Black TPEE sunshade film and preparation method thereof

Abstract

The invention relates to the technical field of sunshade films, in particular to a black TPEE sunshade film and a preparation method thereof. The problem that an existing sunshade film is poor in heat insulation performance and shading performance is solved. The preparation method comprises the following steps: blending TPEE slices with nano carbon black, graphene and titanium black to prepare a heat-insulating master batch A; blending the TPEE slices with the modified boron nitride and the hollow glass beads to obtain a heat-insulating master batch B; a layer A is prepared from TPEE slices, a compatilizer, a compound additive and modified calcium carbonate, a layer B is prepared from the TPEE slices and two master batches, a layer C is prepared from the TPEE slices, and the black TPEE sunshade film is obtained through three-layer co-extrusion molding and aging treatment. The modified boron nitride and the modified calcium carbonate are modified through KH-550, so that the compatibility is improved. The product combines the synergistic effect of the shading component and the heat insulation filler, gives consideration to excellent shading and heat insulation effects, and is suitable for the requirements of shading scenes.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of sunshade films, in particular to a black TPEE sunshade film and a preparation method thereof. BACKGROUND

[0002] A sunshade film refers to a functional polymer composite film applied to the surface of an automobile or building glass. The core value thereof lies in blocking solar radiation to realize multiple functions such as heat insulation, ultraviolet protection and anti-glare. Early sunshade films mainly use dyed films, which absorb visible light by adding dyes in the glue layer or film layer, but the heat insulation performance is poor and the color fades easily. The subsequent vacuum coating technology reflects sunlight by evaporating a thin layer of aluminum, which improves the heat insulation performance, but has problems such as metal oxidation, signal shielding and high internal reflection.

[0003] Although the sunshade film technology has made great progress, in the field of dark or black sunshade films, a long-standing technical problem has not been perfectly solved, that is, the sharp contradiction between heat insulation performance and light shielding performance. In order to obtain excellent light shielding effect and privacy, the traditional technical route relies heavily on adding high-concentration carbon black or dark dye in the film body. However, as a typical wide-spectrum absorption material, carbon black not only absorbs visible light, but also absorbs near-infrared radiation, which accounts for more than 50% of the heat content in solar energy. This absorption mode causes the temperature of the thin film to rise sharply, and the absorbed huge heat energy will be continuously transmitted in the form of secondary heat radiation, greatly reducing the heat insulation effect.

[0004] Therefore, a black TPEE sunshade film and a preparation method thereof are provided. SUMMARY

[0005] The purpose of the application is to design a black TPEE sunshade film and a preparation method thereof.

[0006] To achieve the above purpose, the application provides the following technical scheme:

[0007] The application provides a preparation method of a black TPEE sunshade film.

[0008] The first TPEE chip, nano carbon black, graphene and titanium black are melt-blended, extruded and cut into particles to obtain heat insulation master batch A; the second TPEE chip, modified boron nitride and hollow glass microspheres are melt-blended, extruded and cut into particles to obtain heat insulation master batch B; the third TPEE chip, a compatibilizer, a composite additive and modified calcium carbonate are prepared to form layer A, the fourth TPEE chip, the heat insulation master batch A and the heat insulation master batch B are prepared to form layer B; the fifth TPEE chip is prepared to form layer C, and the three layers are co-extruded to form a film; the film is subjected to aging treatment, and then cut and rolled to obtain a black TPEE sunshade film.

[0009] The modified boron nitride is obtained by modifying hexagonal boron nitride with a silane coupling agent; and the modified calcium carbonate is obtained by modifying nano calcium carbonate with a silane coupling agent.

[0010] Preferably, the average molecular weight of the TPEE chip is 30000-45000.

[0011] Preferably, the preparation method of the heat insulation master batch A is as follows: 100 parts of TPEE chip, 10-20 parts of nano carbon black, 3-7 parts of graphene and 15-25 parts of titanium black are put into a double screw extruder, the temperature of each zone of the extruder is set as 180℃→195℃→210℃→220℃→215℃→210℃, the screw rotation speed is 350-450 rpm, and the heat insulation master batch A is obtained by water cooling, drawing, and granulating.

