Flame-retardant colorful adhesive film for building outer wall and preparation method of flame-retardant colorful adhesive film

Abstract

The invention relates to the technical field of photovoltaics, in particular to a flame-retardant colorful adhesive film for a building outer wall and a preparation method thereof.The adhesive film comprises a flame-retardant impact-resistant adhesive film layer and a colorful flame-retardant adhesive film layer which are arranged in a stacked mode; the flame-retardant impact-resistant adhesive film layer comprises a polyolefin elastomer, a polyolefin plastomer, an ethylene-methacrylate copolymer, polyvinyl butyral, a first flame-retardant master batch, an impact-resistant master batch, an initiator, silane, an acrylic monomer, an antioxidant and a light stabilizer; the colorful flame-retardant adhesive film layer comprises the following raw materials: a polyolefin elastomer, a second flame-retardant master batch, a colorful crystal master batch, an initiator, silane, an acrylic monomer, an antioxidant and a light stabilizer. The flame-retardant colorful adhesive film for the building outer wall has good flame retardance, high bonding force with glass, good impact resistance and ultraviolet aging and yellowing resistance, high permeability of the adhesive film is guaranteed, the light utilization rate is increased, and the power generation power of a building integrated photovoltaics (BIPV) assembly is guaranteed.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and in particular, to a flame-retardant and colorful adhesive film for building exterior walls and a preparation method thereof. Background Art

[0002] With the continuous development of photovoltaic technology, photovoltaic modules are not only applied in places such as deserts and gobi; in order to reduce the energy consumption of buildings, photovoltaic modules are also applied to buildings, that is, BIPV modules (Building Integrated Photovoltaics, specifically referring to: modules that integrate a photovoltaic power generation system into a building, with both power generation and building functions) have emerged as the times require.

[0003] The adhesive film is an important component of BIPV modules. However, the adhesive films provided by related technologies have poor flame retardancy, weak adhesion to glass, and poor impact resistance, making it difficult to ensure the power of BIPV modules. Summary of the Invention

[0004] The purpose of the present invention is to provide a flame-retardant and colorful adhesive film for building exterior walls and a preparation method thereof. The flame-retardant and colorful adhesive film for building exterior walls of the present invention has good flame retardancy, strong adhesion to glass, good impact resistance, can resist ultraviolet aging and yellowing, ensure the high transparency of the adhesive film, improve the utilization rate of light, so as to ensure the power generation power of BIPV modules, and also has aesthetics; the preparation method of the present invention is simple and easy to operate.

[0005] The present invention is implemented as follows:

[0006] In a first aspect, the present invention provides a flame-retardant and colorful adhesive film for building exterior walls, including: a flame-retardant and impact-resistant adhesive film layer and a colorful and flame-retardant adhesive film layer that are stacked on top of each other; wherein,

[0007] The raw materials of the flame-retardant and impact-resistant adhesive film layer, calculated by weight, include: 10-20 parts of polyolefin elastomer, 2-10 parts of polyolefin plastomer, 2-10 parts of ethylene-methyl acrylate copolymer, 10-20 parts of polyvinyl butyral (hereinafter referred to as: PVB), 15-25 parts of a first flame-retardant masterbatch, 20-50 parts of an impact-resistant masterbatch, 0.1-0.7 parts of an initiator, 0.1-0.5 parts of silane, 0.6-1 part of an acrylic monomer, 0.1-0.15 parts of an antioxidant, and 0.05-0.09 parts of a light stabilizer;

[0008] The raw materials of the colorful and flame-retardant adhesive film layer, calculated by weight, include: 60-85 parts of polyolefin elastomer, 5-25 parts of a second flame-retardant masterbatch, 5-15 parts of a colorful crystal masterbatch, 0.3-0.7 parts of an initiator, 0.1-0.5 parts of silane, 0.6-1 part of an acrylic monomer, 0.1-0.15 parts of an antioxidant, and 0.05-0.09 parts of a light stabilizer.

[0009] In an alternative embodiment, the raw materials of the impact-resistant masterbatch, by weight, include: 25-35 parts of polyvinyl butyral, 15-25 parts of polyolefin elastomer, 20-30 parts of polyolefin plastomer, and 20-30 parts of polymethacrylate.

[0010] In an alternative embodiment, the preparation method of the impact-resistant masterbatch includes: mixing polyvinyl butyral, polyolefin elastomer, polyolefin plastomer, and polymethacrylate, and performing underwater pelletizing by a screw extruder at a temperature of 150-170 °C with a screw rotation speed of 50-70 r / min, and drying and isothermal crystallization at a temperature of 45-55 °C after pelletizing.

[0011] In an alternative embodiment, the preparation method of at least one of the first flame-retardant masterbatch and the second flame-retardant masterbatch includes: mixing a flame-retardant raw material with a polyolefin elastomer and extruding and pelletizing.

[0012] In an alternative embodiment, the preparation method of the flame-retardant raw material includes:

[0013] Mixing ODOPB and aluminum chloride under the condition of introducing nitrogen to obtain a premix;

[0014] Dropping phenyl dichlorophosphate into the premix within a first set time, raising the temperature to a first preset temperature after dropping, then raising the temperature to a second preset temperature, and maintaining the temperature at the second preset temperature for a second set time, and then raising the temperature to a third preset temperature and continuously stirring.

[0015] In an alternative embodiment, the first preset temperature is 75-85 °C, the second preset temperature is 135-145 °C, and the third preset temperature is 195-205 °C.

[0016] In an alternative embodiment, the temperature for mixing the flame-retardant raw material and the polyolefin elastomer is 60-70 °C, and the flame-retardant raw material accounts for 3-7% of the total weight of the first flame-retardant masterbatch or the second flame-retardant masterbatch; the temperature for extruding and pelletizing to prepare at least one of the first flame-retardant masterbatch and the second flame-retardant masterbatch is 115-125 °C, and the screw rotation speed is 55-65 r / min.

[0017] In an alternative embodiment, the preparation method of the colorful crystal masterbatch includes: mixing a dazzling powder and a polyolefin elastomer and extruding and pelletizing at a temperature of 115-125 °C and a screw rotation speed of 55-65 r / min; wherein, the raw materials of the colorful crystal masterbatch, by weight, include 8-12 parts of the dazzling powder and 88-92 parts of the polyolefin elastomer.

[0018] In an alternative embodiment, the method for preparing the flame-retardant impact-resistant film layer includes: blending and extruding the raw materials of the flame-retardant impact-resistant film layer with a casting extruder at a temperature of 110-150 °C and drawing them into a film;

[0019] The method for preparing the colorful flame-retardant film layer includes: blending and extruding the raw materials of the colorful flame-retardant film layer with a casting extruder at a temperature of 110-150 °C and drawing them into a film.

