Flexible composite materials, methods for manufacturing the same, and uses

Abstract

This invention provides a flexible composite material, a method for producing the same, and a use thereof, belonging to the field of functional materials technology. The flexible composite material provided by this invention comprises a fibrous fabric and a strontium titanate nanomicromaterial composited to the fibrous fabric. The raw materials for producing the strontium titanate nanomicromaterial include a matrix material and a dispersant, wherein the mass of the dispersant is 0.05 to 0.2% of the mass of the matrix material, and the matrix material comprises the following raw materials by mass: 50 to 90 parts of powdered resin, 10 to 50 parts of curing agent, 0 to 20 parts of antioxidant auxiliary, 0.05 to 0.2 parts of catalyst, 0 to 10 parts of surface modifier, 0 to 20 parts of light stabilizer, and 0.05 to 5 parts of strontium titanate nanoauxiliary. Here, the strontium titanate nanoauxiliary is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate in specific ratios. The flexible composite material provided by this invention has excellent weather resistance.

Description

[Technical Field]

[0001] This application was filed with the Chinese National Intellectual Property Office on June 29, 2023, claiming priority to the Chinese Patent Application No. CN202310778172.0, with the title of the invention "Flexible Composite Material, Method for Manufacturing the Same and Use thereof," all of which are incorporated herein by reference.

[0002] This invention relates to the field of functional materials technology, and more particularly to flexible composite materials, methods for producing the same, and uses thereof. [Background technology]

[0003] Conventional photovoltaic modules consist of a TPT backsheet, EVA adhesive film, solar cells, glass panels, and a frame. Conventional photovoltaic modules are rigid modules that are resistant to deformation and are relatively heavy, making them unsuitable for applications requiring bending or lightweight design. Flexible solar panels are an emerging technology in the global solar energy industry. Specifically, they use flexible composite materials instead of the glass panels and TPT backsheet of conventional photovoltaic modules to protect and support the solar cells. Flexible solar panels are highly flexible and easy to bend, so they can be bent to conform to the shape of the roof, even if the average roof slope is less than 60° and the bending radius of the panel exceeds 13m. Furthermore, because flexible solar panels are lightweight, their installation does not place an excessive load on the roof, and does not cause significant changes to the main structure of the roof. However, the weather resistance of flexible composite materials in conventional technology still has room for improvement. [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to provide a flexible composite material, a method for producing the same, and a method for using the same. The flexible composite material provided by the present invention has excellent weather resistance. [Means for solving the problem]

[0005] To achieve the objectives of the above invention, the present invention provides the following technical solutions. The present invention provides a flexible composite material comprising a fibrous fabric and a strontium titanate nanomicro material compounded with the fibrous fabric. The raw materials for producing the strontium titanate nanomicromaterial include a matrix material and a dispersant, wherein the mass of the dispersant is 0.05 to 0.2% of the mass of the matrix material. The matrix material comprises 50 to 90 parts by mass of powdered resin, 10 to 50 parts by mass of curing agent, 0 to 20 parts by mass of antioxidant auxiliary agent, 0.05 to 0.2 parts by mass of catalyst, 0 to 10 parts by mass of surface modifier, 0 to 20 parts by mass of light stabilizer, and 0.05 to 5 parts by mass of strontium titanate nano-auxiliary agent. Here, the strontium titanate nano-auxiliary agent is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate, and the mass ratio of the octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate is 3 to 4:4 to 6:1 to 2.

[0006] Preferably, the fiber cloth is a glass fiber cloth.

[0007] Preferably, the weight of the fiber cloth is 100 to 400 g / m². 2 That is the case.

[0008] Preferably, the particle size of the strontium titanate nano-additive is 50 to 300 nm.

[0009] Preferably, the particle size of the octahedral strontium titanate is 100 to 200 nm, the particle size of the hexahedral strontium titanate is 100 to 200 nm, and the particle size of the irregular strontium titanate is 50 to 100 nm.

[0010] Preferably, the powdered resin contains one or more of acrylic resin, polyurethane resin, and polyester resin.

[0011] Preferably, the acrylic resin is an epoxy acrylic resin.

[0012] Preferably, the curing agent comprises one or more of dodecandioic acid, triglycidyl isocyanurate, and isocyanate.

[0013] Preferably, the antioxidant adjuvant includes one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecanol propionate, benzofuranone derivatives, and thioester antioxidants.

[0014] Preferably, the catalyst comprises tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole.

[0015] Preferably, the surface modifier contains benzoin.

[0016] Preferably, the particle size of the matrix material is 30 to 150 μm.

