength, but the presence of a small amount of peroxide in the thermally conductive filler can initiate slight polymerization of the adhesive film, enhance the melt strength of the adhesive film, and solve the problem of difficult production; finally , The increase in the melt strength of the adhesive film also solves the problem of migration of thermally conductive fillers in the adhesive film to the upper layer during lamination.

As the above-mentioned thermally conductive filler, relative to 100 parts by mass of the above-mentioned base resin olefin polymer, when its dosage is 5 to 30 parts by mass, the thermal conductivity of the sealant film is better. There is no thermal conduction path in the system, the thermal conductivity of the adhesive film does not increase, and the thermal conduction effect cannot be improved; when the amount exceeds 30 parts by mass, on the one hand, the insulation performance of the sealing adhesive film decreases significantly; on the other hand, the sealing adhesive film During melt extrusion, the melt strength of the adhesive film is not enough, and it is difficult to make a uniform film material.

Olefin polymers are non-polar and do not bond to glass by themselves. They need to be modified with adhesion-promoting polymers to bond polyolefins to glass. The adhesion promoting polymer used in the high performance sealant film of the present invention contains Branched chain structure, the branched chain structure of the adhesion promoting polymer is prone to hydrolysis reaction to form silanol branched chains , The silanol branch chain can bond with the hydroxyl group on the glass surface, so that the adhesive film and the glass can be chemically bonded, and play a role in increasing the adhesion of the polyolefin adhesive film.

As an adhesion promoting polymer with The branched chain structure, n=1~10, m=1~4, more detailed branched chain structure can be listed , , , , or , The adhesion-promoting polymer may contain one or more of these branched chain structures, and may not be limited to the above-listed branched chain structures.

As an adhesion promoting polymer, its main structure is composed of olefin copolymers or olefin homopolymers.

As the olefin copolymer, the following materials can be listed, but not limited to the following materials: ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene- 1-octene copolymer, ethylene-propylene-hexene copolymer, ethylene-pentene-hexene copolymer, ethylene-propylene-1,6-hexadiene copolymer, etc., in consideration of the moldability of the material, it is preferable Ethylene-1-octene copolymer was used as the backbone for the adhesion promoting polymer.

As the olefin homopolymer, the following materials can be listed, but not limited to the following materials: ethylene homopolymer, propylene homopolymer, isoprene homopolymer, 4-methyl-1-pentene homopolymer, etc., In view of the low temperature processing of the material, it is preferred to use ethylene homopolymer as the host structure of the adhesion promoting polymer.

As the above-mentioned adhesion-promoting polymers, SX522A: CM401 (silane-grafted LDPE) and SX720: CM488 (silane-grafted MDPE) of AEI Compounds; LINKLON XLE815N (silane-grafted LLDPE) of Mitsubishi Chemical Corporation, LINKLON QS241HZ (silane grafted HDPE), LINKLON XPF860G (silane grafted PP); Zhejiang Wanma Polymer Materials Co., Ltd. YJG-3 (silane grafted PE), etc.

With respect to 100 parts by mass of the olefin polymer in the solar cell module sealant film, the content of the adhesion-promoting polymer is preferably between 1 and 20 parts by mass. When the content of the adhesion-promoting polymer exceeds 20 parts by mass, the cost of the product will be uneconomical; when the amount is less than 1 part by mass, the effect of improving the adhesion of the solar sealant film is not obvious , and can not guarantee the long-term use of the film; when its dosage is controlled at 1 to 20 parts by mass, it can solve the problem of non-adhesive force of olefin polymers, and can also provide durable adhesion for the film.

In order to prolong the service life of the sealant film, the present invention adds an anti-aging agent when the film is prepared, and the anti-aging agent in the present invention consists of an ultraviolet absorber, a light stabilizer and an antioxidant.