[0020] In a second aspect, the present invention provides a method for preparing a flame-retardant colorful film for building exterior walls. The preparation method is used to prepare the flame-retardant colorful film for building exterior walls according to any one of the foregoing embodiments. The preparation method includes:

[0021] Put the flame-retardant impact-resistant film layer and the colorful flame-retardant film layer into the first hopper and the second hopper of a co-extrusion extruder respectively, and extrude and wind up at a temperature of 90-100 °C and a screw rotation speed of 60-70 r / min.

[0022] The flame-retardant colorful film for building exterior walls according to the embodiments of the present invention has the following beneficial effects: The flame-retardant colorful film for building exterior walls provided by the embodiments of the present invention includes a flame-retardant impact-resistant film layer and a colorful flame-retardant film layer that are stacked on top of each other; wherein, the flame-retardant impact-resistant film layer with the first flame-retardant masterbatch as the raw material and the colorful flame-retardant film layer with the second flame-retardant masterbatch as the raw material both have good flame-retardant capabilities, effectively extending the ignition time of the film; moreover, the raw materials of the flame-retardant impact-resistant film layer are also compounded with POE (polyolefin elastomer), POP (polyolefin plastomer), EMA (ethylene-methyl acrylate copolymer), and PVB (polyvinyl butyral), effectively improving the impact resistance of the film and ensuring that the film can be firmly bonded to the glass, which is beneficial to improving the overall impact resistance of the BIPV module using the film of the present invention; on the one hand, the colorful flame-retardant film layer can improve the ability of the film to resist ultraviolet aging and yellowing, and ensure the high transparency of the film to improve the power generation efficiency of the BIPV module using the film of the present invention, and on the other hand, it can use the colorful crystal masterbatch to refract light to achieve a colorful effect, improving the aesthetics and facilitating the BIPV module using the film to match the appearance of the surrounding buildings in terms of appearance, ensuring the overall aesthetics.

[0023] The beneficial effects of the method for preparing the flame-retardant colorful film for building exterior walls according to the embodiments of the present invention include: The preparation process is simple and easy to operate. Description of the Drawings

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other relevant drawings can be obtained based on these drawings.

[0025] Figure 1 It is a schematic structural diagram of a flame-retardant and colorful adhesive film for building exterior walls of the present disclosure;

[0026] Figure 2 It is an enlarged schematic diagram of the colorful flame-retardant adhesive film layer of the present disclosure.

[0027] Reference numerals: 010 - Flame-retardant and colorful adhesive film for building exterior walls; 100 - Flame-retardant and impact-resistant adhesive film layer; 200 - Colorful flame-retardant adhesive film layer; 210 - Colorful crystal masterbatch. Detailed embodiments

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial purchase.

[0029] The inventors have found through research that the adhesive film provided by the related technology for BIPV components (wherein the adhesive film is used to bond glass and photovoltaic cells) still has problems such as poor flame retardancy, poor impact resistance, poor adhesion, which has an adverse effect on the power generation of BIPV components, and poor aesthetics; among them, if the glass of the BIPV component is directly set to be colored, it has an obvious adverse effect on the power generation of the BIPV component, and the firing of colored glass is difficult, and it also has an obvious adverse effect on the light transmittance of the glass, etc.

[0030] To improve the above problems, please refer to Figure 1 , the present invention provides a flame-retardant and colorful adhesive film 010 for building exterior walls, which includes a flame-retardant and impact-resistant adhesive film layer 100 and a colorful flame-retardant adhesive film layer 200 that are stacked on top of each other.

[0031] Among them, the raw materials of the flame-retardant and impact-resistant adhesive film layer, by weight, include: 10-20 parts of polyolefin elastomer (such as 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc., not specifically limited herein), 2-10 parts of polyolefin plastomer (such as 2 parts, 4 parts, 5 parts, 7 parts, 8 parts, 10 parts, etc., not specifically limited herein), 2-10 parts of ethylene-methyl acrylate copolymer (such as 2 parts, 4 parts, 5 parts, 7 parts, 8 parts, 10 parts, etc., not specifically limited herein), 10-20 parts of polyvinyl butyral (such as 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc., not specifically limited herein), 15-25 parts of the first flame-retardant masterbatch (such as 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, etc., not specifically limited herein), 20-50 parts of impact-resistant masterbatch (such as 20 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc., not specifically limited herein), 0.1-0.7 parts of initiator (such as 0.1 part, 0.3 part, 0.5 part, 0.7 part, etc., not specifically limited herein), 0.1-0.5 parts of silane (such as 0.1 part, 0.3 part, 0.5 part, etc., not specifically limited herein), 0.6-1 part of acrylic monomer (such as 0.6 part, 0.8 part, 1 part, etc., not specifically limited herein), 0.1-0.15 parts of antioxidant (such as 0.1 part, 0.12 part, 0.15 part, etc., not specifically limited herein), 0.05-0.09 parts of light stabilizer (such as 0.05 part, 0.07 part, 0.09 part, etc., not specifically limited herein).

[0032] Among them, the raw materials of the colorful flame-retardant adhesive film layer, by weight, include: 60-85 parts of polyolefin elastomer (such as 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, etc., not specifically limited herein), 5-25 parts of the second flame-retardant masterbatch (such as 5 parts, 10 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, etc., not specifically limited herein), 5-15 parts of colorful crystal masterbatch (such as 5 parts, 7 parts, 10 parts, 13 parts, 15 parts, etc., not specifically limited herein), 0.3-0.7 parts of initiator (such as 0.3 part, 0.5 part, 0.7 part, etc., not specifically limited herein), 0.1-0.5 parts of silane (such as 0.1 part, 0.3 part, 0.5 part, etc., not specifically limited herein), 0.6-1 part of acrylic monomer (such as 0.6 part, 0.8 part, 1 part, etc., not specifically limited herein), 0.1-0.15 parts of antioxidant (such as 0.1 part, 0.12 part, 0.15 part, etc., not specifically limited herein), 0.05-0.09 parts of light stabilizer (such as 0.05 part, 0.07 part, 0.09 part, etc., not specifically limited herein).