[0017] Preferably, the particle size of the dispersant is 2 to 8 μm.

[0018] Preferably, the dispersant comprises one or more of alumina, fumed silica, and glass microspheres.

[0019] Preferably, the content of strontium titanate nanomicromaterial in the flexible composite material is 50 to 80% by weight.

[0020] The present invention provides a method for manufacturing a flexible composite material as described in the above technical solution, The process includes the step of impregnating a fiber cloth with molten strontium titanate nanomicromaterial and curing it to obtain a flexible composite material.

[0021] Preferably, the method for impregnating the molten strontium titanate nanomicro material into the fiber cloth is: Laying the strontium titanate nano / micro material on the surface of the fiber cloth, heating it using a laminating device or a rolling device, and melting the strontium titanate nano / micro material to impregnate the fiber cloth.

[0022] Preferably, the method of impregnating the melted strontium titanate nano / micro material into the fiber cloth is Extruding the strontium titanate nano / micro material to obtain a resin film, laminating and compounding the resin film on the surface of the fiber cloth, heating it with a laminating device or a rolling device, and melting the resin film to impregnate the fiber cloth.

[0023] Preferably, the curing temperature is 130 - 200 °C, the pressure is 1 - 20 MPa, and the time is 10 - 90 minutes.

[0024] The present invention provides the use of the flexible composite material described in the above technical solution, or the flexible composite material manufactured by the manufacturing method described in the above technical solution, as a sealing material for a solar power generation module.

[0025] Preferably, the sealing material is a sealing material for the front panel or the backsheet of a solar power generation module.

Effects of the Invention

Modes for Carrying Out the Invention

[0027] The present invention provides a flexible composite material comprising a fibrous fabric and a strontium titanate nanomicro material compounded with the fibrous fabric. The raw materials for producing the strontium titanate nanomicromaterial include a matrix material and a dispersant, wherein the mass of the dispersant is 0.05 to 0.2% of the mass of the matrix material. The matrix material comprises 50 to 90 parts by mass of powdered resin, 10 to 50 parts by mass of curing agent, 0 to 20 parts by mass of antioxidant auxiliary agent, 0.05 to 0.2 parts by mass of catalyst, 0 to 10 parts by mass of surface modifier, 0 to 20 parts by mass of light stabilizer, and 0.05 to 5 parts by mass of strontium titanate nano-auxiliary agent. Here, the strontium titanate nano-auxiliary agent is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate, and the mass ratio of the octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate is 3 to 4:4 to 6:1 to 2.

[0028] The strontium titanate nanomicromaterial described in the present invention is used as a encapsulant for photovoltaic modules and has a weather-resistant powder coating. The nanomicromaterial described in the present invention is based on the size of the material, i.e., nanometer-scale material and micrometer-scale material, rather than the amount of strontium titanate nano-auxiliary material used.

[0029] In the present invention, unless otherwise specifically described, all raw materials used are commercially available products well known to those skilled in the art or are obtained by methods well known to those skilled in the art.

[0030] The flexible composite material provided by the present invention includes a fibrous fabric. In the present invention, the fibrous fabric is preferably a glass fiber fabric, and the glass fiber fabric is preferably a machine-woven glass fiber fabric. The weight of the fibrous fabric is preferably 100 to 400 g / m². 2 Specifically, 100g / m 2 200g / m 2 300g / m 2 or 400g / m2 It may also be the case that the thickness of the flexible composite material described in the present invention is mainly influenced by the weight of the fiber cloth. Specifically, in the present invention, the thickness of the flexible composite material is preferably 0.1 to 0.4 mm, more preferably 0.15 to 0.31 mm, and specifically may be 0.15 mm, 0.22 mm, or 0.31 mm.

[0031] The flexible composite material provided by the present invention comprises a strontium titanate nanomicromaterial compounded with the fibrous fabric, wherein the strontium titanate nanomicromaterial is specifically impregnated into the fibers in the fibrous fabric. In the present invention, the content of the strontium titanate nanomicromaterial in the flexible composite material is preferably 50 to 80% by weight, more preferably 51 to 78% by weight, even more preferably 52 to 75% by weight, even more preferably 53 to 70% by weight, then even more preferably 54 to 65% by weight, and still even more preferably 55 to 60% by weight. In the present invention, the raw material for producing the strontium titanate nanomicro material includes a matrix material, the raw material for producing the matrix material comprising 50 to 90 parts by mass of powdered resin, preferably 55 to 80 parts, more preferably 60 to 78 parts, more preferably 65 to 75 parts, and even more preferably 70 to 72 parts. In the present invention, the powdered resin preferably comprises one or more of acrylic resin, polyurethane resin, and polyester resin, and more preferably acrylic resin.

