Glass fiber composite film as well as preparation method and application thereof

Abstract

The invention relates to the field of photovoltaic technology, and discloses a glass fiber composite film and a preparation method and application thereof, the composite film comprises a glass fiber base material layer, a flame retardant layer, a reflecting layer, a light diffusion layer and a polyvinylidene fluoride protective layer which are stacked in sequence; a first material for forming the flame-retardant layer contains 40 wt%-80 wt% of polyurethane, 13 wt%-51 wt% of aluminum hydroxide, 0.2 wt%-1.2 wt% of a silane coupling agent and 3 wt%-21 wt% of phosphate; a second material for forming the light diffusion layer contains 80 wt%-95 wt% of polyurethane and 5 wt%-20 wt% of microsphere particles with hollow structures. The composite film has the advantages of high reflectivity, high weather resistance, high flame retardance and no pollution.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and in particular to a glass fiber composite film and a preparation method and application thereof. Background Art

[0002] The back of the double-glass photovoltaic module uses reflected light or scattered light from the ground to generate electricity. The higher the reflectivity of the ground, the stronger the light received by the back of the battery, and the better the power generation effect. In addition to having a high reflectivity, the reflective film also needs to have good weather resistance, flame retardancy and self-cleaning properties. In the prior art, the diffuse reflection of polished and oxidized aluminum plates with a purity of 99.5% can only reach about 50%, and the diffuse reflection of white tiles with better reflectivity is about 55%; moreover, both aluminum plates and tiles are relatively hard, and the laying scenes are very limited, and the seamless splicing of aluminum plates and tiles is cumbersome and wastes man-hours; in addition, the mirror reflection of aluminum plates and tiles will cause the temperature of photovoltaic panels to rise, thereby affecting the service life of photovoltaic panels.

[0003] In order to solve the above problems, CN114551622A proposes a flexible reflective material composed of a polyester base cloth, a PVC paste resin slurry, and a polyvinylidene fluoride coating. The prepared flexible reflective material can produce high diffuse reflectivity at 380-780nm (visible light) and 280nm-1100nm (ultraviolet UVA and UVB to near infrared), which can reach 91% and 82% or more respectively; but due to the poor outdoor weather resistance and flame retardant effect of the product, the material turns yellow, ages and cracks due to long-term outdoor exposure to wind and sun, and has a short service life, which limits the application scope and economic benefits of the material, and the polyvinyl chloride layer thereof will decompose toxic gases such as chlorine and hydrogen chloride at high temperatures, which are difficult to recycle and treat in the later stage, causing great environmental pollution. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem that the reflective film in the prior art cannot have high reflectivity, high weather resistance, high flame retardancy and no pollution.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a glass fiber composite film, which comprises a glass fiber substrate layer, a flame retardant layer, a reflective layer, a light diffusion layer and a polyvinylidene fluoride protective layer stacked in sequence;

[0006] The first material forming the flame retardant layer contains 40wt%-80wt% of polyurethane, 13wt%-51wt% of aluminum hydroxide, 0.2wt%-1.2wt% of silane coupling agent, and 3wt%-21wt% of phosphate;

[0007] The second material forming the light diffusion layer contains 80wt%-95wt% of polyurethane and 5wt%-20wt% of microsphere particles with a hollow structure;

[0008] The true density of the microsphere particles is 1.0-1.45 g / cm 3 The refractive index is 1.42-1.45 (in the visible light range of 400-700nm, the medium is air), and the average particle diameter is 0.5-1.5μm.

[0009] Preferably, the aluminum hydroxide has an average particle size D50 of 9-12 μm, an oil absorption value of ≤24 mL / 100 g, and a bulk density of 0.7-0.9 g / cm 3 .

[0010] Preferably, the viscosity of the polyurethane at 25° C. is 800-5000 mPa·s.