[0033] The flame-retardant and colorful film for building exterior walls ensures good flame-retardant ability through a flame-retardant and impact-resistant film layer with raw materials including a first flame-retardant masterbatch and a colorful flame-retardant film layer with raw materials including a second flame-retardant masterbatch, effectively extending the ignition time of the film (i.e., the time when open flames appear during the combustion of the film, specifically, the time when open flames appear > 20 s); moreover, the raw materials of the flame-retardant and impact-resistant film layer are also compounded with POE (polyolefin elastomer), POP (polyolefin plastomer), EMA (ethylene-methyl acrylate copolymer), and PVB (polyvinyl butyral), effectively improving the impact resistance of the film and ensuring that the film can be firmly bonded to the glass, which is beneficial to improving the overall impact resistance of the BIPV module using the film of the present invention; on the one hand, the colorful flame-retardant film layer can improve the ability of the film to resist ultraviolet aging and yellowing, ensure the high transparency of the film, and enhance the utilization of light at the grid line position of the BIPV module to improve the power generation efficiency of the BIPV module using the film of the present invention. On the other hand, it can also refract light using the colorful crystal masterbatch 210 (such as Figure 2 shown) to achieve a colorful effect, improve the aesthetics, and facilitate the BIPV module using this film to match the appearance of the surrounding buildings in appearance, ensuring the overall aesthetics.

[0034] It should be noted that by adjusting the dosage of the colorful crystal masterbatch and the type of color powder in the raw materials of the colorful flame-retardant film layer, the film can also present different colors as needed.

[0035] It should also be noted that the specific types of initiators, antioxidants, and light stabilizers are similar to those used in the related art and are products that can be purchased on the market, so they will not be listed one by one here.

[0036] Optionally, the initiator is a peroxide, such as: one or a combination of more of tert-butyl peroxy 2-ethylhexyl carbonate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxide succinate, tert-butyl peroxyacetate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and tert-butyl peroxybenzoate, which are resistant to high-temperature shearing.

[0037] Optionally, the preparation method of the flame-retardant and impact-resistant film layer includes: blending and extruding the raw materials of the flame-retardant and impact-resistant film layer with a casting extruder under the condition of a temperature of 110 - 150 °C (for example: 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc., which are not specifically limited here) to draw into a film. Casting and extruding into a film within the above temperature range is beneficial to ensuring that the prepared flame-retardant and impact-resistant film layer has good impact resistance and flame-retardant performance.

[0038] Optionally, the preparation method of the colorful flame-retardant film layer includes: blending and extruding the raw materials of the colorful flame-retardant film layer with a casting extruder under the condition of a temperature of 110-150 °C (for example: 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc., which are not specifically limited here) to draw into a film. Casting and extruding into a film within the above temperature range is beneficial to ensure that the obtained colorful flame-retardant film layer has good flame-retardant properties.

[0039] Optionally, the preparation method of the flame-retardant colorful film for building exterior walls includes: respectively putting the flame-retardant impact-resistant film layer and the colorful flame-retardant film layer into the first hopper (also known as hopper A) and the second hopper (also known as hopper B) of a co-extrusion extruder, and extruding and winding up under the conditions of a temperature of 90-100 (for example: 90 °C, 92 °C, 95 °C, 97 °C, 100 °C, etc., which are not specifically limited here) and a screw rotation speed of 60-70 r / min (for example: 60 r / min, 63 r / min, 65 r / min, 67 r / min, 70 r / min, etc., which are not specifically limited here).

[0040] Optionally, the total thickness of the flame-retardant colorful film for building exterior walls is 550-570 μm (for example: 550 μm, 555 μm, 560 μm, 565 μm, 570 μm, etc., which are not specifically limited here), wherein the thicknesses of both the flame-retardant impact-resistant film layer and the colorful flame-retardant film layer are controlled within 275-285 μm (for example: 275 μm, 280 μm, 285 μm, etc., which are not specifically limited here).

[0041] Optionally, the raw materials for preparing the impact-resistant masterbatch in the raw materials of the flame-retardant impact-resistant film layer, by weight, include: 25-35 parts of polyvinyl butyral (for example: 25 parts, 27 parts, 30 parts, 33 parts, 35 parts, etc., which are not specifically limited here), 15-25 parts of polyolefin elastomer (for example: 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, etc., which are not specifically limited here), 20-30 parts of polyolefin plastomer (for example: 20 parts, 23 parts, 25 parts, 27 parts, 30 parts, etc., which are not specifically limited here), and 20-30 parts of polymethyl methacrylate (for example: 20 parts, 23 parts, 25 parts, 27 parts, 30 parts, etc., which are not specifically limited here). Mixing PVB, POE, POP, and PMA to prepare an impact-resistant masterbatch, and then mixing with other raw materials such as POE, POP, EMA, and PVB to prepare a flame-retardant impact-resistant film layer can ensure that the film has better impact resistance.

[0042] Further, the preparation method of the impact-resistant masterbatch includes: mixing polyvinyl butyral, polyolefin elastomer, polyolefin plastomer and polymethacrylate, and performing water ring cutting granulation by a screw extruder under the conditions of a temperature of 150-170 °C (for example, 150 °C, 160 °C, 170 °C, etc., which are not specifically limited herein) and a screw rotation speed of 50-70 r / min (for example, 50 r / min, 60 r / min, 70 r / min, etc., which are not specifically limited herein), and drying and isothermal crystallization under the conditions of a temperature of 45-55 °C (for example, 45 °C, 50 °C, 55 °C, etc., which are not specifically limited herein) after granulation. Preparing the impact-resistant masterbatch under the above process can effectively ensure the impact resistance of the impact-resistant masterbatch, thereby improving the impact resistance of the flame-retardant impact-resistant film layer.

[0043] Optionally, the preparation methods of the first flame-retardant masterbatch and the second flame-retardant masterbatch include: mixing a flame-retardant raw material with a polyolefin elastomer and extruding and granulating. Mixing the flame-retardant raw material with POE particles and extruding to prepare the flame-retardant masterbatch can ensure that the flame-retardant masterbatch has good flame retardancy and good impact resistance at the same time.

[0044] Further, the preparation method of the flame-retardant raw material includes: mixing ODOPB (i.e., the flame retardant 10-(2,5-dihydroxyphenyl)-10-H-9-oxa-10-phosphaphenanthrene-10-oxide, whose English name is 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-xa-10-phospha phenanthrene-10-oxide) with aluminum chloride under the condition of introducing nitrogen to obtain a premix; dropping phenyl dichlorophosphate into the premix within the first set time, raising the temperature to the first preset temperature after the dropping is completed, then raising the temperature to the second preset temperature, and keeping the temperature at the second preset temperature for the second set time, and then raising the temperature to the third preset temperature and continuously stirring until stirring is no longer possible, and then stopping stirring to obtain a POPP solid product (i.e., polyphenoxyphosphoric acid-2-10-hydrogen-9-oxa-phosphaphenanthryl hydroquinone ester).

[0045] Furthermore, the dropping of phenyl dichlorophosphate can be completed within 30 min.