As the above-mentioned ultraviolet light absorber, it is possible to suppress aging of olefin polymer materials caused by ultraviolet rays emitted by the sun. The ultraviolet absorber used in the present invention can be selected from the ultraviolet absorbers commonly used in this field, such as various types of ultraviolet absorbers such as benzophenones, benzotriazoles, triazines, salicylates and the like. Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octyloxy Base benzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-Hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methanone Oxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc.; as benzotriazoles The ultraviolet absorber is a benzotriazole compound substituted by a hydroxyphenyl group, such as 2-(2-hydroxyl-5-methylphenyl)benzotriazole, 2-(2-hydroxyl-5-tert-butyl phenyl)benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)benzotriazole, 2-(2-methyl-4-hydroxyphenyl)benzotriazole, 2-(2-Hydroxy-3-methyl-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2- (2-Hydroxy-3,5-dimethylphenyl)-5-methoxybenzotriazole, (2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzo Triazole, (2-hydroxy-5-tert-butylphenyl)-5-chlorobenzotriazole, etc. Examples of triazine UV absorbers include 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy ) phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol and the like. Examples of salicylates include phenyl salicylate, p-octylphenyl salicylate, and the like; as the ultraviolet light absorber, benzophenone-based ultraviolet light absorbers are preferred, and 2,2'-bis Hydroxy-4-methoxybenzophenone as UV absorber for high-performance solar cell module sealant film.

The light stabilizer mainly refers to hindered amine organic substances. It is generally believed that hindered amine light stabilizers have the functions of free radical capture, singlet oxygen quenching, and hydroperoxide decomposition, and can provide effective protection for polymers. The hindered amine light stabilizers commonly used in this field can be listed: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, succinic acid and (4-hydroxy-2 , 2,6,6-tetramethyl-1-piperidinol) polymer, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3, 5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexadiene[(2,2,6,6-tetra Methyl-4-piperidinyl)imino]}, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2 , 2,6,6-pentamethyl-4-piperidinyl) sebacate, the products on the market can enumerate CYASORB UV-3346, SYASORB UV-3529 (CYTEC company), Lowilite-62, Lowilite-94 , Lowilite-6294, Lowilite-92, Lowilite-77 (Chemtura), Tinuvin 744, Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622LD, CHIMASSORB 944LD (Ciba Specialty Chemicals) and so on. The above light stabilizers may be used alone or in combination.

As the photostabilizer, it is preferable to use two kinds of photostabilizers in combination, specifically, it is preferable to use Lowilite-62 and Lowilite-94 in combination.

As the above-mentioned antioxidant, there are mainly two kinds of hindered phenol antioxidant and phosphite antioxidant.

As the aforementioned hindered phenolic antioxidant, it is generally considered to have the function of capturing free radicals, terminating the thermo-oxidative aging chain reaction, and improving the thermo-oxidative aging resistance of polymer materials. The commercial products of hindered phenol antioxidants commonly used in this field can be cited: CYANOX-1790, CYANOX 2246, CYANOX 425 (CYTEC Company), Anox-20, Anox-330, Lowinox-1790, LowinoxCA-22, Lowinox GP -45, Lowinox HD-98, Naugard PS-48 (Chemtura), IRGANOX-1010, IRGANOX-1076, RGANOX-1098, IRGANOX-1135 (Ciba Specialty Chemicals), etc. The hindered phenolic antioxidants mentioned above can be used alone or in combination, and the specific ratio is not limited. IRGANOX-1010 is preferably used in the present invention.

As the above-mentioned phosphite antioxidant, it is generally believed that it has the function of decomposing hydroperoxides and inhibiting the yellowing of polymer materials during processing. Commonly used phosphite antioxidant marketable products in this area can be listed: STAB-1178, STAB-317, STAB-517, STAB-2112, STAB-1500, STAB-AS4500 (Taiwan Changchun Chemical Co., Ltd.), Weston-705, Weston-430, Weston-TNPP, Ultranox-619F, Ultranox-626 (Chemtura), IRGAFOS-168, IRGAFOS P-EPQ, IRGAFOS TNPP (Ciba Specialty Chemicals), etc. The above-mentioned phosphite antioxidants can be used alone or in combination, and the specific ratio is not limited. IRGAFOS-168 is preferably used in the present invention.

The aforementioned hindered phenol antioxidant and phosphite antioxidant can be used alone or in combination, and the specific ratio is not limited. In the present invention, IRGAFOS-168 is preferably used as the antioxidant.

In the present invention, the specific usage amount of each component in the anti-aging agent is not particularly limited.