[0012] Preferably, the preparation method of the heat insulation master batch B is as follows: 100 parts of TPEE chip and 25-35 parts of modified boron nitride are added from the main material port of a double screw extruder, 6-10 parts of hollow glass microspheres are added from the side material port, the temperature of each zone of the extruder is set as 180℃→195℃→210℃→215℃→210℃→205℃, the screw rotation speed is 200-300 rpm, and the heat insulation master batch B is obtained by water cooling, drawing, and granulating.

[0013] Preferably, the preparation method of the modified boron nitride is as follows: hexagonal boron nitride is immersed in a 5mol / L NaOH solution, reacted at 110℃ for 10h, then filtered and washed repeatedly with deionized water, and dried at 70℃ for 10h to obtain pretreated boron nitride; 100 parts of anhydrous ethanol, 10 parts of deionized water and 0.5-1.5 parts of KH-550 are added into a three-necked flask, and reacted for 10min to obtain a hydrolysis solution; 20-30 parts of the pretreated boron nitride is added into the hydrolysis solution, and the reaction is continued for 1-3h, after the reaction is completed, the product is filtered, washed and dried to obtain the modified boron nitride.

[0014] Preferably, the specific preparation method of the film is as follows: 100 parts of TPEE chip, 5 parts of a compatibilizer, 3-7 parts of a composite additive and 8-12 parts of modified calcium carbonate are used as the A layer, 100 parts of TPEE chip, 25-35 parts of heat insulation master batch A and 35-45 parts of heat insulation master batch B are used as the B layer, and 100 parts of TPEE chip is used as the C layer, the temperature of the extruder is set as 180℃→200℃→215℃, the die temperature is 210℃, the temperature of the casting roller is 20-30℃, the production line speed is 15-25m / min, and the film is obtained by three-layer co-extrusion molding; the average thickness of the film is 100μm.

[0015] Preferably, the preparation method of modified calcium carbonate is as follows: 400 parts of anhydrous ethanol and 15 parts of deionized water are added into a three-necked flask, 1-3 parts of KH-550 is added dropwise, and hydrolysis is carried out in a 40℃ water bath for 45 minutes to obtain a hydrolysis solution; 95-105 parts of nano calcium carbonate is added into the hydrolysis solution, stirring and dispersing for 15 minutes until the suspension is uniform, the temperature is increased to 70℃, and stirring reaction is carried out under nitrogen protection for 2-4 hours; after the reaction is completed, the filter cake is washed with anhydrous ethanol for 3 times, and the filter cake is dried in an oven at 80℃ for 6 hours; after being crushed, the modified calcium carbonate is obtained.

[0016] Preferably, the compatilizer is MAH-g-SEBS; the composite aid includes ultraviolet absorber UV-326, light stabilizer HALS-944 and antioxidant 1010, and the weight ratio of ultraviolet absorber UV-326, light stabilizer HALS-944 and antioxidant 1010 is 3:2:1.

[0017] Preferably, the specific process of the aging treatment is as follows: the film is placed in a constant-temperature aging room at 50℃ for 36 hours, and then cutting and rolling are carried out to obtain the black TPEE sunshade film.

[0018] Another aspect of the present application provides a black TPEE sunshade film, and the synthetic raw materials include TPEE chips, nano carbon black, graphene, titanium black, modified boron nitride, hollow glass microbeads, a compatilizer, a composite aid and modified calcium carbonate.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] 1. In the heat insulation master batch A, the titanium black pigment first plays a "cold black" effect, actively reflects most of the invisible near-infrared heat radiation, and reduces heat absorption from the source. For the remaining absorbed solar energy, the graphene with high thermal conductivity immediately plays a role in heat dissipation, rapidly conducts and diffuses heat along the film plane direction, avoiding the formation of local hot spots. Finally, the nano carbon black provides the core shading function of stable and pure black color, and the absorbed heat is also effectively shared by the graphene.

[0021] 2. The hollow glass microbeads in the heat insulation master batch B form a heat insulation channel in the material with the internal vacuum / low thermal conductivity gas, greatly cutting the heat transfer path mainly by conduction. On this basis, the flaky hexagonal boron nitride makes the distribution of hollow glass microbeads more uniform, and itself can reflect heat radiation. The uniformly distributed boron nitride also cannot form a heat conduction path, thereby further reducing the macroscopic thermal conductivity perpendicular to the film direction. The synergy of the two materials realizes the composite heat insulation effect.