[0046] The flame-retardant mechanism of the ODOPB-based polyphosphate flame retardant in the POP resin includes:

[0047] The ODOPB-based polyphosphate flame retardant mainly generates polyphosphoric acid substances through the decomposition of ODOPB (containing a phosphorus heterophthalic structure) and the polyphosphate main chain at high temperatures, catalyzes the dehydration and carbonization of the POP resin surface, and forms a dense and continuous carbon layer; this carbon layer can isolate oxygen and heat transfer and inhibit the release of combustible volatiles. The molecular weight range (2000 - 4000) and the high molecular chain structure of the ODOPB flame retardant can enhance the stability of the carbon layer, such as a significant increase in the limiting oxygen index (LOI) (from 25 to 30 and above), and the vertical burning reaches UL-94V-0 level. During combustion, the phosphorus compound decomposes to generate phosphorus-containing free radicals (such as PO·, HPO·), which combine with the active free radicals (·H, ·OH) in the flame to interrupt the chain reaction. The flame retardant (flame retardant raw material) does not contain halogens, but achieves efficient flame retardancy through the action of pure phosphorus series without relying on the synergy of nitrogen or halogens. The high molecular weight polyphosphate is uniformly dispersed in the matrix to form a physical barrier to delay thermal decomposition; at the same time, the phosphoric acid substances generated by decomposition cover the surface of the material to dilute the concentration of combustible gases.

[0048] The synergistic mechanism of the ODOPB-based polyphosphate flame retardant and the initiator in impact resistance and flame retardancy includes:

[0049] Introducing a peroxide initiator containing free radicals into the POP resin can regulate the polymerization reaction or cross-linked structure. The ODOPB-based flame retardant and the initiator can promote the formation of the cross-linked network of the POP resin, enhance the mechanical strength of the carbon layer, and reduce the dripping phenomenon during combustion. At the same time, the polyphosphate chain segment of the flame retardant is compatible with the cross-linked network, which can prevent the migration of the flame retardant. In the present disclosure, the flame retardant has good compatibility with the polymer matrix (such as polycarbonate, epoxy resin), and there will be no problem of exudation of the flame retardant or polymer. Moreover, the high molecular weight flame retardant (molecular weight 2000 - 4000) can be uniformly dispersed in the matrix to reduce the restriction on the movement of resin segments, that is, it can avoid the increase in brittleness caused by adding the flame retardant. In addition, the cross-linking induced by the initiator can form a tough network to compensate for the adverse effect of the flame retardant on the impact performance.

[0050] The impact resistance function mechanism of the ODOPB-based flame retardant and the acrylic monomer includes:

[0051] The acrylic monomer forms a rubber phase (such as a core-shell structure) through copolymerization or grafting, absorbs impact energy and initiates the termination of crazes, and improves toughness. The polar groups (such as ester groups) of the acrylic monomer have chemical affinity with the polyphosphate chain segment of the flame retardant, promoting the uniform dispersion of the two in the matrix and avoiding phase separation, that is, the balance between flame retardancy and toughness can be achieved; while the carbon layer protection effect of the flame retardant can reduce the degradation of the acrylic phase during combustion, and at the same time, the toughening effect of the acrylic phase offsets the brittleness caused by the flame retardant, achieving the balance between flame retardancy and impact resistance.

[0052] The beneficial effects of the flame retardant and colorful film for building exterior walls of the present disclosure are summarized as follows:

[0053] 1. Flame retardant mechanism: ODOPB-based polyphosphate achieves efficient halogen-free flame retardancy through condensed-phase carbonization and gas-phase free radical capture, and is applicable to POP resins.

[0054] 2. Initiator synergy: The crosslinked network induced by the initiator can enhance the stability of the carbon layer while maintaining impact resistance.

[0055] 3. Acrylic monomer synergy: The acrylic toughening phase is dispersed and compatible with the flame retardant, balancing flame retardancy and mechanical properties.

[0056] 4. Comprehensive advantages: High molecular weight design, halogen-free and environmentally friendly, wide applicability (polyolefins, epoxy resins, etc.), meeting the industrial requirements for high-performance flame retardants.

[0057] It should be noted that the above-mentioned flame retardant (flame retardant raw material) does not contain halogen, which means:

[0058] When preparing the flame retardant raw material, aluminum chloride is a Lewis acid used as a catalyst. It binds to the hydroxyl group (-OH) or phosphate group in the reactant by providing an empty orbital, thereby activating the reaction site; for example, the hydroxyl group in ODOPB is deprotonated under the catalysis of AlCl3 to form an oxygen anion (O - ), enhancing its nucleophilicity and promoting the condensation reaction with the phosphoryl group (P=O) of PDCP.

[0059] In promoting the dehydration condensation reaction in esterification or polycondensation reactions, AlCl3 absorbs the water molecules released by the reaction, promotes the reaction to proceed in the direction of forming the product, and reduces the occurrence of the reverse reaction at the same time. This characteristic is particularly important in the high-temperature reaction stage, which can improve the reaction efficiency and product purity. Aluminum chloride, a substance with amphoteric properties, can maintain the stability of the reaction system by neutralizing the acidic by-products generated in the neutralization reaction, preventing side reactions caused by an overly acidic environment.

[0060] Phenyl dichlorophosphate is a phosphorylating reagent in the reaction. The two chlorine atoms (Cl - ) in its molecule can be replaced by the hydroxyl group of ODOPB to form a phosphate ester bond (P—O—C), thereby constructing the polymer backbone of POPP. This polycondensation reaction is the core step in the synthesis of POPP.

[0061] The phosphoryl chloride group (POCl2) of PDCP that provides the reaction active site has high reactivity and can quickly combine with the phenolic hydroxyl group of ODOPB under the catalysis of AlCl3 to form a stable phosphate ester structure. The HCl released in the reaction can be further absorbed through the acidic environment of AlCl.

[0062] Therefore, the Cl content in the finally obtained product is extremely low and can be ignored.

[0063] Optionally, the above solid product can be washed with distilled water, filtered, and dried in vacuo (for example, dried for about 24 h) to obtain POPP solid powder, which is used as a flame retardant raw material for mixing with POE particles and extruded to prepare a flame retardant masterbatch.

[0064] Optionally, the first preset temperature is 75 - 85 °C (for example: 75 °C, 77 °C, 80 °C, 83 °C, 85 °C, etc., which are not specifically limited herein), the second preset temperature is 135 - 145 °C (for example: 135 °C, 138 °C, 140 °C, 142 °C, 145 °C, etc., which are not specifically limited herein), and the third preset temperature is 195 - 205 °C (for example: 195 °C, 198 °C, 200 °C, 202 °C, 205 °C). Adding phenyl dichlorophosphate dropwise to the premix at a lower temperature and then raising the temperature can improve the flame retardancy of the prepared flame retardant raw material and effectively extend the time of open flame generation during the combustion of the adhesive film.