[0011] Preferably, the thickness of the polyvinylidene fluoride protective layer is 7-20 μm, the thickness of the light diffusion layer is 20-100 μm, the thickness of the reflective layer is 5-10 μm, the thickness of the flame retardant layer is 50-200 μm, and the thickness of the glass fiber substrate layer is 200-400 μm.

[0012] Preferably, the silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-isocyanatopropyltriethoxysilane.

[0013] Preferably, the microsphere particles are selected from at least one of silicone microspheres, glass microspheres, and polycarbonate microspheres.

[0014] Preferably, the phosphate is selected from at least one of melamine polyphosphate, ammonium polyphosphate and tributyl phosphate.

[0015] Preferably, the reflective layer is made of aluminum foil.

[0016] The second aspect of the present invention provides the use of the glass fiber composite film described in the first aspect in a reflective film of a double-glass photovoltaic module.

[0017] The third aspect of the present invention provides a method for preparing the glass fiber composite film according to the first aspect, the method comprising:

[0018] (1) first stirring polyurethane, silane coupling agent, aluminum hydroxide and phosphate to obtain a first material, and

[0019] The polyurethane and the microsphere particles having a hollow structure are stirred for a second time to obtain a second material;

[0020] (2) coating the first material onto the upper surface of the glass fiber substrate layer to form a flame retardant layer on the upper surface of the glass fiber substrate layer, and bonding the reflective layer to the flame retardant layer; then coating the second material onto the lower surface of the reflective layer that is not bonded to the flame retardant layer to form a light diffusion layer on the surface of the reflective layer; and then bonding the polyvinylidene fluoride protective layer to the light diffusion layer to obtain the glass fiber composite material.

[0021] Preferably, the method further comprises the following steps: subjecting the product obtained by laminating the polyvinylidene fluoride protective layer and the light diffusion layer to a first drying treatment and a first curing treatment in sequence to obtain the glass fiber composite material;

[0022] The operation of the first drying treatment includes: subjecting the product to first heating, second heating, third heating and fourth heating in sequence, wherein the temperature of the second heating is 5-15°C higher than the temperature of the first heating, the temperature of the third heating is 5-15°C higher than the temperature of the second heating, and the temperature of the fourth heating is 3-7°C higher than the temperature of the third heating.

[0023] Preferably, the glass fiber substrate layer is prepared by the following method:

[0024] The glass fiber cloth is subjected to shaping, impregnation, gelling and drying and plasticization treatments in sequence to obtain the glass fiber substrate layer.

[0025] Preferably, the shaping conditions include: a temperature of 170-190° C. and a time of 120-170 seconds.

[0026] Preferably, the operation of the dipping treatment includes: using epoxy resin slurry as the dipping liquid to perform the dipping treatment.

[0027] Preferably, the gel treatment conditions include: temperature of 160-180° C. and time of 35-55 s.

[0028] The present invention has at least the following advantages:

[0029] (1) The polyvinylidene fluoride protective layer in the glass fiber composite film of the present invention is located at the outermost layer of the material, is stable at high temperatures, does not decompose toxic substances, has the advantages of safety and environmental protection, and has good corrosion resistance, aging resistance, mechanical properties and self-cleaning properties, and can meet the needs of photovoltaic installation in desertified areas;

[0030] (2) The glass fiber composite film of the present invention has the advantages of high reflectivity and good plasticity, which provides a guarantee for photovoltaic power generation gain and outdoor laying;

[0031] (3) The reflective layer and the light diffusion layer in the glass fiber composite film of the present invention cooperate to ensure the uniform divergence of the reflected light; under the premise of ensuring high reflectivity, the diffuse reflection ratio is greatly improved, the back light rate of the photovoltaic module is enhanced, and the safety of the glass fiber composite film is ensured;

[0032] (4) The glass fiber composite film of the present invention has high reflectivity, high weather resistance and high flame retardancy while ensuring pollution-free use and recycling. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a structural diagram of the glass fiber reflective film material prepared in Example 1 of the present invention.

