Two-component organic silicon adhesive, preparation method thereof and photovoltaic module

Abstract

The invention provides a double-component organic silicon adhesive which comprises a component A and a component B. The component A comprises the following components in parts by weight: 40-50 parts of hydroxyl-terminated polydimethylsiloxane, 5-10 parts of dimethyl silicone oil, 20-30 parts of surface modified nano calcium carbonate, 10-20 parts of alkoxy modified MQ resin and 0.5-1.5 parts of a curing accelerator. The component B is prepared from the following components in parts by weight: 40 to 50 parts of hydroxyl-terminated polydimethylsiloxane, 1 to 5 parts of dimethyl silicone oil, 40 to 45 parts of surface modified nano calcium carbonate, 6 to 8 parts of a cross-linking agent, 0.8 to 1.4 parts of a silane coupling agent and 0.2 to 0.6 part of a catalyst. The double-component organic silicon adhesive provided by the technical scheme of the invention not only can better improve the bearing capacity of an assembly and prolong the service life of the assembly, but also can be rapidly and completely cured in the use process.

Description

Technical Field

[0001] The present application relates to the field of solar energy technology, and in particular to a two-component organic silicone adhesive and a preparation method thereof, and a photovoltaic module. Background Art

[0002] Organic silicone adhesive has excellent resistance to cold and heat, durability and sealing performance, and is widely used in the packaging process of photovoltaic modules. When encapsulating photovoltaic modules, organic silicone adhesive is mainly used between photovoltaic laminates and photovoltaic frames to bond the laminates to the photovoltaic frames.

[0003] In recent years, photovoltaic modules have gradually developed in the direction of high-power and large-format modules. As the size of the modules increases, the modules deform significantly due to their own weight, and are prone to deformation when subjected to wind loads, which leads to a significant increase in the risk of tearing and de-framing of the laminate and the frame. If the load-bearing force of the module is too large and the module is deformed greatly, the conventional organic silicone adhesive is easily torn due to the external strength being higher than its body strength, resulting in the phenomenon of laminate de-framing, affecting the normal use of the module and causing the module to fail. In addition, during the preparation of the module, the curing time of the organic silicone adhesive is a restrictive factor affecting the rapid flow of the production line. The single-component organic silicone adhesive currently used takes about 3.75-4 hours to complete deep curing in an environment with a temperature of 25°C and a humidity of 80%. Therefore, during the preparation of the module, it takes a long time to achieve complete curing, which will lead to a decrease in the flow efficiency of the production line. Moreover, incomplete deep curing can easily lead to secondary glue overflow at the frame of the module, thereby affecting the appearance of the module. Summary of the invention

[0004] The present application provides a two-component organic silicone adhesive and a preparation method thereof, and a photovoltaic module to solve or alleviate the technical problems mentioned above. The two-component organic silicone adhesive provided by the technical solution of the present application can not only better improve the bearing capacity of the module and extend the service life of the module, but also can be quickly and completely cured during use, thereby improving the flow efficiency of the production line.

[0005] In a first aspect, the present application provides a two-component organic silicone adhesive, including component A and component B, wherein: The A component comprises the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, 10-20 parts by weight of alkoxy-modified MQ resin, and 0.5-1.5 parts by weight of curing accelerator; The B component includes the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, 40-45 parts by weight of surface modified nano calcium carbonate, 6-8 parts by weight of crosslinking agent, 0.8-1.4 parts by weight of silane coupling agent, and 0.2-0.6 parts by weight of catalyst.

[0006] Optionally, the viscosity of the hydroxy-terminated polydimethylsiloxane of component A is 40000-60000 mPa·s.

[0007] Optionally, the viscosity of the terminal hydroxyl polydimethylsiloxane of component B is 40000-60000 mPa·s.

[0008] Optionally, the viscosity of the dimethyl silicone oil of component A is 500-2000 mPa·s.

[0009] Optionally, the viscosity of the dimethyl silicone oil of component B is 500-2000 mPa·s.

[0010] Optionally, the surface-modified nano-calcium carbonate of component A is nano-calcium carbonate surface-modified with γ-glycidyloxypropyltrimethoxysilane.

[0011] Optionally, the surface-modified nano-calcium carbonate of component B is nano-calcium carbonate surface-modified with γ-glycidyloxypropyltrimethoxysilane.

[0012] Optionally, the surface modified nano calcium carbonate of component A has a specific surface area of ​​25-35 m 2 / g.

[0013] Optionally, the surface modified nano calcium carbonate of component B has a specific surface area of ​​25-35 m 2 / g.

[0014] Optionally, the alkoxy-modified MQ resin is one or both of methoxy MQ resin and ethoxy MQ resin.

[0015] Optionally, the M / Q molar ratio of the alkoxy-modified MQ resin is 1.0-1.5.

[0016] Optionally, the curing accelerator includes one or more of water, hydrated aluminum oxide, and hydrated calcium chloride.

[0017] Optionally, the crosslinking agent includes one or more of ethyl orthosilicate, methyl orthosilicate, vinyl trimethoxysilane, vinyl triethoxysilane, and methyl trimethoxysilane.