[0065] Optionally, after the dropwise addition of phenyl dichlorophosphate at room temperature is completed, heating to the first preset temperature range (75 - 85 °C) at a heating rate of 1 - 3 °C / min can ensure the priority of the stability of the POPP solid powder; heating from the first preset temperature range to the second preset temperature range (135 - 145 °C) at a rate of 3 - 5 °C / min can ensure the balance between efficiency and the system; and then heating from the second preset temperature range to the third preset temperature range (195 - 205 °C) at a rate of 1 - 2 °C / min, with the core of material protection and performance optimization, can ensure good flame retardancy of the material.

[0066] Optionally, the temperature for mixing the flame retardant raw material and the polyolefin elastomer is 60 - 70 °C (for example: 60 °C, 62 °C, 65 °C, 68 °C, 70 °C, etc., which are not specifically limited herein), and the flame retardant raw material accounts for 3 - 7% of the total weight of the first flame retardant masterbatch or the second flame retardant masterbatch (for example: 3%, 5%, 7%, etc., which are not specifically limited herein); the temperature for extruding and pelletizing at least one of the first flame retardant masterbatch and the second flame retardant masterbatch is 115 - 125 °C (for example: 115 °C, 118 °C, 120 °C, 123 °C, 125 °C, etc., which are not specifically limited herein), and the rotation speed of the screw is 55 - 65 r / min (for example: 55 r / min, 57 r / min, 60 r / min, 62 r / min, 65 r / min, etc., which are not specifically limited herein). When mixing the flame retardant raw material and the polyolefin elastomer (POE) at 60 - 70 °C, the polyolefin elastomer (POE) has higher viscosity, which can ensure the uniformity of the mixing of the flame retardant raw material and the polyolefin elastomer (POE), and thus improve the flame retardancy of the prepared flame retardant masterbatch.

[0067] Optionally, the preparation method of the colorful crystal masterbatch includes: mixing the glare powder and the polyolefin elastomer, and extruding and pelletizing under the conditions of a temperature of 115-125°C (for example: 115°C, 118°C, 120°C, 123°C, 125°C, etc., which are not specifically limited here) and a screw rotation speed of 55-65 r / min (for example: 55 r / min, 57 r / min, 60 r / min, 62 r / min, 65 r / min, etc., which are not specifically limited here); wherein, the raw materials of the colorful crystal masterbatch include 8-12 parts by weight of glare powder (for example: 8 parts, 10 parts, 12 parts, etc., which are not specifically limited here) and 88-92 parts by weight of polyolefin elastomer (for example: 88 parts, 90 parts, 92 parts, etc., which are not specifically limited here).

[0068] It should be noted that the glare powder can be selected according to the color requirements of the prepared film, such as: rare earth aluminate, luminous powder, flash powder (europium-doped multi-layer coated aluminate), etc., which are not specifically limited here. By selecting different glare powders, colorful flame-retardant film layers with different refractive properties can be formed, that is, different types of glare powders have differences in crystal form, arrangement mode of crystal grains and refractive index, etc., and can make the prepared colorful flame-retardant film layer present different colors under the action of light at different incident angles.

[0069] Detect the initial power, PID192h power and power after DH2000h of the BIPV module prepared by using the flame-retardant colorful film for building exterior walls of the present disclosure to obtain the power attenuation percentage of the module after PID192h and the power attenuation percentage of the module after DH2000h; at the same time, also detect the adhesion between the flame-retardant colorful film for building exterior walls of the present disclosure and glass, the initial light transmittance and the light transmittance after aging of the film.

[0070] The initial power, adhesion and the power of the module after DH2000h are all tested according to GB / T 29848-2018.

[0071] The light transmittance of the film is measured using a Shimadzu UV6800S ultraviolet spectrophotometer, and the ignition experiment of the film is detected using a vertical burning tester.

[0072] The impact resistance of the film is tested using a small ball impact tester IDM-I0003-M1 and referring to the ISO 4586-2 test standard.

[0073] The test results meet Table 1.

[0074] Table 1

[0075]

[0076] The present invention will be further described in detail below in conjunction with embodiments.

[0077] Example 1

[0078] This example provides a flame-retardant and colorful film for building exterior walls and a preparation method thereof. The overall film is sequentially laminated with a flame-retardant and impact-resistant film layer and a colorful flame-retardant film layer from top to bottom. Among them, the thickness of the overall film layer is 560 μm, the thickness of the flame-retardant and impact-resistant film layer is 280 μm, the thickness of the colorful flame-retardant film layer is 280 μm, and the thickness ratio of the two layers is 1:1.

[0079] Components and preparation method of the flame-retardant and impact-resistant film layer: 20 parts of POE, 10 parts of POP, 10 parts of EMA, 20 parts of PVB, 20 parts of flame-retardant masterbatch, 20 parts of impact-resistant masterbatch, 0.7 part of initiator, 0.1 part of silane (570), 0.6 part of acrylic monomer, 0.15 part of antioxidant, and 0.09 part of light stabilizer are melt-blended and extruded into a film by a casting extruder at 150 °C.

[0080] Among them, the preparation method of the impact-resistant masterbatch: 30 parts of PVB, 20 parts of POE, 25 parts of POP, and 25 parts of PMA are placed in a mixing kettle for mixing, and then granulated by a twin-screw extruder at 160 °C and 60 r / min. During the granulation process, water ring cutting is used for cutting, and after cutting into particles, they are placed in an oven at 50 °C for moisture removal and further isothermal crystallization.

[0081] Preparation method of the flame-retardant masterbatch: 1 mol (320.24 g) of ODOPB and 0.01 mol [1.33 g, n(ODOPB)∶n(AlCl3) = 1∶100] of aluminum chloride are added to a three-necked flask equipped with a condenser, a stirrer, and nitrogen inlets and outlets. N2 is introduced, and under stirring conditions, 1 mol (210.98 g, 1.412 mL / mol) of phenyl dichlorophosphate is added dropwise within 30 min. After the addition, the temperature is raised from 80 °C at a heating rate of 3 °C / min, and then the temperature is further raised to 140 °C at a heating rate of 3 °C / min and reacted at 140 °C for 1.5 h. After the reactant becomes viscous, the temperature is raised to 200 °C at a heating rate of 1 °C / min, and stirring reaction is continued until stirring is no longer possible, then the stirring is stopped to obtain a POPP solid product; the POPP solid product is washed with distilled water and filtered, and vacuum dried for 24 h to obtain a POPP solid powder. The POPP solid powder is mixed with POE particles in a mixing kettle at 70 °C according to 5% of the total mass fraction; then the premixed material is added to a twin-screw extruder and extruded and granulated at 120 °C and 60 r / min.