[0034] Description of Reference Numerals

[0035] Figure 1 Here, 1 represents a polyvinylidene fluoride protective layer, 2 represents a light diffusion layer, 3 represents a reflective layer, 4 represents a flame retardant layer, and 5 represents a glass fiber base material layer. DETAILED DESCRIPTION

[0036] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] As mentioned above, the first aspect of the present invention provides a glass fiber composite film, which includes a glass fiber substrate layer, a flame retardant layer, a reflective layer, a light diffusion layer and a polyvinylidene fluoride protective layer stacked in sequence;

[0038] The first material forming the flame retardant layer contains 40wt%-80wt% of polyurethane, 13wt%-51wt% of aluminum hydroxide, 0.2wt%-1.2wt% of silane coupling agent, and 3wt%-21wt% of phosphate;

[0039] The second material forming the light diffusion layer contains 80wt%-95wt% of polyurethane and 5wt%-20wt% of microsphere particles with a hollow structure;

[0040] The true density of the microsphere particles is 1.0-1.45 g / cm 3 The refractive index is 1.42-1.45 (in the visible light range of 400-700nm, the medium is air), and the average particle diameter is 0.5-1.5μm.

[0041] According to a preferred embodiment, the first material contains 70wt%-80wt% of polyurethane, 15wt%-20wt% of aluminum hydroxide, 0.3wt%-0.5wt% of silane coupling agent, and 4wt%-10wt% of phosphate. The inventors of the present invention have found that under this preferred condition, the glass fiber composite film of the present invention has better flame retardancy, reflectivity and weather resistance.

[0042] Preferably, the aluminum hydroxide has an average particle size D50 of 9-12 μm, an oil absorption value of ≤24 mL / 100 g, and a bulk density of 0.7-0.9 g / cm 3 The inventors of the present invention have found that under this preferred condition, the glass fiber composite film of the present invention has more excellent flame retardancy.

[0043] Preferably, the viscosity of the polyurethane at 25° C. is 800-5000 mPa·s. The inventors of the present invention have found that under this preferred condition, the glass fiber composite film of the present invention has better flame retardancy.

[0044] According to a preferred embodiment, the thickness of the polyvinylidene fluoride protective layer is 7-20 μm, the thickness of the light diffusion layer is 20-100 μm, the thickness of the reflective layer is 5-10 μm, the thickness of the flame retardant layer is 50-200 μm, and the thickness of the glass fiber substrate layer is 200-400 μm. The inventors of the present invention have found that under this preferred condition, the glass fiber composite film of the present invention has better flame retardancy, reflectivity and weather resistance.

[0045] Preferably, the silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-isocyanatopropyltriethoxysilane.

[0046] Preferably, the microsphere particles are selected from at least one of silicone microspheres, glass microspheres, and polycarbonate microspheres.

[0047] Preferably, the phosphate is selected from at least one of melamine polyphosphate, ammonium polyphosphate and tributyl phosphate.

[0048] Preferably, the reflective layer is made of aluminum foil.

[0049] Further preferably, the weight of the aluminum foil is 50-70 g / m 2 .

[0050] According to a preferred embodiment, the silane coupling agent is γ-methacryloxypropyltrimethoxysilane, the phosphate is melamine polyphosphate, the microsphere particles are silicone microspheres, and the material of the reflective layer is aluminum foil. The inventors of the present invention have found that under this preferred condition, the glass fiber composite film of the present invention has better flame retardancy, reflectivity and weather resistance.

[0051] The present invention exemplarily provides a structural diagram of a glass fiber composite membrane, such as Figure 1 shown. Figure 1 Here, 1 represents a polyvinylidene fluoride protective layer, 2 represents a light diffusion layer, 3 represents a reflective layer, 4 represents a flame retardant layer, and 5 represents a glass fiber base material layer.

[0052] As mentioned above, the second aspect of the present invention provides the use of the glass fiber composite film described in the first aspect in the reflective film of a double-glass photovoltaic module.