[0018] Optionally, the silane coupling agent includes one or more of N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-(ethylenediamino)propyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N,N-diethyl-γ-aminopropyltrimethoxysilane, and γ-diethylenetriaminopropyltrimethoxysilane.

[0019] Optionally, the catalyst includes one or more of dibutyltin bis(acetylacetonate), dibutyltin dilaurate, dibutyltin dilaurate, and dibutyltin diacetoacetate.

[0020] In a second aspect, an embodiment of the present application provides a method for preparing the two-component organic silicone adhesive described in any one of the above embodiments, comprising: 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, and 10-20 parts by weight of alkoxy-modified MQ resin are uniformly mixed to obtain a first mixture; Mixing 0.5-1.5 parts by weight of a curing accelerator and the first mixture to obtain component A; 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, and 40-45 parts by weight of surface-modified nano-calcium carbonate are uniformly mixed to obtain a second mixture; Mixing 6-8 parts by weight of a cross-linking agent with the second mixture to obtain a third mixture; 0.8-1.4 parts by weight of a silane coupling agent and 0.2-0.6 parts by weight of a catalyst are uniformly mixed with the third mixture to obtain a B component.

[0021] In a third aspect, an embodiment of the present application provides a photovoltaic module, comprising the two-component organic silicone adhesive described in any of the above embodiments.

[0022] The above technical solution adopted in the embodiment of the present application may have the following advantages: The two-component organic silicone adhesive of the embodiment of the present application includes component A and component B, both of which include terminal hydroxyl polydimethylsiloxane, dimethyl silicone oil and surface-modified nano calcium carbonate, and the A combination also includes alkoxy-modified MQ resin, and the B component also includes a crosslinking agent, a silane coupling agent and a catalyst. Under the action of the air environment and the catalyst, the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane react with each other to improve the bonding strength, initial tensile strength and tensile strength after aging of DH1000 of the organic silicone adhesive, thereby improving the load-bearing capacity and service life of the photovoltaic module formed by the two-component organic silicone adhesive. In addition, component A also includes a curing accelerator. When component A and component B are mixed, the curing accelerator can accelerate the reaction of the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane, thereby effectively improving the curing speed inside the two-component organic silicone adhesive, avoiding the secondary glue overflow phenomenon caused by slow internal curing; and its curing depth is not affected by its own water-blocking properties, which can avoid the risk of secondary glue overflow in the later stage. DETAILED DESCRIPTION

[0023] The embodiments of the present application are described in detail below, which are only used to explain the present application and cannot be understood as limiting the present application. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other in the absence of conflict.

[0024] The present application embodiment provides a two-component organic silicone adhesive, including component A and component B, wherein: Component A includes the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, 10-20 parts by weight of alkoxy-modified MQ resin, and 0.5-1.5 parts by weight of curing accelerator; Component B includes the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, 40-45 parts by weight of surface modified nano calcium carbonate, 6-8 parts by weight of crosslinking agent, 0.8-1.4 parts by weight of silane coupling agent, and 0.2-0.6 parts by weight of catalyst.

[0025] The functions and contents of each component in the two-component silicone adhesive are described as follows: End-hydroxyl polydimethylsiloxane is the main component of two-component organic silicone adhesive. Its molecular chain is composed of silicon-oxygen bonds and has end-hydroxyl groups, which provide a basic three-dimensional network structure for the two-component organic silicone adhesive. It also reacts chemically with cross-linking agents and silane coupling agents to form a cross-linked structure, enhance bonding strength and cohesion, and improve the mechanical properties of the two-component organic silicone adhesive. An appropriate amount of end-hydroxyl polydimethylsiloxane can have good compatibility with alkoxy-modified MQ resin, which is beneficial to the mechanical properties of the two-component organic silicone adhesive. In the two-component organic silicone adhesive of the present application, the content of end-hydroxyl polydimethylsiloxane of component A is 40-50 parts by weight, preferably 43-48 parts by weight; the content of end-hydroxyl polydimethylsiloxane of component B is 40-50 parts by weight, preferably 43-48 parts by weight.

[0026] Dimethyl silicone oil can improve the rheological properties of two-component organic silicone adhesives, improve the extrusion properties of two-component organic silicone adhesives, and thus improve the quality of the finished two-component organic silicone adhesives. The amount of dimethyl silicone oil used should not be too large, otherwise it will increase the surface drying time of the two-component organic silicone adhesive and reduce the mechanical properties of photovoltaic modules; the amount of dimethyl silicone oil used should not be too small, otherwise the two-component organic silicone adhesive will not be able to achieve the required rheological properties. In the two-component organic silicone adhesive of the present application, the content of dimethyl silicone oil in component A is 5-10 parts by weight, preferably 6-8 parts by weight; the content of dimethyl silicone oil in component B is 1-5 parts by weight, preferably 2-4 parts by weight.