[0082] Components and preparation method of the colorful flame-retardant adhesive film layer: 70 parts of POE, 20 parts of flame-retardant masterbatch, 10 parts of colorful crystal masterbatch, 0.3 parts of initiator, 0.5 parts of silane (570), 0.6 parts of acrylic monomer, 0.15 parts of antioxidant, and 0.05 parts of light stabilizer are melt-extruded and drawn into an adhesive film by a casting extruder at 150 °C.

[0083] Among them, the preparation method of the colorful crystal masterbatch: 10 parts of dazzling powder (Shenzhen Photonic Crystal Technology Co., Ltd.) are mixed with 90 parts of POE, and then extruded and granulated by a twin-screw extruder at 120 °C and 60 r / min.

[0084] Preparation of the flame-retardant colorful adhesive film for building exterior walls: The flame-retardant impact-resistant adhesive film layer and the colorful flame-retardant adhesive film layer are respectively put into the A bin and B bin of a co-extrusion extruder, and extrusion and winding are realized at 95 °C and 65 r / min.

[0085] Adhesive film test: The bonding strength between the encapsulation adhesive film and the glass is 146 N / cm; the ignition time of the encapsulation adhesive film is 57 s; Initial light transmittance: 86.15% at 280 - 380 nm, 91.89% at 380 - 1100 nm; After DH2000 aging, the light transmittance: 84.75% at 280 - 380 nm, 91.14% at 380 - 1100 nm; After UV60kwh aging, the light transmittance: 84.31% at 280 - 380 nm, 90.97% at 380 - 1100 nm; For the BIPV module using the adhesive film of Example 1, the power attenuation after DH2000h is 1.8%; The power attenuation after PID192h (potential-induced degradation) is 2.1%; The above test results all meet the requirements of Table 1. The impact resistance (detected by the small ball impact test) is 43 N.

[0086] Example 2

[0087] Example 2 is similar to Example 1. Only the differences between Example 2 and Example 1 are recorded as follows:

[0088] In the components of the colorful flame-retardant adhesive film layer, the dosage of POE is 85 parts, and the dosage of the flame-retardant masterbatch is 5 parts by weight.

[0089] Encapsulant film test: The adhesion between the encapsulant film and the glass is 132 N / cm; the ignition time of the film is 23 s; Initial light transmittance: 86.78% at 280 - 380 nm, 92.16% at 380 - 1100 nm; After DH2000 aging, the light transmittance: 85.23% at 280 - 380 nm, 91.23% at 380 - 1100 nm; After UV60 kwh aging, the light transmittance: 84.78% at 280 - 380 nm, 91.01% at 380 - 1100 nm; For the BIPV module using the encapsulant film of Example 2, the power attenuation after DH2000 h is 1.3%; the power attenuation after PID192 h is 1.7%; All the above test results meet the requirements in Table 1. The impact resistance (detected by the small ball impact test) is 37 N.

[0090] Example 3

[0091] Example 3 is similar to Example 1. Only the differences between Example 3 and Example 1 are described below:

[0092] Components and preparation method of the flame-retardant and impact-resistant encapsulant film layer: Mix 10 parts of POE, 2 parts of POP, 2 parts of EMA, 10 parts of PVB, 15 parts of flame retardant masterbatch, 30 parts of impact-resistant masterbatch, 0.1 part of initiator, 0.5 part of silane (570), 1 part of acrylic monomer, 0.1 part of antioxidant, and 0.05 part of light stabilizer, and then co-extrude and draw into a film through a casting extruder at 110 °C.

[0093] Among them, the preparation method of the impact-resistant masterbatch: Mix 25 parts of PVB, 15 parts of POE, 20 parts of POP, and 20 parts of PMA in a mixing kettle, and then granulate through a twin-screw extruder under the conditions of 150 °C and 50 r / min. During the granulation process, water ring cutting is used for cutting, and after cutting into particles, they are placed in an oven at 45 °C for moisture removal and further isothermal crystallization.

[0094] Preparation method of flame retardant masterbatch: Add 1 mol (320.24 g) of ODOPB and 0.01 mol [1.33 g, n(ODOPB)∶n(AlCl3) = 1∶100] of aluminum chloride into a three-necked flask equipped with a condenser, a stirrer, and nitrogen inlets and outlets. Introduce N2, and under stirring conditions, add dropwise 1 mol (210.98 g, 1.412 mL / mol) of phenyl dichlorophosphate in 30 min. After the addition, heat to 75 °C at a heating rate of 1 °C / min, and then heat to 135 °C at a heating rate of 5 °C / min. React at 135 °C for 1.5 h. After the reactant becomes viscous, heat to 195 °C at a heating rate of 2 °C / min, continue stirring and reacting until stirring is no longer possible, then stop stirring to obtain a POPP solid product; Wash the POPP solid product with distilled water, filter, and vacuum dry for 24 h to obtain a POPP solid powder. Mix the POPP solid powder with POE particles in a mixing kettle at 60 °C according to 3% of the total mass fraction; Then add the premix to a twin-screw extruder and extrude and pelletize under the conditions of 115 °C and 55 r / min.

[0095] Components and preparation method of the colorful flame retardant film layer: Mix 60 parts of POE, 25 parts of flame retardant masterbatch, 5 parts of colorful crystal masterbatch, 0.7 part of initiator, 0.1 part of silane (570), 1 part of acrylic monomer, 0.1 part of antioxidant, and 0.09 part of light stabilizer, and co-extrude and draw into a film by a casting extruder at 110 °C.

[0096] Among them, the preparation method of the colorful crystal masterbatch: Mix 8 parts of dazzling powder (Shenzhen Photonic Crystal Technology Co., Ltd.) with 92 parts of POE, and then use a twin-screw extruder to extrude and pelletize under the conditions of 115 °C and 55 r / min.

[0097] Preparation of the flame retardant colorful film for building exterior walls: Put the flame retardant and impact-resistant film layer and the colorful flame retardant film layer into the A bin and B bin of a co-extrusion extruder respectively, and carry out extrusion and winding at 90 °C and 60 r / min.

[0098] Example 4

[0099] Example 4 is similar to Example 1. The following only records the differences between Example 4 and Example 1:

[0100] Components and preparation method of the flame retardant and impact-resistant film layer: Mix 15 parts of POE, 5 parts of POP, 5 parts of EMA, 15 parts of PVB, 25 parts of flame retardant masterbatch, 50 parts of impact-resistant masterbatch, 0.5 part of initiator, 0.3 part of silane (570), 0.8 part of acrylic monomer, 0.12 part of antioxidant, and 0.07 part of light stabilizer, and co-extrude and draw into a film by a casting extruder at 120 °C.