[0053] As mentioned above, the third aspect of the present invention provides a method for preparing the glass fiber composite film according to the first aspect, the method comprising:

[0054] (1) first stirring polyurethane, silane coupling agent, aluminum hydroxide and phosphate to obtain a first material, and

[0055] The polyurethane and the microsphere particles having a hollow structure are stirred for a second time to obtain a second material;

[0056] (2) coating the first material onto the upper surface of the glass fiber substrate layer to form a flame retardant layer on the upper surface of the glass fiber substrate layer, and bonding the reflective layer to the flame retardant layer; then coating the second material onto the lower surface of the reflective layer that is not bonded to the flame retardant layer to form a light diffusion layer on the surface of the reflective layer; and then bonding the polyvinylidene fluoride protective layer to the light diffusion layer to obtain the glass fiber composite material.

[0057] The definitions and amounts of polyurethane, silane coupling agent, aluminum hydroxide, phosphate, polyurethane, and microsphere particles described in the third aspect of the present invention are the same as the definitions and contents of the corresponding components described in the glass fiber composite film described in the first aspect of the present invention. For example, based on the total weight of the first material, the amount of the polyurethane is 40wt%-80wt%, the amount of the aluminum hydroxide is 13wt%-51wt%, the amount of the silane coupling agent is 0.2wt%-1.2wt%, and the amount of the phosphate is 3wt%-21wt%; based on the total weight of the second material, the amount of the polyurethane is 80wt%-95wt%, and the amount of the microsphere particles is 5wt%-20wt%; the true density of the microsphere particles is 1.0-1.45g / cm 3, the refractive index is 1.42-1.45 (in the visible light range of 400-700nm, the medium is air), and the average particle diameter is 0.5-1.5μm. In order to avoid redundancy, the present invention will not be repeated in the third aspect, and those skilled in the art should not be understood as limiting the present invention.

[0058] According to a preferred embodiment, the coating amounts of the first material and the second material are controlled so as to satisfy the thicknesses of the flame retardant layer and the light diffusion layer to be 50-200 μm and 20-100 μm, respectively.

[0059] Further preferably, the thickness of the polyvinylidene fluoride protective layer is 7-20 μm, the thickness of the light diffusion layer is 20-100 μm, the thickness of the reflective layer is 5-10 μm, the thickness of the flame retardant layer is 50-200 μm, and the thickness of the glass fiber substrate layer is 200-400 μm.

[0060] It should be noted that the present invention has no special requirements for the first stirring and the second stirring methods, and the stirring operation can be performed by conventional methods in the art, which should not be construed as a limitation to the present invention by those skilled in the art.

[0061] According to a preferred embodiment, the method further comprises the following steps: subjecting the product obtained by laminating the polyvinylidene fluoride protective layer and the light diffusion layer to a first drying treatment and a first curing treatment in sequence to obtain the glass fiber composite material.

[0062] Preferably, the operation of the first drying treatment includes: subjecting the product to first heating, second heating, third heating and fourth heating in sequence, and the temperature of the second heating is 5-15°C higher than the temperature of the first heating, the temperature of the third heating is 5-15°C higher than the temperature of the second heating, and the temperature of the fourth heating is 3-7°C higher than the temperature of the third heating. The inventors of the present invention have found that under this preferred condition, the obtained glass fiber composite film has better flame retardancy, reflectivity and weather resistance.

[0063] Further preferably, the first heating temperature is 25-65°C, the second heating temperature is 30-70°C, the third heating temperature is 35-75°C, and the fourth heating temperature is 40-80°C.

[0064] Preferably, the first heating time is 30-45 s, the second heating time is 30-45 s, the third heating time is 30-45 s, and the fourth heating time is 30-45 s.

[0065] Preferably, the temperature of the first curing treatment is 50-60° C. and the time is 60-70 hours.