[0027] Surface-modified nano-calcium carbonate is a reinforcing filler that can improve the physical properties of two-component silicone adhesives, enhance the hardness and wear resistance of two-component silicone adhesives, and can also improve the tensile strength of two-component silicone adhesives and reduce material costs. In two-component silicone adhesives, if the amount of surface-modified nano-calcium carbonate is too large, the surface-modified nano-calcium carbonate particles will aggregate, affecting the mechanical properties and rheological properties of the two-component silicone adhesive; if the amount of surface-modified nano-calcium carbonate is too small, its reinforcing effect cannot be exerted. In the two-component silicone adhesive of the present application, the content of surface-modified nano-calcium carbonate in component A is 20-30 parts by weight, preferably 23-27 parts by weight; the content of surface-modified nano-calcium carbonate in component B is 40-45 parts by weight, preferably 42-44 parts by weight.

[0028] MQ resin is composed of monofunctional chain segments (R3SiO 1 / 2 M) and tetrafunctional segments (SiO 4 / 2That is, an organic / inorganic hybrid polyorganosiloxane with a special structural ratio composed of alkoxy functional groups (Q). Alkoxy-modified MQ resin is a reinforcing agent for two-component organic silicone adhesives. By introducing alkoxy functional groups, the compatibility with terminal hydroxyl polydimethylsiloxane is enhanced, thereby improving the mechanical strength of the two-component organic silicone adhesive and making the two-component organic silicone adhesive have good light transmittance and fluidity. In the two-component organic silicone adhesive of the present application, component A contains alkoxy-modified MQ resin, and the content of alkoxy-modified MQ resin is 10-20 parts by weight, preferably 13-18 parts by weight.

[0029] The cross-linking agent contains multiple functional groups and can form chemical bonds between linear or slightly branched macromolecules, so that the terminal hydroxyl polydimethylsiloxane and the silane coupling agent are cross-linked to form a three-dimensional network structure, thereby improving the molding speed, mechanical strength, wear resistance, and high temperature resistance of the two-component organic silicone adhesive, and improving the adsorption performance and softness of the two-component organic silicone adhesive. If the amount of the cross-linking agent is too large, the cross-linking density of the two-component organic silicone adhesive will be too high, making the two-component organic silicone adhesive too hard and brittle, thereby reducing its flexibility and impact resistance; if the amount of the cross-linking agent is too small, the cohesion of the two-component organic silicone adhesive will be reduced. In the two-component organic silicone adhesive of the present application, component B contains a cross-linking agent, and the content of the cross-linking agent is 6-8 parts by weight, preferably 6.5-7.5 parts by weight.

[0030] Silane coupling agents contain silicon-hydrogen bonds. When contacting the adherend material, the silane coupling agent reacts with the adherend and the terminal hydroxyl polydimethylsiloxane through the silicon-philic group to form a strong and durable covalent bond, thereby improving the interfacial adhesion, weather resistance, chemical corrosion resistance, and improving wettability and dispersibility. Too much silane coupling agent will increase the viscosity of the two-component organic silicone adhesive, which is not conducive to rheology; too little silane coupling agent will lead to insufficient bonding strength of the two-component organic silicone adhesive. In the two-component organic silicone adhesive of the present application, component B contains a silane coupling agent, and the content of the silane coupling agent is 0.8-1.4 parts by weight, preferably 1.0-1.2 parts by weight.

[0031] The catalyst can reduce the activation energy of the reaction, thereby accelerating the curing reaction, shortening the curing time of the two-component organic silicone adhesive, and improving the strength of the two-component organic silicone adhesive. If the amount of catalyst is too much, it is difficult to control the reaction process, affecting the quality of the product; if the amount of catalyst is too little, the curing time cannot be controlled within a reasonable range, affecting production efficiency. In the two-component organic silicone adhesive of the present application, component B contains a catalyst, and the content of the catalyst is 0.2-0.6 parts by weight, preferably 0.3-0.5 parts by weight.

[0032] When component A and component B are mixed, the hydroxy-terminated polydimethylsiloxane reacts with the crosslinking agent under the action of the catalyst and is cured, wherein the curing accelerator can accelerate the curing reaction rate and shorten the curing time, thereby achieving rapid curing. In the two-component organic silicone adhesive of the present application, component A contains a curing accelerator, and the content of the curing accelerator is 0.5-1.5 parts by weight, preferably 0.8-1.3 parts by weight.

[0033] The two-component organic silicone adhesive of the embodiment of the present application includes component A and component B, both of which include terminal hydroxyl polydimethylsiloxane, dimethyl silicone oil and surface-modified nano calcium carbonate. Moreover, the A combination also includes alkoxy-modified MQ resin, and the B component also includes a crosslinking agent, a silane coupling agent and a catalyst. Under the action of the air environment and the catalyst, the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane react with each other to improve the bonding strength, initial tensile strength and tensile strength of the two-component organic silicone adhesive after aging of DH1000, thereby improving the bearing capacity and service life of the corresponding photovoltaic module. In addition, component A also includes a curing accelerator. When component A and component B are mixed, the curing accelerator can accelerate the reaction of the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane, thereby effectively improving the curing speed inside the two-component organic silicone adhesive, avoiding the secondary glue overflow phenomenon caused by slow internal curing; and its curing depth is not affected by its own water-blocking properties, which can avoid the risk of secondary glue overflow in the later stage.