[0022] 3、A layer of which the composite additive system plays a core chemical protection role: the ultraviolet absorber is responsible for absorbing high-energy ultraviolet light to prevent it from damaging the polymer chain from the source; the light stabilizer captures free radicals generated by a small amount of leaked ultraviolet light to terminate the chain degradation reaction; the antioxidant prevents thermal aging of the material during processing and long-term use. At the same time, the surface-modified nano calcium carbonate is well combined with the TPEE matrix, improving the mechanical properties of the surface layer. The compatibilizer, like super glue, ensures that layer A is firmly combined with the core functional layer B to resist the erosion of the external environment.

[0023] 4、When solar energy penetrates layer A to layer B, most of the infrared heat is first reflected by the titanium black in the master batch A; then, the two-dimensional sheet structure of graphene in master batch A and boron nitride in master batch B work together to quickly horizontally conduct the remaining absorbed heat; finally, the strong thermal barrier composed of hollow glass microspheres and boron nitride sheets in master batch B provides the final and most effective barrier to the residual heat flow trying to penetrate layer B. This interlocking and progressive synergistic mechanism fundamentally solves the contradiction between light shielding and heat insulation.

[0024] 5、A layer as a "protective shell" provides a stable working environment for layer B with its excellent weather resistance, protecting it from ultraviolet light and oxidation, thereby ensuring the long-term and durable heat-shielding and light-shielding performance; layer C ensures the flexibility and low internal stress of the film. The interaction between the three layers avoids the bubbling or cracking caused by mismatched interlayer stress when the temperature changes. This clear division of labor and cooperation improves the overall performance of the entire film. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The figure shows the light-shielding performance of Example 1 and Comparative Examples 5-8 in the present invention. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the present invention.

[0027] Specific reference Figure 1 The present invention provides a black TPEE sunshade film and a preparation method thereof, and the technical solutions are as follows:

[0028] Example 1

[0029] The hexagonal boron nitride is immersed in a 5 mol / L NaOH solution, and reacted at 110 DEG C for 10 hours, then filtered and washed repeatedly with deionized water, and dried at 70 DEG C for 10 hours to obtain pretreated boron nitride; 100 parts of anhydrous ethanol, 10 parts of deionized water and 1 part of KH550 are added into a three-necked flask, and reacted for 10 minutes to obtain a hydrolysis solution; 25 parts of pretreated boron nitride is added into the hydrolysis solution, and the reaction is continued for 2 hours; after the reaction is completed, the product is filtered, washed and dried to obtain modified boron nitride.

[0030] 400 parts of anhydrous ethanol and 15 parts of deionized water are added into a three-necked flask, and 2 parts of KH-550 is added dropwise, and the hydrolysis is stirred in a 40 DEG C water bath for 45 minutes to obtain a hydrolysis solution; 100 parts of nano calcium carbonate is added into the hydrolysis solution, and stirred and dispersed for 15 minutes until the suspension is uniform, and then heated to 70 DEG C, and stirred for 3 hours under nitrogen protection; after the reaction is completed, the product is filtered and washed with anhydrous ethanol for 3 times, and the filter cake is dried in an oven at 80 DEG C for 6 hours, and then crushed to obtain modified calcium carbonate.

[0031] The composite auxiliary agent includes ultraviolet absorber UV-326, light stabilizer HALS-944 and antioxidant 1010, and the weight ratio of the ultraviolet absorber UV-326, the light stabilizer HALS-944 and the antioxidant 1010 is 3:2:1.