In addition to the ultraviolet absorbers, light stabilizers, and antioxidants described above, the above-mentioned antiaging agents may also include lactones, tertiary amine free radical scavengers, carbodiimide antihydrolysis agents, and the like.

The content of the anti-aging agent is generally 0.05-2 parts by mass relative to 100 parts by mass of the olefin polymer in the solar module sealant film. When the amount of the anti-aging agent exceeds 2 parts by mass, the problem of excessive use of the anti-aging agent will occur, causing the surface of the high-performance solar cell module sealing film to migrate out of the additive; when the amount is less than 0.05 parts by mass, the aging resistance of the film will be reduced The effect is insufficient, and it is difficult to guarantee the long service life of the solar module.

The solar sealant film provided by the present invention can be prepared by known methods: olefin polymer, anti-aging agent, adhesion promoting polymer, and heat-conducting filler are mixed, extruded, formed into a film, and slit and rolled to obtain a sealed sealant. film.

Generally, the solar cell module sealant film of the present invention is applied to the back sheet side of the crystalline silicon solar cell module.

The present invention will be described in further detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

65 parts by mass of ethylene octene copolymer (ENGAGE 8130 from Dow Chemical, glass transition temperature -59°C, melting peak temperature 50°C), 35 parts by mass of ethylene-α-olefin block copolymer (ENGAGE 8130 from Dow Chemical INFUSE 9000, melting peak temperature 120°C, melt flow rate measured under the condition of 190°C 2.16kg is 0.5g/10min), 5 parts by mass of silane coupling agent with an average particle size of 40nm, peroxide-modified oxidation Zinc, 1 mass part of silane-grafted LDPE (SX522A of AEI Compounds: CM401) and 0.1 mass part of anti-aging agent [containing 0.05 mass part of 2,2'-dihydroxy-4-methoxybenzophenone (Taiwan Yongguang Chemical Eversorb 52) as a UV absorber, 0.03 parts by mass of Lowilite-62 (Chemtura Corporation) as a light stabilizer, 0.02 parts by mass of tris (2,4-di-tert-butylphenyl) phosphite ( Ciba Specialty Chemical IRGAFOS-168) as an antioxidant] fully mixed, the mixed material is added to the melt extrusion casting machine for extrusion, and the extruded product is cast, cooled, drawn, and curled to obtain the film thickness. 0.6mm solar cell module sealant film.

Example 2

90 parts by mass of ethylene-butylene copolymer (ENR 7380 from Dow Chemical, glass transition temperature -52°C, melting peak temperature 48°C), 10 parts by mass of linear low-density polyethylene (LINATHENE LL110 from Taiwan Polymer, melting peak Melt flow rate measured under the condition of 122°C, 190°C and 2.16kg is 1g/10min), 15 parts by mass of stearic acid with an average particle size of 100μm, peroxide-modified silicon carbide whiskers, 5 parts by mass Silane-grafted MDPE (SX720 from AEI Compounds: CM488) and 0.5 parts by mass of anti-aging agent [containing 0.1 part by mass of 2,2'-dihydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) As a UV absorber, 0.2 parts by mass of a mixture of Lowilite-62 and Lowilite-94 with a weight ratio of 1:1 (Chemtura Company) As a light stabilizer, 0.4 parts by mass of tetrakis[methyl-β-(3,5 -di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (IRGANOX-1010 from Ciba Specialty Chemicals) and 0.3 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite ( Ciba Specialty Chemical IRGAFOS-168) mixture as an antioxidant] fully mixed, the mixed material is added to the melt extrusion casting machine for extrusion, and the extruded product is cast, cooled, drawn, and curled to obtain Solar cell module sealing adhesive film with a film thickness of 0.6mm.