[0034] In some embodiments, the viscosity of the hydroxy-terminated polydimethylsiloxane of component A is 40,000-60,000 mPa·s.

[0035] In some embodiments, the viscosity of the hydroxy-terminated polydimethylsiloxane of component B is 40,000-60,000 mPa·s.

[0036] The larger the molecular weight of the hydroxy-terminated polydimethylsiloxane, the higher its viscosity, which generally means that the molecular chain is longer and the interaction between molecules is stronger. Higher viscosity may help improve the cohesion and bonding properties of the two-component silicone adhesive, but too high viscosity will reduce its compatibility with the alkoxy-modified MQ resin, thereby affecting the performance of the two-component silicone adhesive. When the viscosity of the hydroxy-terminated polydimethylsiloxane of component A and the hydroxy-terminated polydimethylsiloxane of component B is 40000-60000 mPa·s respectively and independently, they have good compatibility with the alkoxy-modified MQ resin, and the two-component silicone adhesive has better cohesion and bonding properties. Specifically, the viscosity of the terminal hydroxyl polydimethylsiloxane of the A component and the viscosity of the terminal hydroxyl polydimethylsiloxane of the B component may be 40000 Pa·s, 45000 Pa·s, 50000 mPa·s, 55000 Pa·s or 60000 mPa·s, respectively and independently.

[0037] In some embodiments, the viscosity of the dimethyl silicone oil of component A is 500-2000 mPa·s.

[0038] In some embodiments, the viscosity of the dimethyl silicone oil of component B is 500-2000 mPa·s.

[0039] In a two-component silicone adhesive, if the viscosity of dimethyl silicone oil is too high, it will increase the viscosity of the two-component silicone adhesive, thereby affecting its fluidity and construction performance; if the viscosity of dimethyl silicone oil is too low, it will cause the bonding strength and cohesion of the two-component silicone adhesive to decrease. When the viscosity of the dimethyl silicone oil of component A and the viscosity of the dimethyl silicone oil of component B are respectively and independently 1000-3000mPa·s, the two-component silicone adhesive can have both fluidity and bonding strength. Specifically, the viscosity of the dimethyl silicone oil of component A and the viscosity of the dimethyl silicone oil of component B can be respectively and independently 1000Pa·s, 1500Pa·s, 2000mPa·s, 2500mPa·s or 3000mPa·s.

[0040] In some embodiments, the surface-modified nano-calcium carbonate of component A is nano-calcium carbonate surface-modified with γ-glycidyloxypropyltrimethoxysilane.

[0041] In some embodiments, the surface-modified nano-calcium carbonate of component B is nano-calcium carbonate surface-modified with γ-glycidyloxypropyltrimethoxysilane.

[0042] By using surfactant γ-aminopropyltriethoxysilane to modify the surface of the nano calcium carbonate of component A and / or component B, the affinity of the corresponding calcium carbonate with silicone resin (terminated hydroxyl polydimethylsiloxane) can be significantly improved, thereby improving its dispersibility and affinity in the silicone adhesive, thereby increasing the reinforcement effect on the silicone adhesive.

[0043] In some embodiments, the specific surface area of ​​the surface-modified nano-calcium carbonate of component A is 25-35 m 2 / g.

[0044] In some embodiments, the specific surface area of ​​the surface-modified nano-calcium carbonate of component B is 25-35 m 2 / g.

[0045] The specific surface area of ​​surface-modified nano-calcium carbonate has an important influence on the tensile strength of two-component organic silicone adhesives. Generally, the tensile strength increases with the increase of specific surface area. However, too large a specific surface area will reduce its dispersion performance and affect the extrusion of the two-component organic silicone adhesive. When the specific surface area of ​​the surface-modified nano-calcium carbonate of component A and the specific surface area of ​​the surface-modified nano-calcium carbonate of component B are 26-34 m 2 / g, not only the extrusion performance of the two-component organic silicone adhesive is suitable for the production line, but also the two-component organic silicone adhesive can be guaranteed to have a high tensile strength. Specifically, the specific surface area of ​​the surface-modified nano-calcium carbonate of component A and the specific surface area of ​​the surface-modified nano-calcium carbonate of component B can be 26m 2 / g, 27m 2 / g, 28m 2 / g, 30m 2 / g, 31m 2 / g, 32m 2 / g, 33m 2 / g or 34m 2 / g.

[0046] In some embodiments, the alkoxy-modified MQ resin is one or both of methoxy MQ resin and ethoxy MQ resin. In methoxy MQ resin and ethoxy MQ resin, since the introduced alkoxy group belongs to a small molecular group, the compatibility with terminal hydroxyl polydimethylsiloxane is better.

[0047] In some embodiments, the M / Q molar ratio of the alkoxy-modified MQ resin is 1.0-1.5. When the M / Q molar ratio of the alkoxy-modified MQ resin is within this range, the alkoxy-modified MQ resin has good compatibility with the hydroxy-terminated polydimethylsiloxane, which is conducive to the dispersion of the alkoxy-modified MQ resin in the hydroxy-terminated polydimethylsiloxane, thereby improving the physical properties of the two-component organic silicone adhesive.