[0066] According to a particularly preferred embodiment, the method further includes the following steps: subjecting the product obtained by bonding the reflective layer and the flame retardant layer to a second drying treatment and a second curing treatment in sequence, and then coating the second material to the lower surface of the reflective layer that is not bonded to the flame retardant layer.

[0067] Preferably, the conditions of the second drying treatment are the same as those of the first drying treatment; and the conditions of the second curing treatment are the same as those of the first curing treatment.

[0068] Preferably, the glass fiber substrate layer is prepared by the following method:

[0069] The glass fiber cloth is subjected to shaping, impregnation, gelling and drying and plasticizing treatments in sequence to obtain the glass fiber substrate layer.

[0070] Preferably, the shaping conditions include: a temperature of 170-190° C. and a time of 120-170 seconds.

[0071] Preferably, the operation of the dipping treatment includes: using epoxy resin slurry as the dipping liquid to perform the dipping treatment.

[0072] In the present invention, there is no particular limitation on the conditions of the immersion treatment, and the immersion treatment can be carried out in a conventional manner in the art, which should not be construed as a limitation to the present invention by those skilled in the art.

[0073] Preferably, the gel treatment conditions include: temperature of 160-180° C. and time of 35-55 s.

[0074] Preferably, the conditions for the drying and plasticizing treatment include: a temperature of 150-170° C. and a time of 20-40 seconds.

[0075] In the following examples, unless otherwise specified, the raw materials involved are all commercially available products.

[0076] Polyurethane: viscosity 1000-4000 mPa·s at 25°C, model TS-9015A, purchased from Dongguan Yantai Chemical Technology Co., Ltd.;

[0077] Silane coupling agent G1: Model KH-570, purchased from Nanjing Nengde New Materials Technology Co., Ltd.;

[0078] Silane coupling agent G2: phenyltrimethoxysilane, model SCA-P61M phenyltrimethoxysilane 2996-92-1, purchased from Nanjing Nengde New Materials Technology Co., Ltd.;

[0079] Aluminum hydroxide H1: brand H-WF-10LV, purchased from China Aluminum Shandong Co., Ltd.;

[0080] Microsphere Y1: Silicone microsphere, true density 1.32g / cm 3 , refractive index is 1.43 (in the range of visible light 400-700nm, the medium is air), the average particle diameter is 0.6μm, model ERAD DF10A0, purchased from Changxing Chemical Industry Co., Ltd.;

[0081] Microsphere Y2: glass microsphere, true density 4.1g / cm 3 , refractive index is 1.9 (in the range of visible light 400-700nm, the medium is air), the average particle diameter is 38μm, model FGF-7 was purchased from Hebei Wensheng New Materials Technology Co., Ltd.;

[0082] Aluminum foil: size 1.2*100 meters, thickness 7μm, aluminum content ≥99%, weight 60g / m 2 ;

[0083] Polyvinylidene fluoride: size 1.2*100 meters, thickness 12 μm, purchased from Hangzhou Fumo New Materials Co., Ltd.;

[0084] Glass fiber cloth, size 1.2*100 meters; model SD-FB-17-11-140, purchased from Ningbo Shengda Fiberglass Co., Ltd.;

[0085] Ink: Solar photovoltaic white ink, Xiamen Hansenda Electronic Technology Co., Ltd.

[0086] Preparation Example 1

[0087] The glass fiber cloth was shaped at 180° C. for 150 seconds, then immersed in epoxy resin slurry for 5 minutes, gelled at 170° C. for 45 seconds, and finally dried and plasticized at 160° C. for 30 seconds to obtain the glass fiber substrate layer with a thickness of 300 μm.