Example 3

Melt 80 parts by mass of propylene-ethylene copolymer (VERSIFY 3401 from Dow Chemical, glass transition temperature -32°C, melting peak temperature at 97°C), 20 parts by mass of low-density polyethylene (COSMOTHENE F410-1 from Singapore Polyolefin, The peak temperature is 111°C, the melt flow rate measured under the condition of 190°C 2.16kg is 5g/10min), 30 parts by mass of hyperbranched polymer with an average particle size of 1 μm, peroxide-modified boron nitride, 20 parts by mass Parts of silane-grafted LLDPE (LINKLON XLE815N from Mitsubishi Chemical Corporation) and 2 parts by mass of anti-aging agent [containing 1 part by mass of 2,2'-dihydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) As a UV absorber, 0.6 parts by mass of Lowilite-94 (Chemtura Corporation) as a light stabilizer, 0.4 parts by mass of tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl ) propionate] pentaerythritol ester (IRGANOX-1010 from Ciba Specialty Chemicals) as an antioxidant] fully mixed, and the uniformly mixed material is added to a melt extrusion casting machine for extrusion, and the extruded product is cast, cooled, The pulling and crimping process can obtain a solar cell module sealing adhesive film with a film thickness of 0.6 mm.

Example 4

75 parts by mass of ethylene octene copolymer (ENGAGE 8480 from Dow Chemical, glass transition temperature -41°C, melting peak temperature 100°C), 25 parts by mass of linear low density polyethylene (UNITHENE LH503 from Taiwan Polymer, melting peak The temperature is 130°C, the melt flow rate measured under the condition of 190°C 2.16kg is 4.1g/10min), 15 parts by mass of silane coupling agent with an average particle size of 100 μm, peroxide-modified silicon carbide whiskers, 5 parts by mass Parts of silane coupling agent with an average particle size of 20nm, peroxide-modified zinc oxide, 10 parts by mass of silane-grafted LLDPE (LINKLON XLE815N from Mitsubishi Chemical Corporation) and 1 part by mass of anti-aging agent [containing 0.7 parts by mass of 2 , 2'-dihydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) as a UV absorber, 0.1 parts by mass of Lowilite-62 (Chemtura Company) as a light stabilizer, 0.2 parts by mass of Tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester (IRGANOX-1010 from Ciba Specialty Chemicals) as an antioxidant] Mix well, mix well The material is added to a melt extrusion casting machine and extruded, and the extruded product is cast, cooled, drawn, and curled to obtain a solar cell module sealing film with a film thickness of 0.6 mm.

Example 5

85 parts by mass of ethylene-butylene copolymer (ENR 7447 from Dow Chemical, glass transition temperature -57°C, melting peak temperature 42°C), 15 parts by mass of low-density polyethylene (COSMOTHENE F410-1 from Singapore Polyolefin, The melting peak temperature is 111°C, the melt flow rate measured under the condition of 190°C 2.16kg is 5g/10min), 20 parts by mass of silane coupling agent with an average particle size of 50 μm, peroxide-modified alumina, 20 parts by mass Silane-grafted PP (LINKLONXPF860G from Mitsubishi Chemical Corporation) and 1.5 parts by mass of anti-aging agent [containing 0.3 parts by mass of 2,2'-dihydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) as UV Light absorber, 0.8 mass parts of Lowilite-62 and Lowilite-94 weight ratio 1:1 mixture (Chemtura Company) as light stabilizer, 0.9 mass parts of three (2,4-di-tert-butylphenyl) The mixture of phosphite (Ciba Precision Chemical IRGAFOS-168) is used as an antioxidant] and fully mixed, and the uniformly mixed material is added to the melt extrusion casting machine for extrusion, and the extrudate is cast, cooled, drawn, curled process, namely to obtain a solar cell module sealing adhesive film with a film thickness of 0.6 mm.

Example 6

70 parts by mass of ethylene-butylene copolymer (ENR 7380 from Dow Chemical, glass transition temperature -52°C, melting peak temperature 48°C) and propylene-ethylene copolymer (VERSIFY 3401 from Dow Chemical, glass transition temperature -32°C ), 30 parts by mass of low-density polyethylene (COSMOTHENE F410-1 from Singapore polyolefin, melting peak temperature 111°C, melt flow rate measured at 190°C under 2.16kg condition is 5g/10min), 15 parts by mass Stearic acid with an average particle diameter of 100 μm, peroxide-modified silicon carbide whiskers, 5 parts by mass of stearic acid with an average particle diameter of 20 nm, peroxide-modified zinc oxide, 30 parts by mass of silane-grafted PP ( LINKLON XPF860G from Mitsubishi Chemical Corporation) and 1.5 parts by mass of anti-aging agent [containing 0.3 parts by mass of 2,2'-dihydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) as a UV absorber, 0.8 The mixture of Lowilite-62 and Lowilite-94 with a weight ratio of 1:1 (Chemtura Company) of parts by mass is used as a light stabilizer, three (2,4-di-tert-butylphenyl) phosphite (vapor) of 0.9 parts by mass IRGAFOS-168) as an antioxidant] fully mixed, the mixed material is added to the melt extrusion casting machine for extrusion, and the extruded product is cast, cooled, drawn, curled, and the film is obtained 0.6mm thick solar cell module sealant film.