[0032] The present invention preferably uses an acrylic resin as the main material, which has the advantages of excellent weather resistance, high film strength, impact resistance, and flexibility. In the present invention, the acrylic resin is preferably an epoxy acrylic resin, more preferably an epoxy acrylic powder coating resin described in Japanese Patent CN 115651473 A. Specifically, the raw materials for the epoxy acrylic powder coating resin include 20 to 70 parts of hard monomer, 10 to 60 parts of soft monomer, 10 to 50 parts of crosslinking monomer, and 0.5 to 8 parts of initiator. The crosslinked monomer comprises an epoxy-containing monomer and / or a hydroxyl-containing monomer, the hard monomer comprises at least one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, dicyclopentadiene acrylate, dicyclopentadiene ethoxyacrylate, styrene, methylstyrene, or acrylonitrile, the soft monomer comprises an alkyl acrylate compound, the epoxy-containing monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, hydroxybutyl glycidyl ether acrylate, or glycidyl ether tert-carbonate, the hydroxyl-containing monomer comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, or N-hydroxymethylacrylamide, and the mass ratio of the epoxy-containing monomer to the hydroxyl-containing monomer in the crosslinked monomer is (2-15):1. The epoxy acrylic powder coating resin is produced by the following method. The method involves dropwise adding a mixture of a hard monomer, a soft monomer, a crosslinked monomer, an initiator in an amount of 40-50%, and an optional molecular weight modifier to a solvent, and after the first reaction, adding the remaining initiator dropwise and continuing the reaction to obtain the epoxy acrylic powder coating resin, wherein the temperature of the first reaction is 80-110°C, the duration is 2-4 hours, and the duration of the continuing reaction is 2-4.5 hours.

[0033] The raw materials for producing the matrix material described in the present invention include 10 to 50 parts, preferably 15 to 30 parts, more preferably 18 to 25 parts, and even more preferably 20 to 21 parts, of curing agent based on the mass of the powder resin. In the present invention, the curing agent preferably includes one or more of dodecanediol (DDDA), triglycidyl isocyanurate (TGIC), and isocyanate, and more preferably DDDA, TGIC, or isocyanate. In the present invention, the above types of curing agents are preferably used, which is advantageous in ensuring the basic physical properties of film formation while simultaneously improving film formation efficiency.

[0034] The raw materials for producing the matrix material described in the present invention contain 0 to 20 parts, preferably 0.3 to 10 parts, more preferably 0.5 to 5 parts, and even more preferably 1 to 2 parts, of an antioxidant auxiliary based on the mass of the powder resin. In the present invention, the antioxidant auxiliary preferably comprises one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecanolpropionate (antioxidant 1076), benzofuranone derivatives, and thioesters, and more preferably antioxidant 1076. In the present invention, the above types of antioxidant auxiliary are preferably used and are advantageous for improving weather resistance.

[0035] The raw materials for producing the matrix material described in the present invention include, based on the mass of the powder resin, 0.05 to 0.2 parts, preferably 0.06 to 0.15 parts, more preferably 0.07 to 0.1 parts, and even more preferably 0.075 to 0.085 parts of catalyst. In the present invention, the catalyst preferably comprises tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole, and more preferably tetrabutylammonium bromide. In the present invention, the above types of catalysts are preferably used and are advantageous in improving film formation efficiency.

[0036] The raw materials for producing the matrix material described in the present invention include, based on the mass of the powder resin, 0 to 10 parts, preferably 0.3 to 5 parts, more preferably 0.5 to 2 parts, and even more preferably 0.8 to 1 part, of a surface modifier. In the present invention, the surface modifier preferably contains benzoin. In the present invention, the above types of surface modifiers are preferably used and are advantageous in improving the surface smoothness and light transmittance after film formation.

[0037] The raw materials for producing the matrix material described in the present invention contain, based on the mass of the powder resin, 0 to 20 parts, preferably 0.5 to 15 parts, more preferably 0.8 to 10 parts, even more preferably 1.2 to 7 parts, and even more preferably 1.66 to 3 parts of a light stabilizer. In the present invention, the light stabilizer preferably includes a triazine-based light stabilizer and a hindered amine-based light stabilizer, and more preferably a triazine-based light stabilizer. The triazine-based light stabilizer is preferably 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (light stabilizer UV-405), and the hindered amine-based light stabilizer is preferably one or more of high molecular weight triazine-piperidine condensate (light stabilizer 119), Tinuvin 622, and Tinuvin 770. In the present invention, the above-mentioned types of light stabilizers are preferably used, which is advantageous for improving weather resistance.