[0088] Example 1

[0089] In this embodiment, the first material and the second material are prepared according to the formula in Table 1, and the glass fiber composite film is prepared according to the following method:

[0090] (1) performing a first stirring on polyurethane, a silane coupling agent (G1), aluminum hydroxide and a phosphate (melamine polyphosphate) to obtain a first material, wherein the first stirring time is 10 min and the stirring speed is 500 rpm; and

[0091] The polyurethane and the microsphere particles (Y1) having a hollow structure are stirred for a second time to obtain a second material, wherein the second stirring time is 10 minutes and the stirring speed is 500 revolutions per minute;

[0092] (2) coating the first material onto the upper surface of the glass fiber substrate layer prepared in Preparation Example 1, controlling the coating amount of the first material so that a 100 μm flame retardant layer is formed on the upper surface of the glass fiber substrate layer, and laminating the 7 μm reflective layer to the flame retardant layer to obtain a product 1, and then sequentially performing a first drying treatment and a first curing treatment on the product 1;

[0093] The operation of the first drying treatment is: subjecting the product 1 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0094] The conditions for the first curing treatment are: temperature 56°C, time 65h;

[0095] (3) coating the second material on the lower surface of the reflective layer that is not bonded to the flame retardant layer, and controlling the coating amount of the second material so that a 50 μm light diffusion layer is formed on the surface of the reflective layer; then bonding the 12 μm polyvinylidene fluoride protective layer to the light diffusion layer to obtain product 2, and then sequentially subjecting product 2 to a second drying treatment and a second curing treatment to obtain a glass fiber composite film, named B1;

[0096] The operation of the second drying treatment is: subjecting the product 2 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0097] The conditions of the second curing treatment are: temperature of 56° C. and time of 65 h.

[0098] Examples 2 to 6 and Comparative Examples 1 to 3 are carried out using the same process as Example 1, except that the types or amounts of the components used in the first material and the second material are different, see Table 1 for details.

[0099] Example 7

[0100] This embodiment adopts the same process as that of embodiment 1, except that the coating amount of the first material is controlled so that a 20 μm flame retardant layer is formed on the upper surface of the glass fiber substrate layer.

[0101] Comparative Example 4

[0102] This comparative example is carried out in a similar process to Example 1, except that the reflective layer in Example 1 is an aluminum foil with a thickness of 7 μm, while the reflective layer in this comparative example is an ink with a thickness of 7 μm. Specifically:

[0103] (1) performing a first stirring on polyurethane, a silane coupling agent (G1), aluminum hydroxide and a phosphate (melamine polyphosphate) to obtain a first material, wherein the first stirring time is 10 min and the stirring speed is 500 rpm; and

[0104] The polyurethane and the microsphere particles (Y1) having a hollow structure are stirred for a second time to obtain a second material, wherein the second stirring time is 10 minutes and the stirring speed is 500 revolutions per minute;

[0105] The ink was stirred at 25° C. for 30 min to obtain a third material;

[0106] (2) coating the first material onto the upper surface of the glass fiber substrate layer prepared in Preparation Example 1, controlling the coating amount of the first material so that a flame retardant layer of 100 μm is formed on the upper surface of the glass fiber substrate layer, to obtain a product 1, and then sequentially subjecting the product 1 to a first drying treatment and a first curing treatment;

[0107] The operation of the first drying treatment is: subjecting the product 1 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0108] The conditions for the first curing treatment are: temperature 56°C, time 65h;

[0109] (3) coating a third material on the lower surface of the flame retardant layer that is not bonded to the glass fiber substrate layer, controlling the coating amount of the third material so that a 7 μm reflective layer is formed on the surface of the flame retardant layer to obtain a product 2, and then sequentially subjecting the product 2 to a second drying treatment and a second curing treatment;

[0110] The operation of the second drying treatment is: subjecting the product 2 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0111] The conditions for the second curing treatment are: temperature 56°C, time 65h;

[0112] (4) coating the second material on the lower surface of the reflective layer not bonded to the flame retardant layer, controlling the coating amount of the second material so that a 50 μm light diffusion layer is formed on the surface of the reflective layer; then bonding a 12 μm polyvinylidene fluoride protective layer to the light diffusion layer to obtain product 3, and then sequentially subjecting product 3 to a third drying treatment and a third curing treatment to obtain a glass fiber composite film, named DB4;

[0113] The operation of the third drying treatment is: subjecting the product 3 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0114] The conditions of the third curing treatment are: temperature of 56° C. and time of 65 h.