[0101] Among them, the preparation method of the impact-resistant masterbatch: 35 parts of PVB, 25 parts of POE, 30 parts of POP, and 30 parts of PMA are placed in a mixing kettle for mixing, and then granulated by a twin-screw extruder under the conditions of 170 °C and 70 r / min. During the granulation process, water ring cutting is used for granulation. After cutting into particles, they are placed in an oven at 55 °C for moisture removal and further isothermal crystallization.

[0102] The preparation method of the flame-retardant masterbatch: 1 mol (320.24 g) of ODOPB and 0.01 mol [1.33 g, n(ODOPB)∶n(AlCl3) = 1∶100] of aluminum chloride are added to a three-necked flask equipped with a condenser, a stirrer, and nitrogen inlets and outlets. N2 is introduced. Under stirring conditions, 1 mol (210.98 g, 1.412 mL / mol) of phenyl dichlorophosphate is added dropwise within 30 min. After the addition, the temperature is raised to 85 °C at a heating rate of 2 °C / min, and then the temperature is raised to 145 °C at a heating rate of 4 °C / min. The reaction is carried out at 145 °C for 1.5 h. After the reactants become viscous, the temperature is raised to 205 °C at a heating rate of 1 °C / min, and the stirring reaction continues until stirring is no longer possible, then the stirring is stopped to obtain the POPP solid product; the POPP solid product is washed with distilled water and filtered, and vacuum dried for 24 h to obtain the POPP solid powder. The POPP solid powder is mixed with POE particles in a mixing kettle at 70 °C according to 7% of the total mass fraction; then the premix is added to a twin-screw extruder and extruded and granulated under the conditions of 125 °C and 65 r / min.

[0103] The components and preparation method of the colorful flame-retardant adhesive film layer: 70 parts of POE, 15 parts of the flame-retardant masterbatch, 8 parts of the colorful crystal masterbatch, 0.5 part of the initiator, 0.3 part of silane (570), 0.8 part of the acrylic monomer, 0.13 part of the antioxidant, and 0.06 part of the light stabilizer are co-extruded and drawn into an adhesive film by a casting extruder under the condition of 130 °C.

[0104] Among them, the preparation method of the colorful crystal masterbatch: 12 parts of the dazzling powder (Shenzhen Photonic Crystal Technology Co., Ltd.) are mixed with 88 parts of POE, and then granulated by a twin-screw extruder under the conditions of 125 °C and 65 r / min.

[0105] The preparation of the flame-retardant colorful adhesive film for building exterior walls: The flame-retardant impact-resistant adhesive film layer and the colorful flame-retardant adhesive film layer are respectively put into the A bin and B bin of a co-extrusion extruder, and extrusion winding is realized under the conditions of 100 °C and 62 r / min.

[0106] Comparative Example 1

[0107] Comparative Example 1 is similar to Example 1, the difference is that: Comparative Example 1 only has the colorful flame-retardant adhesive film layer and no flame-retardant impact-resistant adhesive film layer.

[0108] Encapsulant film test: The bonding strength between the encapsulant film and the glass is 116 N / cm; the impact resistance (detected by the small ball impact test) is 12 N; the ignition time of the film is 13 s; the initial light transmittance: 82.15% for 280 - 380 nm, 90.89% for 380 - 1100 nm, the light transmittance after DH2000 aging: 74.52% for 280 - 380 nm, 88.14% for 380 - 1100 nm; the light transmittance after UV60 kwh aging: 74.14% for 280 - 380 nm, 86.37% for 380 - 1100 nm; for the BIPV module using the encapsulant film of Comparative Example 1, the power attenuation after DH2000 h is 5.2%, and the power attenuation after PID192 h is 5.3%.

[0109] Comparing the test results of Comparative Example 1 and Example 1, it can be seen that adding a flame-retardant and impact-resistant encapsulant film layer can improve the impact resistance of the film, enhance the anti-aging property of the film, and also improve the flame retardancy of the film (manifested as a longer ignition time of the film in Example 1).

[0110] Comparative Example 2

[0111] Comparative Example 2 is similar to Example 1, except that: instead of preparing the impact-resistant masterbatch separately, 25 parts by weight of PMA is directly used to prepare the flame-retardant and impact-resistant encapsulant film layer. Other preparation processes and raw materials refer to Example 1.

[0112] Encapsulant film test: The bonding strength between the encapsulant film and the glass is 127 N / cm; the ignition time of the film is 23 s; the initial light transmittance: 85.46% for 280 - 380 nm, 91.94% for 380 - 1100 nm, the light transmittance after DH2000 aging: 84.72% for 280 - 380 nm, 91.09% for 380 - 1100 nm; the light transmittance after UV60 kwh aging: 883.29% for 280 - 380 nm, 90.78% for 380 - 1100 nm; for the BIPV module using the encapsulant film of Comparative Example 2, the power attenuation after DH2000 h is 4.6%; the power attenuation after PID192 h is 7.2%.

[0113] Since there is no additional addition of the impact-resistant masterbatch, the impact resistance of the prepared material (detected by the small ball impact test) is 8 N, which is significantly worse than the impact resistance of the material in Example 1.

[0114] Comparative Example 3 is similar to Example 1, except that: when preparing the flame-retardant raw material, the temperature is first raised from 80 °C to 140 °C, and then diphenyl phosphate dichloride is added dropwise. Other preparation processes and raw materials refer to Example 1.

[0115] Encapsulant film test:

[0116] Encapsulant film test: The adhesion between the encapsulant film and the glass is 146 N / cm; the ignition time of the film is 7 s; the initial light transmittance: 86.10% for 280 - 380 nm, 92.02% for 380 - 1100 nm, after DH2000 aging, the light transmittance: 85.77% for 280 - 380 nm, 91.47% for 380 - 1100 nm; after UV60kwh aging, the light transmittance: 85.25% for 280 - 380 nm, 91.52% for 380 - 1100 nm; for the BIPV module using the encapsulant film of Comparative Example 3, the power attenuation after DH2000h is 2.7%; the power attenuation after PID192h is 4.8%; the impact resistance (detected by the small ball impact test) is 21 N.

[0117] From the comparison of the test results of Comparative Example 3 and Example 1, it can be seen that when preparing the flame retardant raw material in Comparative Example 3, the method of first raising the temperature from 80°C to 140°C and then dropping phenyl dichlorophosphate was not adopted, resulting in the ignition time of the finally prepared material being significantly shorter than that of Example 1, and the impact resistance of the finally prepared material being relatively poor.

[0118] Comparative Example 4

[0119] Comparative Example 4 is similar to Example 1, except that: the raw materials of the flame retardant and impact resistant encapsulant film layer do not include POP, acrylic monomer and initiator. Other preparation processes and raw materials refer to Example 1.