[0038] The raw materials for producing the matrix material described in the present invention include, based on the mass parts of the powder resin, 0.05 to 5 parts, preferably 0.1 to 4.8 parts, more preferably 0.5 to 4.5 parts, even more preferably 1 to 4 parts, even more preferably 1.5 to 3.5 parts, and then even more preferably 2 to 3.45 parts of strontium titanate nano-auxiliary agent. In the present invention, the strontium titanate nano-auxiliary agent is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate, and the mass ratio of the octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate is 3 to 4:4 to 6:1 to 2, preferably 3 to 3.5:5 to 6:1 to 1.5, and more preferably 3:6:1. In the present invention, the particle size of the strontium titanate nano-auxiliary material is preferably 50 to 300 nm, more preferably 50 to 200 nm. In the present invention, the particle size of the octahedral strontium titanate is preferably 100 to 200 nm, the particle size (edge ​​length) of the hexahedral strontium titanate is preferably 100 to 200 nm, and the particle size of the irregular strontium titanate is preferably 50 to 100 nm. In the present invention, the strontium titanate nano-auxiliary material is obtained by mixing specific forms of strontium titanate, thereby enabling the strontium titanate nanomicromaterial to have excellent weather resistance. Furthermore, by mixing and using different forms of strontium titanate, different crystal planes can be provided, which helps in the efficient separation of photo-induced charges and holes, and improves photoelectric conversion efficiency.

[0039] In the present invention, the raw material for producing the strontium titanate nanomicromaterial includes a dispersant, which preferably includes one or more of alumina, fumed silica, and glass microspheres, and more preferably alumina. In the present invention, the mass of the dispersant is 0.05 to 0.2% of the mass of the matrix material, and preferably 0.1 to 0.15%. In the present invention, the above types of dispersants are preferably used to avoid aggregation and are advantageous in improving the processing performance of the product.

[0040] In the present invention, the particle size of the matrix material is preferably 30 to 150 μm, and the particle size of the dispersant is preferably 2 to 8 μm, more preferably 2 to 4 μm. The present invention provides a method for producing strontium titanate nanomicromaterials as described in the above technical solution, The process includes the steps of: mixing raw materials for the production of a matrix material, and sequentially performing melt extrusion, cooling, pulverization, and sieving to obtain a matrix material; and mixing the matrix material with a dispersant to obtain the strontium titanate nanomicro material. Alternatively, the process includes the step of obtaining the strontium titanate nanomicro material by mixing the raw materials for the matrix material with a dispersant and sequentially performing melt extrusion, cooling, pulverization, and sieving.

[0041] In the present invention, the strontium titanate nanomicromaterial can be manufactured by different methods depending on the timing of the addition of the dispersant. This will be explained in detail below. Method 1: The present invention provides a matrix material obtained by mixing raw materials for the production of a matrix material, followed by sequentially performing melt extrusion, cooling, grinding, and sieving, and then mixing the matrix material with a dispersant to obtain the strontium titanate nanomicro material. In the present invention, the method for mixing the raw materials for the production of the matrix material is preferably mechanical mixing. In the present invention, there are no special restrictions on the conditions of the mechanical mixing as long as each production material is mixed uniformly. In the present invention, the temperature of the melt extrusion is preferably 90 to 130°C, more preferably 110 to 120°C. In the present invention, there are no particular restrictions on the cooling, and any cooling method known to those skilled in the art may be used. In the present invention, the grinding preferably includes performing first grinding and second grinding in sequence. In the first grinding, the material is preferably ground to a particle size of 0.2 to 1 cm, and in the second grinding, the material is preferably ground to a particle size of 30 to 150 μm. In the present invention, there are no special restrictions on the sieving as long as a matrix material having the required particle size is obtained. In the present invention, the method for mixing the matrix material and the dispersant is preferably mechanical mixing. In the present invention, there are no special restrictions on the conditions for the mechanical mixing, as long as the matrix material and the dispersant are mixed uniformly. Method II: The present invention provides a strontium titanate nanomicro material by mixing the raw materials for the matrix material with a dispersant, and then sequentially performing melt extrusion, cooling, grinding, and sieving. In the present invention, the method for mixing the raw materials for the matrix material and the dispersant is preferably mechanical mixing. In the present invention, there are no special restrictions on the conditions of the mechanical mixing, as long as each raw material is mixed uniformly. In the present invention, the specific operations of melt extrusion, cooling, grinding, and sieving according to Method II are preferably the same as the specific operations of melt extrusion, cooling, grinding, and sieving according to Method I, and are not repeated here.