[0032] 100 parts of TPEE chips, 15 parts of nano carbon black, 5 parts of graphene and 20 parts of titanium black are put into a double-screw extruder, and the temperature of each zone of the extruder is set as 180 DEG C→195 DEG C→210 DEG C→220 DEG C→215 DEG C→210 DEG C, and the screw rotation speed is 400 rpm; after water cooling, drawing, granulating and cutting, heat insulation master batch A is obtained;

[0033] 100 parts of TPEE chips and 30 parts of modified boron nitride are added from the main material port of a double-screw extruder, and 8 parts of hollow glass microspheres are added from the side material port; the temperature of each zone of the extruder is set as 180 DEG C→195 DEG C→210 DEG C→215 DEG C→210 DEG C→205 DEG C, and the screw rotation speed is 250 rpm; after water cooling, drawing and granulating, heat insulation master batch B is obtained;

[0034] 100 parts of TPEE chips, 5 parts of a compatibilizer, 5 parts of a composite auxiliary agent and 10 parts of modified calcium carbonate are used as the A layer, 100 parts of TPEE chips, 30 parts of heat insulation master batch A and 40 parts of heat insulation master batch B are used as the B layer, and 100 parts of TPEE chips are used as the C layer; the temperature of the extruder is set as 180 DEG C→200 DEG C→215 DEG C, the die temperature is 210 DEG C, the temperature of the casting roller is 25 DEG C, and the production line speed is 20 m / min; three-layer co-extrusion molding is carried out to obtain a film;

[0035] The film was placed in a constant temperature aging room at 50°C for 36h, and then cut and rolled to obtain a black TPEE sunshade film. Examples 2-5 refer to the parameter conditions in Example 1, with specific differences as shown in Table 1.

[0036] Table 1 Parameter conditions of Examples 1-5

[0037]

[0038] Comparative Example 1 refers to the parameter conditions in Example 1, with the difference being that 40 parts of nano carbon black is added instead of 15 parts of nano carbon black, 5 parts of graphene, and 20 parts of titanium black.

[0039] Comparative Example 2 refers to the parameter conditions in Example 1, with the difference being that no graphene is added.

[0040] Comparative Example 3 refers to the parameter conditions in Example 1, with the difference being that no titanium black is added.

[0041] Comparative Example 4 refers to the parameter conditions in Example 1, with the difference being that no heat insulation masterbatch A is prepared, and is directly added in the subsequent process.

[0042] Experimental Example 1 Heat insulation and light shielding performance test

[0043] The thermal conductivity of Examples 1-5 and Comparative Examples 1-4 was tested according to the GB / T 10294-2008 standard; the visible light transmittance and infrared transmittance of Examples 1-5 and Comparative Examples 1-4 were tested using an LS183 optical transmittance measuring instrument; the results are shown in Table 2.

[0044] Table 2 Heat insulation and light shielding performance test of Examples 1-5 and Comparative Examples 1-4

[0045] Examples Thermal conductivity / W / m-K Visible light transmittance / % Infrared transmittance / % Example 1 0.926 8 5 Example 2 0.832 15 11 Example 3 0.875 12 9 Example 4 0.856 10 8 Example 5 0.897 8 6 Comparative Example 1 0.815 3 25 Comparative Example 2 0.781 9 8 Comparative Example 3 0.905 20 35 Comparative Example 4 0.852 18 22

[0046] It can be found from Table 2 that the comparative example 1 uses 40 parts of ordinary nano carbon black to replace the composite system of nano carbon black, graphene and titanium black. From the data, it obtains extremely strong light shielding effect. This is because high concentration of carbon black has almost complete absorption capacity for visible light. However, the heat insulation performance appears cliff-like drop, which fully proves that single carbon black only realizes shielding by absorbing full-band solar energy, and itself will accumulate a large amount of heat energy and produce secondary radiation, which cannot effectively block infrared heat penetration. The reduction of thermal conductivity is due to the lack of high thermal conductivity graphene in the formula. The comparative example 2 removes only graphene based on the example 1, and the visible light transmittance and infrared transmittance both appear slight rise, which shows that graphene itself also contributes to certain light shielding and infrared absorption capacity. The most significant change is the thermal conductivity, which clearly confirms the key role of graphene in the present application, that is, to build an efficient horizontal heat conduction path. Without graphene, the film body cannot quickly conduct the absorbed heat in the plane direction, although the infrared transmittance test value changes little, but in actual use, the surface temperature of the film body will be higher, and the secondary heat radiation inward will be more serious. The comparative example 3 removes titanium black based on the example 1, and the visible light transmittance increases greatly, which is because the important black pigment component is lacking in the formula, and the total coloring power decreases. At the same time, the infrared transmittance increases sharply, which decisively proves that without the active reflection of titanium black, the infrared heat in the sunlight can easily penetrate the film, and the absorption and barrier of carbon black and boron nitride are far from enough. The comparative example 4 directly adds all powders into the extruder, and the results show that the visible light transmittance and infrared transmittance both appear to decrease, and the thermal conductivity also decreases obviously. This is because the nano carbon black, graphene, titanium black and other nano powders are prone to agglomeration. Without being prepared into master batch by double screw high shear pre-dispersion, they cannot be effectively dispersed when added subsequently. The agglomerates not only reduce the specific surface area of the functional fillers, greatly reducing their optical shielding and heat management capacity, but also cannot form an effective heat conduction network.