[0048] In some embodiments, the curing accelerator includes one or more of water, hydrated aluminum oxide, and hydrated calcium chloride, wherein the water may be deionized water.

[0049] When the two-component organic silicone adhesive is cured, water vapor is required. When the curing accelerator of component A includes one or more of water, hydrated aluminum oxide, and hydrated calcium chloride, the curing accelerator can not only promote the hydrolysis of the cross-linking agent and the silane coupling agent, but also help the cross-linking agent and the silane coupling agent to react with the terminal hydroxyl polydimethylsiloxane under the action of the catalyst, so that the two-component organic silicone adhesive can be cured quickly.

[0050] In some embodiments, the crosslinking agent includes one or more of ethyl orthosilicate, methyl orthosilicate, vinyl trimethoxysilane, vinyl triethoxysilane, and methyl trimethoxysilane. These crosslinking agents are all linear polymer chains formed by connecting siloxane units, and have a similar structure to terminal hydroxyl polydimethylsiloxane. Therefore, these crosslinking agents have good compatibility with terminal hydroxyl polydimethylsiloxane, which is conducive to further improving the bonding performance of the two-component organic silicone adhesive.

[0051] In some embodiments, when the crosslinking agent includes a first crosslinking agent (ethyl orthosilicate and / or methyl orthosilicate), a second crosslinking agent (vinyl trimethoxy silane and / or vinyl triethoxy silane) and a third crosslinking agent (methyl trimethoxy silane), the mass ratio of the first crosslinking agent, the second crosslinking agent and the third crosslinking agent is 1:1:1-5:1:1, specifically 1:1:1, 2:1:1, 3:1:1, 4:1:1 or 5:1:1.

[0052] In some embodiments, when the crosslinking agent includes tetraethyl orthosilicate, vinyl triethoxysilane, and methyl trimethoxysilane, the mass ratio of the three is 1:1:1-5:1:1, specifically 1:1:1, 2:1:1, 3:1:1, 4:1:1 or 5:1:1.

[0053] In some embodiments, the silane coupling agent includes one or more of N-β-aminoethyl-γ-aminopropyl trimethoxysilane, γ-(ethylenediamino)propyl trimethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-(methacryloyloxy)propyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyldimethoxysilane, N,N-diethyl-γ-aminopropyl trimethoxysilane, and γ-diethylenetriaminopropyl trimethoxysilane. These silane coupling agents have good compatibility with terminal hydroxyl polydimethylsiloxane and react fully with terminal hydroxyl polydimethylsiloxane, which is beneficial to improve the bonding strength of the two-component organic silicone adhesive.

[0054] In some embodiments, when the silane coupling agent includes multiple (two or more) of N-β-aminoethyl-γ-aminopropyltrimethoxysilane oligomer, γ-(ethylenediamino)propyltrimethoxysilane oligomer, γ-glycidyloxypropyltrimethoxysilane oligomer, γ-(methacryloyloxy)propyltrimethoxysilane oligomer, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N,N-diethyl-γ-aminopropyltrimethoxysilane, and γ-diethylenetriaminopropyltrimethoxysilane, the mass ratio of any two silane coupling agents is 1:1.

[0055] In some embodiments, the catalyst includes one or more of dibutyltin bis(acetylacetonate), dibutyltin diacetylate, dibutyltin dilaurate, and dibutyltin dilaurate. These catalysts can significantly accelerate the curing reaction of the two-component organic silicone adhesive, thereby improving the bonding effect.

[0056] In some embodiments, when the catalyst includes multiple (two or more) of dibutyltin bis(acetylacetonate), dibutyltin diacetoacetate, dibutyltin dilaurate, and dibutyltin dilaurate, the mass ratio of any two catalysts is 1:1.

[0057] The embodiment of the present application provides a method for preparing a two-component organic silicone adhesive, which is used to prepare the two-component organic silicone adhesive described in any of the above embodiments, including: a method for preparing component A and a method for preparing component B.

[0058] The preparation method of component A comprises: 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, and 10-20 parts by weight of alkoxy-modified MQ resin are uniformly mixed to obtain a first mixture; 0.5-1.5 parts by weight of a curing accelerator is uniformly mixed with the first mixture to obtain component A.

[0059] The preparation method of component B comprises: 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, and 40-45 parts by weight of surface-modified nano-calcium carbonate are uniformly mixed to obtain a second mixture; Mixing 6-8 parts by weight of a cross-linking agent with the second mixture to obtain a third mixture; 0.8-1.4 parts by weight of a silane coupling agent and 0.2-0.6 parts by weight of a catalyst are uniformly mixed with the third mixture to obtain a B component.

[0060] In some embodiments, the method for preparing component A comprises: 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, and 10-20 parts by weight of alkoxy-modified MQ resin are stirred for 1-2 hours in an environment with a temperature of 110-120° C. and a vacuum degree of less than or equal to -0.095 MPa to obtain a first mixture; 0.5-1.5 parts by weight of the curing accelerator and the first mixture are stirred for 15-20 minutes in an environment with a vacuum degree of -0.10 MPa to -0.09 MPa to mix evenly to obtain component A.