[0115] Comparative Example 5

[0116] This comparative example is carried out in a similar process to Example 1, except that the arrangement order of the functional layers (glass fiber substrate layer, light diffusion layer, reflection layer, flame retardant layer and polyvinylidene fluoride protective layer) is different, specifically:

[0117] (1) performing a first stirring on polyurethane, a silane coupling agent (G1), aluminum hydroxide and a phosphate (melamine polyphosphate) to obtain a first material, wherein the first stirring time is 10 min and the stirring speed is 500 rpm; and

[0118] The polyurethane and the microsphere particles (Y1) having a hollow structure are stirred for a second time to obtain a second material, wherein the second stirring time is 10 minutes and the stirring speed is 500 revolutions per minute;

[0119] (2) coating the second material onto the upper surface of the glass fiber substrate layer prepared in Preparation Example 1, controlling the coating amount of the second material so that a 50 μm light diffusion layer is formed on the upper surface of the glass fiber substrate layer, and laminating the 7 μm reflective layer to the light diffusion layer to obtain a product 1, and then sequentially performing a first drying treatment and a first curing treatment on the product 1;

[0120] The operation of the first drying treatment is: subjecting the product 1 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0121] The conditions for the first curing treatment are: temperature 56°C, time 65h;

[0122] (3) coating the first material on the lower surface of the reflective layer that is not bonded to the light diffusion layer, and controlling the coating amount of the second material so that a 100 μm flame retardant layer is formed on the surface of the reflective layer; then bonding a 12 μm polyvinylidene fluoride protective layer to the flame retardant layer to obtain product 2, and sequentially subjecting product 2 to a second drying treatment and a second curing treatment to obtain a glass fiber composite film, named DB5;

[0123] The operation of the second drying treatment is: subjecting the product 2 to first heating, second heating, third heating and fourth heating in sequence; the conditions of the first heating are: temperature of 45°C and time of 30s; the conditions of the second heating are: temperature of 50°C and time of 30s; the conditions of the third heating are: temperature of 55°C and time of 30s; the conditions of the fourth heating are: temperature of 60°C and time of 30s;

[0124] The conditions of the second curing treatment are: temperature of 56° C. and time of 65 h.

[0125] Table 1

[0126]

[0127] Table 1

[0128]

[0129]

[0130] Test Example 1

[0131] The reflectivity of B1 to B8 and DB1 to DB5 were tested according to the ASTM E903 standard, and the flame retardancy was tested according to the UL94 standard. The test results are shown in Table 2.

[0132] Test Example 2

[0133] B1 to B8, DB1 to DB5 were subjected to UV aging test, damp heat test and thermal cycle test according to IEC 61215-2:2016 standard, and the test results are shown in Table 3;

[0134] The UV aging test (UV60) conditions are: UV irradiance: 100w / m 2 The sample surface temperature is controlled at 60℃±5℃, and the cumulative irradiation is 60kwh / m 2 ;

[0135] Damp heat test (DH1000) conditions: indoor air temperature: (85±2)℃, relative humidity (85±5)%RH, test time 1000 hours;

[0136] Thermal cycle test (TC200) conditions: Cycle between (-40±2)℃ and (+85±2)℃, the temperature change rate between the low and high extremes does not exceed 100℃ / h, the sample temperature remains stable at each extreme for 10 minutes, the cycle time is 6 hours, and the total cycle is 200 times.

[0137] Table 2

[0138]

[0139]

[0140] Table 3

[0141]

[0142] From the analysis of the results in the above table, it can be seen that the diffuse reflectivity, weather resistance and flame retardancy of the product prepared by the technical solution of the present invention are significantly better.