[0047] Examples 6-9 refer to the parameter conditions in example 1, and the specific differences are shown in Table 3.

[0048] Table 3 Parameter conditions of example 1 and examples 6-9

[0049]

[0050] Comparative example 5 refers to the parameter conditions in example 1, and the difference is that the boron nitride is not modified.

[0051] Comparative example 6 refers to the parameter conditions in example 1, and the difference is that the modified boron nitride is not added.

[0052] Comparative example 7 refers to the parameter conditions in example 1, and the difference is that the hollow glass microsphere is not added.

[0053] Comparative Example 8 refers to the parameters conditions in Example 1, with the difference that the heat shield masterbatch B is not prepared, being added directly in the subsequent process.

[0054] Example 2 Heat shield and light shield performance test

[0055] The performance of Example 1, Examples 6-9 and Comparative Examples 5-8 was tested following the method of Example 1, the results obtained being shown in Table 4, the light shield performance of Example 1 and Comparative Examples 5-8 being shown in Figure 1

[0056] Table 4 Heat shield and light shield performance test of Example 1, Examples 6-9 and Comparative Examples 5-8

[0057]

[0058]

[0059] Table 4 and Figure 1 ​It can be found that the comparative example 5 uses unmodified boron nitride by silane coupling agent, and both the visible light and infrared transmittance are greatly increased, and the performance is obviously deteriorated, because the surface of unmodified boron nitride is inorganic, and the compatibility between the organic TPEE matrix is poor, which leads to serious agglomeration during the blending process, and the interface bonding force is weak, the agglomerates not only cannot form an effective heat barrier, but also become stress concentration points and optical defects, thereby reducing the comprehensive performance. The infrared transmittance of comparative example 6 is significantly increased, and the heat insulation performance is greatly decreased, which directly proves that boron nitride plays a crucial role in the present application: first, it reflects heat radiation with its sheet structure; second, the uniformly dispersed boron nitride does not form a heat conduction path, and the heat insulation ability in the B layer is severely weakened without boron nitride; at the same time, the thermal conductivity coefficient also decreases sharply, which also reversely proves the important contribution of boron nitride to the construction of efficient horizontal heat management network. The infrared transmittance of comparative example 7 is obviously increased, indicating that the heat insulation performance is significantly deteriorated, because the hollow glass microsphere blocks the heat transfer in the form of heat conduction through its internal micro-vacuum structure, and even if there are other materials such as boron nitride, heat can still be more easily conducted through the vibration of polymer chains. The performance of comparative example 8 is significantly deteriorated, and the infrared transmittance is obviously increased, which fully shows the necessity of preparing the heat insulation master batch B, because the hollow glass microsphere is a fragile shear-sensitive material, and boron nitride needs high shear to disperse uniformly, and the processing conditions required by the two materials are contradictory. By preparing the master batch B, the microspheres can be protected from being damaged while the boron nitride is preliminarily and well dispersed, if they are mixed directly in the final extrusion step, both cannot be considered, which will inevitably lead to uneven dispersion and microsphere breakage, and cannot form an effective heat insulation structure.

[0060] Examples 10-13 refer to the parameter conditions in example 1, and the specific differences are shown in table 5.

[0061] Table 5 Parameter conditions of example 1 and examples 10-13

[0062]

[0063]

[0064] Comparative example 9 refers to the parameter conditions in example 1, and the difference is that the nano calcium carbonate is not modified.