[0061] In some embodiments, the method for preparing component B comprises: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, and 40-45 parts by weight of surface-modified nano-calcium carbonate are stirred for 1-2 hours in an environment with a temperature of 110-120° C. and a vacuum degree of less than or equal to -0.095 MPa to obtain a second mixture; 6-8 parts by weight of the cross-linking agent and the second mixture are stirred and reacted for 20-30 minutes to obtain a third mixture; 0.8-1.4 parts by weight of a silane coupling agent, 0.2-0.6 parts by weight of a catalyst and the third mixture are stirred for 20-30 minutes in an environment with a vacuum degree of -0.10 MPa to -0.09 MPa to mix evenly to obtain component B.

[0062] It should be noted that there is no fixed order for the preparation of component A and component B, that is, A can be prepared first and then B; B can be prepared first and then A; A and B can also be prepared at the same time. The two-component organic silicone adhesive of the embodiment of the present application can be obtained without mixing component A and component B, but component A and component B are mixed in a mass ratio of 1:2-2:1 during use.

[0063] The following specific examples further illustrate the present application in detail, but should not be construed as limiting the present application. Without departing from the spirit and substance of the present application, modifications or substitutions made to the methods, steps or conditions of the present application are within the scope of the present application. The following further lists the formulas of the two-component organic silicone adhesives of Examples 1-14 of the present application and Comparative Example 1, and the specific formulas are shown in Table 1.

[0064] Table 1

[0065] Table 1 (continued)

[0066] In Examples 1 to 14 of the present application, the viscosity of the terminal hydroxyl polydimethylsiloxane of component A is 40000-60000 mPa·s; the viscosity of the terminal hydroxyl polydimethylsiloxane of component B is 40000-60000 mPa·s; the viscosity of the dimethyl silicone oil of component A is 500-2000 mPa·s; the viscosity of the dimethyl silicone oil of component B is 500-2000 mPa·s; the specific surface area of ​​the surface modified nano-calcium carbonate of component A is 25-35 m 2 / g; the specific surface area of ​​the surface modified nano calcium carbonate of component B is 25-35m 2 / g; the curing accelerator includes one or more of water, hydrated aluminum oxide, and hydrated calcium chloride.

[0067] The preparation methods of Examples 1 to 14 include: Preparation of component A: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, and 10-20 parts by weight of alkoxy-modified MQ resin are stirred for 1-2 hours in an environment with a temperature of 110-120° C. and a vacuum degree of less than or equal to -0.095 MPa to obtain a first mixture; 0.5-1.5 parts by weight of a curing accelerator and the first mixture are stirred for 15-20 minutes in an environment with a vacuum degree of -0.10 MPa to -0.09 MPa to mix evenly to obtain component A; Preparation of component B: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, and 40-45 parts by weight of surface-modified nano-calcium carbonate are stirred for 1-2 hours in an environment with a temperature of 110-120° C. and a vacuum degree of less than or equal to -0.095 MPa to obtain a second mixture; 6-8 parts by weight of the cross-linking agent and the second mixture are stirred and reacted for 20-30 minutes to obtain a third mixture; 0.8-1.4 parts by weight of a silane coupling agent, 0.2-0.6 parts by weight of a catalyst and the third mixture are stirred for 20-30 minutes in an environment with a vacuum degree of -0.10 MPa to -0.09 MPa to mix evenly to obtain component B.

[0068] When using the two-component silicone adhesive of Example 1 to Example 14, component A and component B are mixed in a mass ratio of 1:1.

[0069] In order to further illustrate the technical effects of the embodiments of the present application, the present application also provides Comparative Example 1, Comparative Example 2 and Comparative Example 3. The specific formulas of the two-component organic silicone adhesives of Comparative Examples 1 to 3 are as follows.

[0070] Comparative Example 1 Component A 48.5 parts by weight of hydroxy-terminated polydimethylsiloxane, 6 parts by weight of dimethyl silicone oil, 45 parts by weight of surface modified nano calcium carbonate, 0.5 parts by weight of curing accelerator, Component B 45.6 parts by weight of hydroxy-terminated polydimethylsiloxane, 2 parts by weight of dimethyl silicone oil, 43 parts by weight of surface modified nano calcium carbonate, Crosslinking agent (ethyl orthosilicate) 3 parts by weight, Silane coupling agent (N-2-aminoethyl-3-aminopropyltrimethoxysilane) 1.5 parts by weight, Catalyst (dibutyltin bis(acetylacetonate)) 0.2 parts by weight.

[0071] Comparative Example 2 Component A 48.5 parts by weight of hydroxy-terminated polydimethylsiloxane, 6 parts by weight of dimethyl silicone oil, Alkoxy modified MQ resin (methoxy MQ silicone resin) 45 parts by weight, 0.5 parts by weight of curing accelerator, Component B 45.6 parts by weight of hydroxy-terminated polydimethylsiloxane, 2 parts by weight of dimethyl silicone oil, Crosslinking agent (ethyl orthosilicate) 3 parts by weight, Silane coupling agent (N-2-aminoethyl-3-aminopropyltrimethoxysilane) 1.5 parts by weight, Catalyst (dibutyltin bis(acetylacetonate)) 0.2 parts by weight.

