Automobile glass protective film as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of automobile glass protective films, and particularly relates to an automobile glass protective film as well as a preparation method and application thereof. The automotive glass protective film comprises a functional layer, a first TPU film layer, a first adhesive layer, a base material layer, a second adhesive layer, a second TPU film layer and a mounting adhesive layer from top to bottom, the functional layer is prepared from the following raw materials: waterborne polyurethane emulsion, a functional compound, a defoaming agent and a flatting agent; the functional compound comprises polyethyleneimine modified filler and cellulose aerogel loaded with an ultraviolet light absorber; the filler comprises hexagonal flaky magnesium hydroxide and nano titanium dioxide. The automobile glass protective film provided by the invention has the advantages of ultraviolet resistance, heat insulation, explosion prevention and long service life.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of automobile glass protection film, and particularly relates to an automobile glass protection film and a preparation method and application thereof. BACKGROUND

[0002] At present, with the rapid development of the automobile industry and the improvement of people's requirements for a better life, the requirement for automobile comfort is also continuously improved. Sunlight passing through the automobile glass not only causes the temperature inside the automobile to rise, but also causes the interior of the automobile to age. In order to solve this problem, automobile glass protection film emerges as the times require. The automobile glass protection film is a thin film attached to the window glass, and its performance requirement is to effectively block ultraviolet and infrared rays and reduce the temperature inside the automobile. In order to endow the automobile glass protection film with ultraviolet resistance and heat insulation performance, it is necessary to add ultraviolet resistance agents and infrared resistance agents in the base resin. However, the conventional organic ultraviolet resistance agent only realizes protection through molecular resonance absorption, and long-term exposure is prone to photodegradation, resulting in yellowing of the film layer and performance degradation. Although inorganic ultraviolet resistance agents and inorganic infrared resistance agents have long-term stable characteristics, they are prone to agglomeration in the base resin, resulting in a decrease in strength and flexibility and poor explosion-proof performance. Therefore, it is necessary to provide an automobile glass protection film with ultraviolet resistance, heat insulation, explosion-proof and long service life.

[0003] The Chinese patent with publication number CN118308021A in the prior art discloses an ultraviolet-proof automobile glass film and a preparation method thereof, which comprises a 4-layer structure, from inside to outside, a base layer, a heat insulation layer, an ultraviolet-proof layer and a wear-resistant layer, the thickness of the base layer is 20-80 microns, the thickness of the heat insulation layer is 3-15 microns, the thickness of the ultraviolet-proof layer is 4-10 microns, and the thickness of the protective film layer is 25-50 microns; the main material component of the ultraviolet-proof layer comprises, by weight, nano-modified zinc oxide loaded PTFE 40-60 parts, p-xylene 25-30 parts, butyl acetate 17-19 parts, styrene acetate 30-40 parts, hollow microbeads 5-8 parts, manganese acetate 0.3-1.5 parts, lignin 0.5-1 part, ultraviolet-resistant agent 10-15 parts, heat stabilizer 0.2-0.3 parts, light sensitizer 4-5 parts, dispersant 1-8 parts and water-based polyurethane 200-300 parts. The problems of poor ultraviolet-proof effect of the automobile glass film and insufficient stability of the ultraviolet-proof glass film in the prior art are solved. The ultraviolet-proof film has the advantages of good ultraviolet absorption effect and good weather resistance. However, the technical solution does not pay attention to explosion-proof and service life. The Chinese patent with publication number CN112538316A discloses a glass explosion-proof shield film and a preparation method thereof. The glass explosion-proof shield film comprises a silica gel protective film layer, a scratch-resistant layer, a base material layer, a pressure-sensitive adhesive layer and a transparent release protective film layer which are sequentially laminated. The shield film can tightly fit the large-radiused front windshield of the automobile, has great toughness and will not cause the glass to break and splash under a great impact, thereby playing a role in explosion-proof. Meanwhile, the glass explosion-proof shield film also has excellent scratch resistance, anti-aging performance, good ultraviolet-proof and heat insulation effects, long service life and easy mass production, but the ultraviolet blocking rate of the technical solution can only reach 97.5%.

[0004] Cellulose aerogel is a thermal insulation material, so it is of great significance to apply it to automobile glass protective film to solve the heat insulation performance of automobile glass protective film. In view of this, the present application is proposed. SUMMARY

[0005] The first object of the present application is to provide an automobile glass protective film. The automobile glass protective film provided by the present application has the advantages of ultraviolet resistance, heat insulation, explosion-proof and long service life.