[0042] The present invention provides a method for manufacturing a flexible composite material as described in the above technical solution, The process includes the step of impregnating a fiber cloth with molten strontium titanate nanomicromaterial and curing it to obtain a flexible composite material.

[0043] The present invention allows for the impregnation of a fibrous fabric with molten strontium titanate nanomicromaterial using different methods, which are described below in detail. Method 1: The strontium titanate nanomicro material is laid on the surface of the fiber cloth, and the cloth is heated using a laminating device or a rolling device to melt the strontium titanate nanomicro material and impregnate the fiber cloth. Preferably, in this invention, the strontium titanate nanomicro material is uniformly scattered on the surface of the fiber cloth using a powder dispensing device, then the fiber cloth with the strontium titanate nanomicro material scattered on its surface is placed into a laminating device, then the device is closed and heated to melt the strontium titanate nanomicro material and impregnate the fiber cloth. Alternatively, a rolling device is used to roll and heat the fiber cloth with the strontium titanate nanomicro material scattered on its surface to melt the strontium titanate nanomicro material and impregnate the fiber cloth. In this invention, a rolling device is used to facilitate continuous production. In the present invention, the powder dispensing speed of the powder dispensing device is preferably 1 to 10 m / min, more preferably 2 to 6 m / min, and even more preferably 3 to 4 m / min. In the present invention, the heating temperature is determined based on ensuring that the strontium titanate nanomicro material melts, and specifically, the heating temperature is preferably 130 to 170°C, more preferably 130 to 160°C, and even more preferably 130 to 150°C. Method 2: The strontium titanate nanomicro material is extruded to obtain a resin film, the resin film is laminated onto the surface of the fiber cloth, and the resin film is heated using a laminating or rolling device to melt and impregnate the fiber cloth. Preferably, in this invention, the strontium titanate nanomicro material is extruded using an extruder to obtain a resin film, the resin film is laminated onto the surface of the fiber cloth, and then the fiber cloth with the laminated resin film is rolled and heated using a rolling device to melt the resin film and impregnate the fiber cloth with the molten strontium titanate nanomicro material. In this invention, a rolling device is used to facilitate continuous production. In this invention, the extrusion speed of the extruder is preferably 1 to 10 m / min, more preferably 1 to 6 m / min. In this invention, the heating temperature is, specifically, based on ensuring that the resin film melts, preferably 130 to 170°C, more preferably 130 to 160°C, and even more preferably 130 to 150°C.

[0044] In this invention, after impregnating a fiber cloth with molten strontium titanate nanomicromaterial, the obtained material is cured to obtain a flexible composite material. In this invention, the curing temperature is preferably 130 to 200°C, more preferably 140 to 170°C, and even more preferably 150 to 160°C, the pressure is preferably 1 to 20 MPa, more preferably 5 to 15 MPa, and even more preferably 8 to 10 MPa, and the time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes, and even more preferably 30 to 40 minutes. In this invention, when the flexible composite material is manufactured using a lamination apparatus, after curing, it is preferably cooled and demolded to obtain the flexible composite material. When the flexible composite material is manufactured using a rolling apparatus, after curing, it is preferably rolled up to the required size or cut to obtain the flexible composite material.

[0045] The present invention provides the use of a flexible composite material described in the above technical solution, or a flexible composite material manufactured by the manufacturing method described in the above technical solution, as a encapsulant for a photovoltaic module. In the present invention, the photovoltaic module is preferably a lightweight photovoltaic module. In the present invention, the encapsulant can be used specifically on the front panel of the photovoltaic module and also on the back sheet of the photovoltaic module.

[0046] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Clearly, the embodiments described are only a subset of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of the protection of the present invention.

[0047] The strontium titanate nano-auxiliary material used in the examples of the present invention is the product manufactured in Production Examples 1 to 3.

[0048] Manufacturing Example 1 The steps for producing hexahedral strontium titanate nanoparticles are as follows: A composite morphogenetic agent was obtained by mixing palmitic acid, ethylene glycol, 1,2-butanediol, and water. The concentration of palmitic acid in the composite morphogenetic agent was 0.2% by weight, the concentration of ethylene glycol was 0.2% by weight, and the concentration of 1,2-butanediol was 2% by weight. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the composite morphogenetic agent, with a volume ratio of 1:2 between the composite morphogenetic agent and the aqueous solution of titanium tetrachloride. The mixture was stirred for 30 minutes, and during stirring, it was cooled with ice water to obtain mixed solution I. The aforementioned mixed solution I was mixed with a 0.033 g / mL aqueous lithium hydroxide solution and a 0.01 g / mL aqueous strontium hydroxide solution in a volume ratio of 3:3:1, and stirred for 15 minutes to obtain mixed solution II with a pH of 13.8. The mixed solution II was heated to 180°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 48 hours, after which it was cooled at a cooling rate of 2°C / min. The substance after the hydrothermal reaction was centrifuged, and the precipitate was washed five times alternately with water and ethanol. Finally, it was dried at 90°C for 4 hours to obtain hexahedral strontium titanate nanoparticles.