[0072] Comparative Example 3 Component A 49 parts by weight of hydroxy-terminated polydimethylsiloxane, 6 parts by weight of dimethyl silicone oil, Alkoxy modified MQ resin (methoxy MQ silicone resin) 45 parts by weight, Component B 45.6 parts by weight of hydroxy-terminated polydimethylsiloxane, 2 parts by weight of dimethyl silicone oil, Crosslinking agent (ethyl orthosilicate) 3 parts by weight, Silane coupling agent (N-2-aminoethyl-3-aminopropyltrimethoxysilane) 1.5 parts by weight, Catalyst (dibutyltin bis(acetylacetonate)) 0.2 parts by weight.

[0073]

Performance test

[0074] Table 2

[0075] The test results of Table 1 show that a two-component high-strength photovoltaic adhesive of Examples 1-14 of the present invention has good mechanical properties, and its initial tensile strength is ≥3.0MPa, and the tensile strength after DH1000 is ≥2.0MPa, which can greatly improve the bearing capacity of the component, thereby extending the service life of the component. In Examples 1-14 of the present application, it contains terminal hydroxyl polydimethylsiloxane, dimethyl silicone oil, surface-modified nano-calcium carbonate, and alkoxy-modified MQ resin at the same time; alkoxy MQ silicone resin (methoxy MQ silicone resin and ethoxy MQ silicone resin) has good storage stability and controllable methoxy or ethoxy content, and the special organic-inorganic structure of methoxy MQ resin or ethoxy MQ silicone resin makes it have good compatibility with terminal hydroxyl polydimethylsiloxane, and at the same time, its surface silanol can condense and react with the silanol at both ends of the terminal hydroxyl polydimethylsiloxane to form a strong chemical bond, which greatly improves the mechanical properties of the enhanced organic silicone adhesive. In addition, the two-component organic silicone adhesive of Examples 1-14 has a good curing depth and can be well adapted to the production line process. However, the organic silicone adhesives of Comparative Examples 1-3 have disadvantages such as poor mechanical properties or low curing depth.

[0076] In summary, the two-component organic silicone adhesive of the embodiment of the present application includes component A and component B, both of which include terminal hydroxyl polydimethylsiloxane, dimethyl silicone oil and surface-modified nano calcium carbonate, and the A combination also includes alkoxy-modified MQ resin, and the B component also includes a crosslinking agent, a silane coupling agent and a catalyst. Under the action of the air environment and the catalyst, the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane react with each other to improve the bonding strength, initial tensile strength and tensile strength after aging of DH1000 of the organic silicone adhesive, thereby improving the load-bearing capacity and service life of the photovoltaic module formed by the two-component organic silicone adhesive. In addition, component A also includes a curing accelerator. When component A and component B are mixed, the curing accelerator can accelerate the reaction of the crosslinking agent, the silane coupling agent and the terminal hydroxyl polydimethylsiloxane, thereby effectively improving the curing speed inside the two-component organic silicone adhesive, and avoiding the secondary glue overflow phenomenon caused by slow internal curing; and its curing depth is not affected by its own water-blocking properties, which can avoid the risk of secondary glue overflow in the later stage.

[0077] The embodiment of the present application also provides a photovoltaic module, including a laminate, a photovoltaic frame, and the two-component organic silicone adhesive described in any of the above embodiments, wherein the two-component organic silicone adhesive bonds the laminate and the photovoltaic frame to ensure the performance and quality of the photovoltaic module. During the preparation of the photovoltaic module, component A and component B in the two-component organic silicone adhesive are mixed in a mass ratio of 1:2-2:1, and are immediately used to bond the laminate and the photovoltaic frame after mixing.

[0078] The embodiment of the present application also provides a photovoltaic system, including the photovoltaic components provided in the above embodiment. The advantages of the above photovoltaic components are also possessed by the photovoltaic system, which will not be repeated here. The above photovoltaic system has a wide range of applications, not only limited to photovoltaic power stations, such as ground power stations, rooftop power stations and water power stations, but also includes various equipment and devices that use solar energy to generate electricity, such as user solar power supplies, solar street lights, solar cars and solar buildings. Of course, it can be understood that the application scenarios of the photovoltaic system are not limited to this, that is to say, the photovoltaic system can be used in all fields where solar energy is required for power generation. Taking the photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a junction box and an inverter. The photovoltaic array may be an array combination of multiple photovoltaic components. For example, multiple photovoltaic components may form multiple photovoltaic arrays. The photovoltaic array is connected to a junction box. The junction box can converge the current generated by the photovoltaic array. The converged current flows through the inverter and is converted into the alternating current required by the mains power grid, and then connected to the mains network to realize solar power supply.

[0079] It should be noted that the terms "first", "second", "third", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device comprising a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0080] It should be noted that: in this article, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device that includes a series of elements includes not only those elements, but also includes other elements that are not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the sentence "comprises a ..." does not exclude the existence of other identical elements in the process, method, article or device that includes the element.