Example 7

90 parts by mass of ethylene-butene copolymer (ENR 7380 from Dow Chemical, glass transition temperature -52°C, melting peak temperature 48°C), 10 parts by mass of ethylene-α-olefin block copolymer (from Dow Chemical INFUSE 9000, melting peak temperature 120°C, melt flow rate measured under the condition of 190°C 2.16kg is 0.5g/10min) and linear low density polyethylene (UNITHENE LH503 of Taiju, melting peak temperature 130°C, 190°C 2.16 The melt flow rate measured under the condition of kg is 4.1g/10min), 15 parts by mass of silane coupling agent with an average particle size of 100μm, peroxide-modified silicon carbide whiskers, and 5 parts by mass with an average particle size of 20nm silane coupling agent, peroxide-modified zinc oxide, 5 parts by mass of silane-grafted MDPE (SX720 from AEI Compounds: CM488) and 0.5 parts by mass of anti-aging agent [containing 0.1 part by mass of 2,2'-di Hydroxy-4-methoxybenzophenone (Eversorb 52 from Taiwan Yongguang Chemical) was used as an ultraviolet light absorber, and 0.2 parts by mass of a mixture of Lowilite-62 and Lowilite-94 with a weight ratio of 1:1 (Chemtura Company) was used as a photostabilizer agent, 0.4 parts by mass of tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (IRGANOX-1010 from Ciba Specialty Chemicals) and 0.3 parts by mass of A mixture of tris(2,4-di-tert-butylphenyl) phosphite (Ciba Specialty Chemicals IRGAFOS-168) is used as an antioxidant] Mix thoroughly, and add the uniformly mixed material to the melt extrusion casting machine for extrusion , The extruded product is cast, cooled, drawn, and curled to obtain a solar cell module sealing film with a film thickness of 0.6mm.

Comparative example 1

With the silane coupling agent of the average particle diameter 40nm of 5 mass parts in embodiment 1, the zinc oxide of peroxide modification, change the zinc oxide of untreated 5 mass parts average particle diameter 40nm, other composition and processing The process has not changed.

Comparative example 2

In Example 2, 90 parts by mass of ethylene-butylene copolymer (ENR 7380 of Dow Chemical, glass transition temperature -52°C, melting peak temperature of 48°C) was replaced by 90 parts by mass of propylene-ethylene copolymer (Dow Chemical's VERSIFY 2200, the glass transition temperature is -23°C, the melting peak temperature is 82.2°C), other ingredients and processing technology remain unchanged.

Comparative example 3

In Example 3, 30 parts by mass of hyperbranched polymers with an average particle size of 1 μm and peroxide-modified boron nitride were taken out of the formula, and other components and processing techniques remained unchanged.

evaluate

Apparent judgment:

For laminated components, if white is found around the cells, the apparent appearance is judged as ○, otherwise judged as ●.

High and low temperature impact test:

According to the IEC-61215 standard, the test is carried out for 200 high and low temperature shocks. If there is no crack in the cell, it is indicated by ●, and if there is a crack, it is indicated by ○.

High temperature creep performance test:

Cut the prepared solar cell sealant film into a size of 75mm×150mm, use two pieces of solar ultra-clear cloth pattern glass (thickness 4mm, size 75mm×150mm) and solar battery backplane (thickness 300um, size 150mm×450mm), in turn Laminate glass/encapsulant film/back sheet to obtain a laminate, and use a vacuum laminator to degas the laminate at a temperature of 145°C for 7 minutes and pressurize to 1kg/ ^cm2 for 13 minutes. minute. Then hang the model in an oven at a temperature of 100°C for 48 hours to check whether the glass on the model slips. If there is no movement, it is indicated by ●, and if it has been moved, it is indicated by ○.