[0049] Manufacturing Example 2 The steps for producing octahedral strontium titanate nanoparticles are as follows: A composite morphogenetic agent was obtained by mixing palmitic acid, ethylene glycol, 1,2-butanediol, and water. The concentration of palmitic acid in the composite morphogenetic agent was 0.2% by weight, the concentration of ethylene glycol was 1% by weight, and the concentration of 1,2-butanediol was 0.2% by weight. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the composite morphogenetic agent, with a volume ratio of 1:2 between the composite morphogenetic agent and the aqueous solution of titanium tetrachloride. The mixture was stirred for 30 minutes, and during stirring, it was cooled with ice water to obtain mixed solution I. The aforementioned mixed solution I was mixed with a 0.033 g / mL aqueous sodium hydroxide solution and a 0.01 g / mL aqueous strontium chloride hexahydrate solution in a volume ratio of 3:3:1, and stirred for 30 minutes to obtain mixed solution II with a pH of 14.2. The mixed solution II was heated to 190°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 24 hours, after which it was cooled at a cooling rate of 2°C / min. The substance after the hydrothermal reaction was centrifuged, and the precipitate was washed three times alternately with water and ethanol. Finally, it was dried at 80°C for 6 hours to obtain octahedral strontium titanate nanoparticles.

[0050] Manufacturing Example 3 The steps for producing irregular strontium titanate are as follows: A composite morphogenetic agent was obtained by mixing palmitic acid, ethylene glycol, 1,2-butanediol, and water. The concentration of palmitic acid in the composite morphogenetic agent was 0.2% by weight, the concentration of ethylene glycol was 1.2% by weight, and the concentration of 1,2-butanediol was 1.6% by weight. A 0.003 g / mL aqueous solution of titanium tetrachloride was added dropwise to the composite morphogenetic agent, with a volume ratio of 1:2 between the composite morphogenetic agent and the aqueous solution of titanium tetrachloride. The mixture was stirred for 30 minutes, and during stirring, it was cooled with ice water to obtain mixed solution I. The aforementioned mixed solution I was mixed with a 0.033 g / mL aqueous sodium hydroxide solution and a 0.01 g / mL aqueous strontium chloride hexahydrate solution in a volume ratio of 3:3:1, and stirred for 30 minutes to obtain mixed solution II with a pH of 14.2. The mixed solution II was heated to 180°C at a heating rate of 4°C / min and subjected to a hydrothermal reaction for 72 hours, after which it was cooled at a cooling rate of 2°C / min. The substance after the hydrothermal reaction was centrifuged, and the precipitate was washed five times alternately with water and ethanol. Finally, it was dried at 80°C for 6 hours to obtain irregular strontium titanate nanoparticles.

[0051] Example 1 The raw materials for producing the strontium titanate nanomicromaterial in this embodiment include a matrix material and a dispersant. The composition is as follows: 72 parts by mass of acrylic resin (specifically, epoxy acrylic powder coating resin manufactured in Example 7 of Patent CN115651473A), 21 parts by mass of curing agent (specifically, DDDA), 1 part by mass of antioxidant auxiliary agent (specifically, antioxidant 1076), 0.085 parts by mass of catalyst (specifically, tetrabutylammonium bromide), 0.8 parts by mass of surface modifier (specifically, benzoin), and 1.66 parts by mass of light stabilizer (specifically, light stabilizer A fixing agent (UV-405) and 3.45 parts of strontium titanate nano-auxiliary material (specifically, a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate in a mass ratio of 3:6:1) were mixed and melt-extruded at 120°C. After the resulting extruded material was cooled, it was pulverized to a particle size of 0.2 to 1 cm, and further pulverization, grading, and sieving were performed to obtain a matrix material with a particle size of 30 to 150 μm. The dispersant is alumina, the particle size of the dispersant is 2 - 4 μm, and the mass of the dispersant is 0.1% of the mass of the matrix material. The matrix material was mixed with the dispersant to obtain the strontium titanate nano / micro material. Using a powder spraying device, the strontium titanate nano / micro material was uniformly sprayed on the surface of a glass fiber cloth (specifically, a woven glass fiber cloth with a weight of 100 g / m 2 at a powder spraying rate of 4 m / min. Next, the glass fiber cloth with the strontium titanate nano / micro material sprayed on its surface was put into a laminating device, the device was closed and heated to 130°C to melt the strontium titanate nano / micro material and infiltrate it into the glass fiber cloth. Then, it was cured at 160°C and a pressure of 10 MPa for 30 minutes. After the curing was completed, it was cooled and demolded to obtain a flexible composite material. The content of the strontium titanate nano / micro material in the flexible composite material was 55% by weight, and the thickness of the flexible composite material was 0.15 mm.