[0065] Comparative example 10 refers to the parameter conditions in example 1, and the difference is that the modified calcium carbonate is not added.

[0066] Comparative Example 11 refers to the parameter conditions in Example 1, the difference is that the ultraviolet absorber UV-326 is not added in the composite auxiliary agent.

[0067] Comparative Example 12 refers to the parameter conditions in Example 1, the difference is that the light stabilizer HALS-944 is not added in the composite auxiliary agent.

[0068] Comparative Example 13 refers to the parameter conditions in Example 1, the difference is that the antioxidant 1010 is not added in the composite auxiliary agent.

[0069] Comparative Example 14 refers to the parameter conditions in Example 1, the difference is that the composite auxiliary agent is not added.

[0070] Comparative Example 15 refers to the parameter conditions in Example 1, the difference is that the compatilizer is not added.

[0071] Comparative Example 16 refers to the parameter conditions in Example 1, the difference is that the three-layer co-extrusion is not carried out, and the whole body is directly melt extruded.

[0072] Experimental Example 3 Mechanical property test

[0073] According to the GB / T 1040.2-2022 standard test, the tensile strength and elongation at break of Example 1, Example 10-13 and Comparative Example 9-16 were tested. The samples were placed in an ultraviolet aging test box for aging for 24 h, and the tensile strength after aging was tested. The results are shown in Table 6.

[0074] Table 6 Tensile strength and elongation at break of Example 1, Example 10-13 and Comparative Example 9-16

[0075]

[0076] From Table 6, it can be found that the comparative example 9 is not modified with nano calcium carbonate, and its tensile strength and elongation at break are significantly lower than those of the example 1, and the tensile strength after aging is only 18.2 MPa, which indicates that the unmodified nano calcium carbonate has strong surface polarity, poor compatibility with the matrix, and is easy to form stress concentration points, resulting in the decrease of mechanical properties, and is more likely to become a degradation starting point during the ultraviolet aging process, accelerating the material degradation. The comparative example 10 does not add modified calcium carbonate, although the initial elongation at break is higher, the tensile strength is lower than that of the example 1, and the tensile strength after aging is reduced to 20.5 MPa, which indicates that the modified calcium carbonate can play a role in rigid support in the system, and improve the structural stability of the material, and the absence of the material will significantly weaken the tensile strength and aging resistance. The comparative example 11 does not add the ultraviolet absorber UV-326, and the tensile strength after aging is reduced by 18.2% compared with the example 1. This verifies that UV-326 can effectively absorb ultraviolet light, reduce the damage of high-energy radiation to the molecular chain, and its absence will lead to more likely photo-oxidative degradation of the material in the ultraviolet aging. The comparative example 12 does not add the light stabilizer HALS-944, and the tensile strength after aging is reduced by 29.2%, which is significantly higher than that of the example 1. HALS-944 can capture free radicals and inhibit the degradation chain reaction, and its absence will make the free radicals accumulate and accelerate during the aging process, resulting in the rapid decrease of the mechanical properties. The comparative example 13 does not add the antioxidant 1010, and the tensile strength after aging is reduced by 19.2% compared with the example 1. The antioxidant 1010 can inhibit the oxidative degradation of the material, and the absence of the antioxidant will aggravate the oxidation reaction, resulting in the accelerated molecular chain rupture and the decrease of the strength retention rate after aging. The comparative example 14 does not add the composite additive at all, and the tensile strength after aging is only 19.7 MPa, which is much higher than the case of the absence of a single additive, indicating that the ultraviolet absorber, the light stabilizer and the antioxidant in the composite additive have a synergistic effect, and are indispensable for delaying the photoaging process of the material. The comparative example 15 does not add the compatibilizer, and the initial tensile strength and elongation at break are significantly reduced, and the strength after aging is only 12.3 MPa. The compatibilizer can improve the interfacial bonding force between the matrix and the filler, and its absence will cause serious interfacial defects, and the mechanical properties and aging resistance of the material will be significantly deteriorated. The comparative example 16 adopts the whole melt extrusion instead of the three-layer co-extrusion, and the tensile strength and elongation at break are significantly reduced. The three-layer co-extrusion structure can optimize the stress distribution and interfacial bonding in the material, and improve the overall performance, while the whole extrusion is easy to cause uneven distribution of the components, and reduce the stability and aging resistance of the material.