[0143] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A glass fiber composite film, characterized in that: The composite film comprises a glass fiber substrate layer, a flame retardant layer, a reflective layer, a light diffusion layer and a polyvinylidene fluoride protective layer which are stacked in sequence; The first material forming the flame retardant layer contains 40wt%-80wt% of polyurethane, 13wt%-51wt% of aluminum hydroxide, 0.2wt%-1.2wt% of silane coupling agent, and 3wt%-21wt% of phosphate; The second material forming the light diffusion layer contains 80wt%-95wt% of polyurethane and 5wt%-20wt% of microsphere particles with a hollow structure; The true density of the microsphere particles is 1.0-1.45 g / cm 3 The refractive index is 1.42-1.45 (in the visible light range of 400-700nm, the medium is air), and the average particle diameter is 0.5-1.5μm.

2. The glass fiber composite membrane according to claim 1, characterized in that: The aluminum hydroxide has a D50 average particle size of 9-12 μm, an oil absorption value of ≤24 mL / 100 g, and a bulk density of 0.7-0.9 g / cm 3 .

3. The glass fiber composite membrane according to claim 1 or 2, characterized in that: The viscosity of the polyurethane at 25° C. is 800-5000 mPa·s.

4. The glass fiber composite membrane according to claim 1 or 2, characterized in that: The thickness of the polyvinylidene fluoride protective layer is 7-20 μm, the thickness of the light diffusion layer is 20-100 μm, the thickness of the reflective layer is 5-10 μm, the thickness of the flame retardant layer is 50-200 μm, and the thickness of the glass fiber substrate layer is 200-400 μm.

5. The glass fiber composite membrane according to claim 1 or 2, characterized in that: The silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-isocyanatopropyltriethoxysilane; And / or, the microsphere particles are selected from at least one of silicone microspheres, glass microspheres, and polycarbonate microspheres; And / or, the phosphate is selected from at least one of melamine polyphosphate, ammonium polyphosphate, and tributyl phosphate; And / or, the material of the reflective layer is aluminum foil.

6. Use of the glass fiber composite film according to any one of claims 1 to 5 in a reflective film for a double-glass photovoltaic module.

7. A method for preparing the glass fiber composite film according to any one of claims 1 to 5, characterized in that: The method includes: (1) first stirring polyurethane, silane coupling agent, aluminum hydroxide and phosphate to obtain a first material, and The polyurethane and the microsphere particles having a hollow structure are stirred for a second time to obtain a second material; (2) coating the first material onto the upper surface of the glass fiber substrate layer to form a flame retardant layer on the upper surface of the glass fiber substrate layer, and bonding the reflective layer to the flame retardant layer; then coating the second material onto the lower surface of the reflective layer that is not bonded to the flame retardant layer to form a light diffusion layer on the surface of the reflective layer; and then bonding the polyvinylidene fluoride protective layer to the light diffusion layer to obtain the glass fiber composite material.

8. The method according to claim 7, characterized in that The method further comprises the following steps: sequentially subjecting the product obtained by laminating the polyvinylidene fluoride protective layer and the light diffusion layer to a first drying treatment and a first curing treatment to obtain the glass fiber composite material; The operation of the first drying treatment includes: subjecting the product to first heating, second heating, third heating and fourth heating in sequence, wherein the temperature of the second heating is 5-15°C higher than the temperature of the first heating, the temperature of the third heating is 5-15°C higher than the temperature of the second heating, and the temperature of the fourth heating is 3-7°C higher than the temperature of the third heating.

9. The method according to claim 7 or 8, characterized in that: The glass fiber substrate layer is prepared by the following method: The glass fiber cloth is subjected to shaping, impregnation, gelling and drying and plasticizing treatments in sequence to obtain the glass fiber substrate layer.

10. The method according to claim 9, characterized in that The shaping conditions include: temperature of 170-190°C and time of 120-170s; And / or, the operation of the impregnation treatment includes: using epoxy resin slurry as an impregnation liquid to perform the impregnation treatment; And / or, the gel treatment conditions include: temperature of 160-180° C. and time of 35-55 s.

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