[0052] Example 2 A flexible composite material was manufactured according to the method of Example 1, except that the weight of the glass fiber cloth used was 200 g / m 2 and the thickness of the flexible composite material was 0.22 mm.

[0053] Example 3 A flexible composite material was manufactured according to the method of Example 1, except that the weight of the glass fiber cloth used was 300 g / m 2 and the thickness of the flexible composite material was 0.31 mm.

[0054] Example 4 A flexible composite material was manufactured according to the method of Example 1, except that the content of the strontium titanate nano / micro material in the flexible composite material was 60% by weight.

[0055] Comparative Example 1 A flexible composite material was manufactured according to the method of Example 1, except that the strontium titanate nano-auxiliary material in the strontium titanate nanomicromaterial was omitted.

[0056] Test Example 1 The strength of the flexible composite materials produced in Examples 1-4 and Comparative Example 1 was tested according to the method of GB / T 13542.2-2021 (product strength requirement ≥ 100 MPa), and the water permeability of the flexible composite materials produced in Examples 1-4 and Comparative Example 1 was tested according to the method of GB / T 21529-2008 (product water permeability requirement ≤ 1.5 g / (m2·24h)). The results are shown in Table 1.

[0057] [Table 1]

[0058] As can be seen from Examples 1-3 in Table 1, the greater the weight of the glass fiber cloth, the thicker the manufactured flexible composite material becomes, increasing its tensile strength and water permeability. As can be seen from Examples 1 and 4, as the content of strontium titanate nanomicromaterial in the flexible composite material increases, the strength of the flexible composite material decreases and its water permeability decreases slightly. As can be seen from Example 1 and Comparative Example 1, even if the strontium titanate nano-auxiliary material is omitted from the strontium titanate nanomicromaterial, the strength and water permeability of the flexible composite material do not change significantly. This indicates that by adding strontium titanate nanomicromaterial during the manufacturing of the flexible composite material, the flexible composite material can maintain good mechanical properties and water impermeability.

[0059] Comparative Example 2 A flexible composite material was manufactured according to the method of Example 1, except that the strontium titanate nanomicro material was replaced with a commercially available flexible solar power generation material.

[0060] Test Example 2 The elongation at break and light transmittance of the flexible composite materials produced in Example 1 and Comparative Example 2 were tested and compared with those of conventional photovoltaic glass. Here, elongation at break was tested according to the method of GB / T 13542.2-2021, and light transmittance according to the method of GB / T 2410-2008. The results are shown in Table 2. As shown in Table 2, although the light transmittance of the flexible composite material produced using strontium titanate nanomicromaterial is not as high as that of conventional photovoltaic glass, the elongation at break and light transmittance are superior to those of flexible composite materials produced using commercially available flexible photovoltaic materials, and the elongation at break is also superior to that of conventional photovoltaic glass.

[0061] [Table 2]

[0062] Test Example 3 The weather resistance of the flexible composite materials produced in Example 1 and Comparative Examples 1-2 was tested according to the method of GB / T 29848-2018, and the results are shown in Table 3. As shown in Table 3, the flexible composite material produced in Example 1 of the present invention is obtained by compounding a strontium titanate nanomicro material with a fibrous fabric and adding a strontium titanate nano-auxiliary to the matrix material of the strontium titanate nanomicro material. As a result, the flexible composite material can have better weather resistance, such as resistance to ultraviolet rays and heat and humidity, than the flexible composite materials produced in Comparative Examples 1 and 2.

[0063] [Table 3]

[0064] As can be seen from the above test examples, the flexible composite material provided by the present invention possesses not only excellent weather resistance but also features such as lightweight, high strength, high light transmittance, and good water-impermeable properties. Furthermore, the flexible composite material provided by the present invention also possesses high stain resistance and easy cleaning. Typically, major dirt can be removed by washing with rainwater, and the outdoor service life is expected to be 25 years or more.

[0065] The above description is merely a preferred embodiment of the present invention. Those skilled in the art should note that various improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications are also within the scope of protection of the present invention.