[0077] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a black TPEE sunshade film, characterized in that: The preparation method includes the following steps: The first batch of TPEE chips, nano carbon black, graphene and titanium black were melt-blended, extruded and granulated to obtain heat insulation masterbatch A; The second batch of TPEE chips, modified boron nitride, and hollow glass microspheres were melt-blended, extruded, and pelletized to obtain thermal insulation masterbatch B; Layer A is prepared by combining the third TPEE chips, compatibilizer, composite additives, and modified calcium carbonate; layer B is prepared by combining the fourth TPEE chips, heat insulation masterbatch A, and heat insulation masterbatch B; layer C is prepared by combining the fifth TPEE chips; and the three layers are co-extruded to obtain a film. The film is subjected to aging treatment, and then cut and rolled to obtain the black TPEE sunshade film; The modified boron nitride is obtained by modifying hexagonal boron nitride with a silane coupling agent; the modified calcium carbonate is obtained by modifying nano-calcium carbonate with the silane coupling agent.

2. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The preparation method of the heat insulation masterbatch A is as follows: the first batch of TPEE chips, the nano carbon black, the graphene and the titanium black are put into a twin-screw extruder, the temperature of each zone of the extruder is set from 180°C to 210°C, and the extruder is granulated by water cooling and pelletizing to obtain the heat insulation masterbatch A.

3. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The preparation method of the heat insulation masterbatch B is as follows: the second part of the TPEE chips and the modified boron nitride are added from the main feed port of the twin-screw extruder, and the hollow glass microspheres are added from the side feed port. After melt extrusion, the mixture is water-cooled, stretched, and granulated to obtain the heat insulation masterbatch B.

4. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The modified boron nitride is prepared as follows: the hexagonal boron nitride is immersed in NaOH solution, reacted, filtered, and repeatedly washed with deionized water, and dried to obtain pretreated boron nitride; anhydrous ethanol, deionized water and silane coupling agent KH-550 are added to a three-necked flask, and the reaction is carried out to obtain a hydrolysis solution; the pretreated boron nitride is added to the hydrolysis solution, and the reaction is continued with stirring. After the reaction is completed, the product is filtered, washed and dried to obtain the modified boron nitride.

5. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The specific preparation method of the film is as follows: the third part of the TPEE chips, the compatibilizer, the composite additive and the modified calcium carbonate are used as the A layer, the fourth part of the TPEE chips, the heat insulation masterbatch A and the heat insulation masterbatch B are used as the B layer, and the fifth part of the TPEE chips are used as the C layer. The temperature of the extruder is set from 180°C to 210°C, and the three layers are co-extruded to obtain the film.

6. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The modified calcium carbonate is prepared as follows: anhydrous ethanol and deionized water are added to a three-necked flask, and then silane coupling agent KH-550 is added dropwise. The mixture is stirred and hydrolyzed in a water bath to obtain a hydrolyzed solution. The nano-calcium carbonate is added to the hydrolyzed solution and stirred and dispersed until the suspension is uniform. Then, the mixture is stirred and reacted under nitrogen protection. After the reaction is completed, the mixture is filtered, washed, dried, and pulverized to obtain the modified calcium carbonate.

7. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The compatibilizer is MAH-g-SEBS; the composite additives include UV absorber UV-326, light stabilizer HALS-944, and antioxidant 1010.

8. The method for preparing a black TPEE sunshade film according to claim 1, characterized in that: The specific process of the aging treatment is as follows: the film is placed in a constant temperature aging chamber, and then cut and rolled up to obtain the black TPEE sunshade film.

9. A black TPEE sunshade film, characterized in that: The raw materials for synthesizing the black TPEE sunshade film include TPEE chips, nano carbon black, graphene, titanium black, modified boron nitride, hollow glass microspheres, compatibilizer, composite additives, and modified calcium carbonate; the black TPEE sunshade film is prepared by the preparation method described in any one of claims 1-8.

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