[0081] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, please refer to the relevant description of other embodiments. The above embodiments are only used to illustrate the technical solution of the present application, rather than to limit it. Although the present application is described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that it is still possible to modify the technical solutions recorded in the aforementioned embodiments, or to replace some of the technical features therein by equivalents; and these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.

[0082] It should also be noted that "one embodiment", "another embodiment", "embodiment", etc. mentioned in this application refer to the specific features, structures or characteristics described in conjunction with the embodiment included in at least one embodiment generally described in this application. The same expression appearing in multiple places in the specification does not necessarily refer to the same embodiment. Further, when describing a specific feature, structure or characteristic in conjunction with any embodiment, it is claimed that the realization of such feature, structure or characteristic in conjunction with other embodiments also falls within the scope of this application.

Claims

1. A two-component organic silicone adhesive, characterized in that: It includes component A and component B, wherein: The A component comprises the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, 10-20 parts by weight of alkoxy-modified MQ resin, and 0.5-1.5 parts by weight of curing accelerator; The B component includes the following components in parts by weight: 40-50 parts by weight of terminal hydroxyl polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, 40-45 parts by weight of surface modified nano calcium carbonate, 6-8 parts by weight of crosslinking agent, 0.8-1.4 parts by weight of silane coupling agent, and 0.2-0.6 parts by weight of catalyst.

2. The two-component organic silicone adhesive according to claim 1, characterized in that: The viscosity of the hydroxy-terminated polydimethylsiloxane of component A is 40000-60000 mPa·s; and / or The viscosity of the terminal hydroxyl polydimethylsiloxane of the B component is 40000-60000 mPa·s.

3. The two-component organic silicone adhesive according to claim 1, characterized in that: The viscosity of the dimethyl silicone oil of component A is 500-2000 mPa·s; and / or The viscosity of the dimethyl silicone oil of component B is 500-2000 mPa·s.

4. The two-component organic silicone adhesive according to claim 1, characterized in that: The surface-modified nano-calcium carbonate of component A is nano-calcium carbonate surface-modified by γ-glycidyloxypropyltrimethoxysilane; and / or The surface-modified nano-calcium carbonate of component B is nano-calcium carbonate surface-modified by γ-glycidyloxypropyltrimethoxysilane.

5. The two-component organic silicone adhesive according to claim 1, characterized in that: The specific surface area of ​​the surface modified nano calcium carbonate of component A is 25-35m 2 / g; and / or The specific surface area of ​​the surface modified nano calcium carbonate of component B is 25-35m 2 / g.

6. The two-component organic silicone adhesive according to claim 1, characterized in that: The alkoxy-modified MQ resin is one or both of methoxy MQ resin and ethoxy MQ resin.

7. The two-component organic silicone adhesive according to claim 1, characterized in that: The M / Q molar ratio of the alkoxy-modified MQ resin is 1.0-1.

5.

8. The two-component organic silicone adhesive according to any one of claims 1 to 7, characterized in that: The curing accelerator includes one or more of water, hydrated aluminum oxide, and hydrated calcium chloride.

9. The two-component organic silicone adhesive according to any one of claims 1 to 7, characterized in that: The crosslinking agent includes one or more of ethyl orthosilicate, methyl orthosilicate, vinyl trimethoxysilane, vinyl triethoxysilane, and methyl trimethoxysilane.

10. The two-component organic silicone adhesive according to any one of claims 1 to 7, characterized in that: The silane coupling agent includes one or more of N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-(ethylenediamino)propyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N,N-diethyl-γ-aminopropyltrimethoxysilane, and γ-diethylenetriaminopropyltrimethoxysilane.

11. The two-component organic silicone adhesive according to any one of claims 1 to 7, characterized in that: The catalyst includes one or more of dibutyltin bis(acetylacetonate), dibutyltin dilaurate, dibutyltin dilaurate, and dibutyltin diacetoacetate.

12. A method for preparing a two-component organic silicone adhesive according to any one of claims 1 to 11, characterized in that: include: 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 5-10 parts by weight of dimethyl silicone oil, 20-30 parts by weight of surface-modified nano-calcium carbonate, and 10-20 parts by weight of alkoxy-modified MQ resin are uniformly mixed to obtain a first mixture; Mixing 0.5-1.5 parts by weight of a curing accelerator and the first mixture to obtain component A; 40-50 parts by weight of hydroxy-terminated polydimethylsiloxane, 1-5 parts by weight of dimethyl silicone oil, and 40-45 parts by weight of surface-modified nano-calcium carbonate are uniformly mixed to obtain a second mixture; Mixing 6-8 parts by weight of a cross-linking agent with the second mixture to obtain a third mixture; 0.8-1.4 parts by weight of a silane coupling agent and 0.2-0.6 parts by weight of a catalyst are uniformly mixed with the third mixture to obtain a B component.

13. A photovoltaic module, characterized in that: It comprises the two-component organic silicone adhesive as described in any one of claims 1 to 11.

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