Claims

1. A flexible composite material comprising a fibrous fabric and a strontium titanate nanomicro material compounded with the fibrous fabric, The manufacturing raw materials for the strontium titanate nanomicromaterial include a matrix material and a dispersant, wherein the mass of the dispersant is 0.05 to 0.2% of the mass of the matrix material, and the matrix material comprises, by mass, 50 to 90 parts of powdered resin, 10 to 50 parts of curing agent, 0 to 20 parts of antioxidant auxiliary, 0.05 to 0.2 parts of catalyst, 0 to 10 parts of surface modifier, 0 to 20 parts of light stabilizer, and 0.05 to 5 parts of strontium titanate nano-auxiliary, wherein the strontium titanate nano-auxiliary is a mixture of octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate, and the mass ratio of the octahedral strontium titanate, hexahedral strontium titanate, and irregular strontium titanate is 3 to 4:4 to 6:1 to 2, characterized in that this is a flexible composite material.

2. The flexible composite material according to claim 1, characterized in that the aforementioned fiber cloth is a glass fiber cloth.

3. The weight of the aforementioned fiber cloth is 100 to 400 g / m ２ The flexible composite material according to claim 2, characterized in that it is the same as described above.

4. The flexible composite material according to claim 1, characterized in that the particle size of the strontium titanate nano-additive is 50 to 300 nm.

5. The flexible composite material according to claim 4, characterized in that the particle size of the octahedral strontium titanate is 100 to 200 nm, the particle size of the hexahedral strontium titanate is 100 to 200 nm, and the particle size of the irregular strontium titanate is 50 to 100 nm.

6. The flexible composite material according to claim 1, characterized in that the powdered resin contains one or more of acrylic resin, polyurethane resin, and polyester resin.

7. The flexible composite material according to claim 6, characterized in that the acrylic resin is an epoxy acrylic resin.

8. The flexible composite material according to claim 1, characterized in that the curing agent comprises one or more of dodecanediic acid, triglycidyl isocyanurate, and isocyanate.

9. The flexible composite material according to claim 1, characterized in that the antioxidant auxiliary agent comprises one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecanolpropionate, benzofuranone derivatives, and thioester antioxidants.

10. The flexible composite material according to claim 1, characterized in that the catalyst comprises tetrabutylammonium bromide, dibutyltin dilaurate, or 2-propylimidazole.

11. The flexible composite material according to claim 1, characterized in that the surface modifier contains benzoin.

12. The flexible composite material according to claim 1, characterized in that the light stabilizer includes a triazine-based light stabilizer and a hindered amine-based light stabilizer.

13. The flexible composite material according to claim 1, characterized in that the particle size of the matrix material is 30 to 150 μm.

14. The flexible composite material according to claim 1, characterized in that the particle size of the dispersant is 2 to 8 μm.

15. The flexible composite material according to claim 1, characterized in that the dispersant comprises one or more of alumina, fumed silica, and glass microspheres.

16. The flexible composite material according to any one of claims 1 to 15, characterized in that the content of strontium titanate nanomicromaterial in the flexible composite material is 50 to 80% by weight.

17. A method for manufacturing a flexible composite material according to any one of claims 1 to 16, A manufacturing method characterized by comprising the step of impregnating a fiber cloth with molten strontium titanate nanomicromaterial and curing it to obtain a flexible composite material.

18. The method for impregnating a fiber cloth with the molten strontium titanate nanomicro material is as follows: The manufacturing method according to claim 17, characterized by comprising the steps of laying the strontium titanate nanomicro material on the surface of the fiber cloth, heating it using a laminating device or a rolling device to melt the strontium titanate nanomicro material and impregnate the fiber cloth.

19. The method for impregnating a fiber cloth with the molten strontium titanate nanomicro material is as follows: The manufacturing method according to claim 17, characterized by comprising the steps of extruding the strontium titanate nanomicro material to obtain a resin film, laminating and compounding the resin film onto the surface of the fiber cloth, and heating with a laminating device or rolling device to melt the resin film and impregnate the fiber cloth.

20. The manufacturing method according to any one of claims 17 to 19, characterized in that the curing temperature is 130 to 200°C, the pressure is 1 to 20 MPa, and the time is 10 to 90 minutes.

21. The use of a flexible composite material according to any one of claims 1 to 16, or a flexible composite material manufactured by the manufacturing method according to any one of claims 17 to 20, as a encapsulant for a solar power generation module.

22. The use according to claim 21, characterized in that the sealing material is a sealing material for the front panel or back sheet of a solar power generation module.

Images