Reflectivity test:

Cut the prepared solar cell sealant film into a size of 50mm×50mm, use a piece of anti-adhesive cloth (size 100mm×100mm) and a piece of TPE solar battery backsheet (thickness 300um, size 50mm×50mm), and laminate the anti-sticking cloth in sequence Adhesive cloth/encapsulation film/back sheet to obtain a laminated body, use a vacuum laminator to degas the laminated body at a temperature of 145°C for 7 minutes, pressurize to 1kg/ ^cm2 and keep for 13 minute. Afterwards, the anti-sticking cloth was removed, and the laminated sample was put into a UV spectrophotometer to test the reflectivity of the encapsulation film surface.

Thermal conductivity test:

Test according to GB/T 10297-1998 standard.

Volume resistivity test:

Test according to GB/T 15662-1995 standard.

The measured results of the examples are shown in Table 1.

Table 1: Film Performance Data Sheet

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Laminated Appearance ● ● ● ● ● ● ● ○ ● ● High and low temperature impact resistance ● ● ● ● ● ● ● ● ○ ● High temperature creep test ● ● ● ● ● ● ● ○ ● ● Thermal conductivity (W/m·k) 0.6 0.9 1.1 1.2 0.5 1.3 1.2 0.3 1.0 0.2 Reflectivity(%) 91% 93% 96% 96% 91% 96% 96% 93% 94% 85% Volume resistivity (10 ¹⁴ Ω.cm) 244 158 68 129 413 117 137 257 146 807

Remarks: the formula of comparative example 1 is difficult to produce stably.

Claims (7)

1. a solar module sealed Cellophane, it is characterised in that each component is according to the mass fraction:

Olefin polymer 100 mass parts；

Heat filling 5～30 mass parts；

Antiaging agent 0.05～2 mass parts；

Adhesion promotes polymer 1～20 mass parts；

Wherein, olefin polymer is made up of the first olefin polymer and the second olefin polymer, and the first olefin polymer uses DSC Between the glass transition temperature range recorded is-59 DEG C～-32 DEG C, melting peak scope is 42 DEG C～100 DEG C；Second alkene Polymer uses the melting peak scope that records of DSC to be 111 DEG C～130 DEG C, at 190 DEG C, the melt flow that records under the conditions of 2.16kg Dynamic speed range is 0.5～5g/10min；The mass ratio of the first olefin polymer and the second olefin polymer is 65:35～90: 10；

Heat filling carries out pretreatment through one of silane coupler, stearic acid, dissaving polymer and peroxide.

Solar module sealed Cellophane the most according to claim 1, it is characterised in that described heat filling is gold Belong at least one in oxide, metal nitride, silicon dioxide, silicon nitride, carborundum.

Solar module sealed Cellophane the most according to claim 2, it is characterised in that described first olefin polymer For one or more in ethylene-alpha-olefin random copolymer, propylene-alpha olefin random copolymer.

Solar module sealed Cellophane the most according to claim 3, it is characterised in that described second olefin polymer For high density polyethylene (HDPE), Low Density Polyethylene, linear low density polyethylene, propylene-alpha olefin copolymer, ethylene-alpha-olefin block One or more in copolymer.

Solar module sealed Cellophane the most according to claim 4, it is characterised in that described adhesion promotes polymerization Thing containsBranched structure, wherein n=1～10, m=1～4, its main chain be olefin copolymer or One in person's olefin homo.

Solar module sealed Cellophane the most according to claim 5, it is characterised in that described adhesion promotes polymerization The main chain of thing is ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hervene copolymer Thing, ethylene-l-octane copolymer, Ethylene-propylene-hexene Copolymer, ethylene-pentene-hervene copolymer thing, ethylene-propylene-1,6- In hexadiene copolymer, Alathon, Noblen, isoprene homopolymer or 4-methyl-1-pentene homopolymer one Kind.

Solar module sealed Cellophane the most according to claim 6, it is characterised in that described antiaging agent is by ultraviolet Light absorber, light stabilizer and antioxidant composition.