[0120] Encapsulant film test:

[0121] Encapsulant film test: The adhesion between the encapsulant film and the glass is 107 N / cm; the ignition time of the film is 5 s; the initial light transmittance: 85.24% for 280 - 380 nm, 91.56% for 380 - 1100 nm, after DH2000 aging, the light transmittance: 85.04% for 280 - 380 nm, 91.04% for 380 - 1100 nm; after UV60kwh aging, the light transmittance: 84.75% for 280 - 380 nm, 90.56% for 380 - 1100 nm; for the BIPV module using the encapsulant film of Comparative Example 4, the power attenuation after DH2000h is 8.7%; the power attenuation after PID192h is 5.7%; the impact resistance (detected by the small ball impact test) is 42 N.

[0122] From the test results of Comparative Example 4 and Example 1, it can be seen that when the raw materials of the flame retardant and impact resistant encapsulant film layer do not include POP, acrylic monomer and initiator, the ignition time of the prepared encapsulant film is significantly shorter than that of the encapsulant film of Example 1, indicating that the raw materials of the flame retardant and impact resistant encapsulant film layer of the encapsulant film of the present invention include POP, acrylic monomer and initiator, which can significantly improve the flame retardancy.

[0123] In summary, the flame-retardant colorful film for building exterior walls of the present invention has good flame retardancy, strong adhesion to glass, good impact resistance, can resist ultraviolet aging and yellowing, ensure the high transparency of the film, improve the utilization rate of light to ensure the power generation of BIPV components, and also has aesthetics; the preparation method of the present invention is simple and easy to operate.

[0124] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A flame-retardant and colorful adhesive film for building exterior walls, characterized in that, Comprising: A flame-retardant impact-resistant adhesive film layer and a colorful flame-retardant adhesive film layer which are stacked on top of each other; wherein, The raw materials of the flame-retardant impact-resistant adhesive film layer, by weight, include: 10-20 parts of polyolefin elastomer, 2-10 parts of polyolefin plastomer, 2-10 parts of ethylene-methyl acrylate copolymer, 10-20 parts of polyvinyl butyral, 15-25 parts of the first flame-retardant masterbatch, 20-50 parts of impact-resistant masterbatch, 0.1-0.7 parts of initiator, 0.1-0.5 parts of silane, 0.6-1 part of acrylic monomer, 0.1-0.15 parts of antioxidant, and 0.05-0.09 parts of light stabilizer; The raw materials of the colorful flame-retardant adhesive film layer, by weight, include: 60-85 parts of polyolefin elastomer, 5-25 parts of the second flame-retardant masterbatch, 5-15 parts of colorful crystal masterbatch, 0.3-0.7 parts of initiator, 0.1-0.5 parts of silane, 0.6-1 part of acrylic monomer, 0.1-0.15 parts of antioxidant, and 0.05-0.09 parts of light stabilizer.

2. The flame-retardant colorful adhesive film for building exterior walls according to claim 1, characterized in that, The raw materials of the impact-resistant masterbatch, by weight, include: 25-35 parts of polyvinyl butyral, 15-25 parts of polyolefin elastomer, 20-30 parts of polyolefin plastomer, and 20-30 parts of polymethacrylate.

3. The flame-retardant colorful adhesive film for building exterior walls according to claim 2, characterized in that, The preparation method of the impact-resistant masterbatch includes: mixing polyvinyl butyral, polyolefin elastomer, polyolefin plastomer, and polymethacrylate, and performing water ring cutting granulation by a screw extruder at a temperature of 150-170 °C with the screw rotation speed of 50-70 r / min, and drying and isothermal crystallization at a temperature of 45-55 °C after granulation.

4. The flame-retardant colorful adhesive film for building exterior walls according to claim 1, characterized in that, The preparation method of at least one of the first flame-retardant masterbatch and the second flame-retardant masterbatch includes: mixing the flame-retardant raw material with the polyolefin elastomer and extruding and granulating.

5. The flame-retardant colorful adhesive film for building exterior walls according to claim 4, wherein The preparation method of the flame-retardant raw material includes: Mixing ODOPB and aluminum chloride under the condition of introducing nitrogen to obtain a premix; Dropping dichlorophenyl phosphate into the premix within the first set time, raising the temperature to the first preset temperature after dropping, then raising the temperature to the second preset temperature, and maintaining the temperature at the second preset temperature for the second set time, and then raising the temperature to the third preset temperature and continuously stirring.

6. The flame-retardant colorful adhesive film for building exterior walls according to claim 5, wherein, The first preset temperature is 75-85 °C, the second preset temperature is 135-145 °C, and the third preset temperature is 195-205 °C.

7. The flame-retardant colorful adhesive film for building exterior walls according to claim 4, wherein The temperature for mixing the flame-retardant raw material with the polyolefin elastomer is 60-70 °C, and the flame-retardant raw material accounts for 3-7% of the total weight of the first flame-retardant masterbatch or the second flame-retardant masterbatch; the temperature for extruding and granulating to prepare at least one of the first flame-retardant masterbatch and the second flame-retardant masterbatch is 115-125 °C, and the screw rotation speed is 55-65 r / min.

8. The flame-retardant colorful adhesive film for building exterior walls according to claim 1, wherein The preparation method of the colorful crystal masterbatch includes: mixing the dazzling powder and the polyolefin elastomer and extruding and granulating at a temperature of 115-125 °C and a screw rotation speed of 55-65 r / min; wherein, the raw materials of the colorful crystal masterbatch, by weight, include 8-12 parts of the dazzling powder and 88-92 parts of the polyolefin elastomer.

9. The flame-retardant colorful adhesive film for building exterior walls according to any one of claims 1-8, characterized in that, The preparation method of the flame-retardant and impact-resistant film layer includes: blending and extruding the raw materials of the flame-retardant and impact-resistant film layer with a casting extruder under the condition of a temperature of 110 - 150 °C and drawing them into a film. The preparation method of the colorful flame-retardant film layer includes: blending and extruding the raw materials of the colorful flame-retardant film layer with a casting extruder under the condition of a temperature of 110 - 150 °C and drawing them into a film.

10. A preparation method of a flame-retardant colorful adhesive film for building exterior walls, characterized in that, The preparation method is used for preparing the flame-retardant and colorful film for building exterior walls according to any one of claims 1 - 9, and the preparation method includes: Putting the flame-retardant and impact-resistant film layer and the colorful flame-retardant film layer into the first hopper and the second hopper of a co-extrusion extruder respectively, and extruding and winding them up under the conditions of a temperature of 90 - 100 °C and a screw rotation speed of 60 - 70 r / min.

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