[0006] The second object of the present application is to provide a preparation method of the automobile glass protective film.

[0007] The third object of the present application is to provide an application of the automobile glass protective film to the rear side window glass or sunroof glass of an automobile.

[0008] In order to achieve the above objects of the present application, the following technical solutions are adopted: The application provides a car glass protection film, which comprises a functional layer, a first TPU film layer, a first adhesive layer, a substrate layer, a second adhesive layer, a second TPU film layer and a mounting adhesive layer from top to bottom. The raw materials of the functional layer comprise a water-based polyurethane emulsion, a functional compound, a defoaming agent and a leveling agent. The functional compound comprises a polyethylene imine modified filler and a cellulose aerogel loaded with an ultraviolet absorber. The filler comprises hexagonal flaky magnesium hydroxide and nano titanium dioxide.

[0009] Further, the raw materials of the functional layer comprise, by mass fraction, 80-100 parts of the water-based polyurethane emulsion, 10-25 parts of the functional compound, 0.5-1.5 parts of the defoaming agent and 0.5-1.5 parts of the leveling agent.

[0010] Further, the water-based polyurethane emulsion is a water-based aliphatic polyurethane emulsion.

[0011] Further, the water-based aliphatic polyurethane emulsion is SEAPUR50K15 of Guangdong Xintong New Material Technology Co., Ltd.

[0012] Further, the mass ratio of the polyethylene imine modified filler and the cellulose aerogel loaded with the ultraviolet absorber is 5-15:5-10.

[0013] Further, the viscosity of the polyethylene imine is 5000-9000 mpa.s at 25 DEG C.

[0014] Further, the mass ratio of the hexagonal flaky magnesium hydroxide and the nano titanium dioxide is 1-2:1.

[0015] Further, the average particle size of the hexagonal flaky magnesium hydroxide is 1-2 µm.

[0016] Further, the average particle size of the hexagonal flaky magnesium hydroxide is 2 µm.

[0017] Further, the average particle size of the nano titanium dioxide is 10-30 nm.

[0018] Further, the average particle size of the nano titanium dioxide is 20 nm.

[0019] Further, the preparation method of the polyethylene imine modified filler comprises the following steps: dissolving polyethylene imine in ethanol, adding a filler under stirring, continuing stirring, washing, drying and obtaining.

[0020] Further, the mass ratio of the polyethylene imine, ethanol and filler is 1-2:5-10:5-10.

[0021] Further, the preparation method of the polyethyleneimine modified filler comprises the following steps: dissolving polyethyleneimine in ethanol, heating to 40-50℃, adding filler under stirring, continuing stirring for 10-12h, washing, drying to obtain.

[0022] Further, the preparation method of the cellulose aerogel loaded with ultraviolet absorber comprises the following steps: S1, dispersing bacterial cellulose in water to obtain a bacterial cellulose solution, adding organic ultraviolet absorber A to the bacterial cellulose solution, stirring, and vacuum freeze-drying after stirring to obtain a cellulose aerogel intermediate; S2, dispersing the cellulose aerogel intermediate in ethanol, adding vinyl silane coupling agent, organic ultraviolet absorber B and initiator, reacting, centrifuging, washing and drying after reaction to obtain a cellulose aerogel loaded with ultraviolet absorber.

[0023] Further, the mass ratio of the bacterial cellulose, the organic ultraviolet absorber A and water in step S1 is 2-5:1:100.

[0024] Further, the diameter of the bacterial cellulose in step S1 is 50-100nm.

[0025] Further, the organic ultraviolet absorber A in step S1 is a benzotriazole ultraviolet absorber.

[0026] Further, the benzotriazole ultraviolet absorber is at least one selected from UV327 (2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole), UV-P (2-(2'-hydroxy-5'-methylphenyl) benzotriazole), UV-320 (2-(3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole) and UV-326 (2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole).

[0027] Further, the temperature of the stirring in step S1 is 25-30℃, the stirring speed is 200-500rpm, and the stirring time is 2-5h.

[0028] Further, the temperature of the vacuum freeze-drying in step S1 is -80℃~-60℃, and the vacuum freeze-drying time is 24-48h.

[0029] Further, the mass ratio of the cellulose aerogel intermediate, vinyl silane coupling agent, organic ultraviolet absorber B, initiator and ethanol in step S2 is 40-50:0.1-0.3:1-2:0.2-0.4:80-100.

[0030] Further, the vinyl silane coupling agent in step S2 is selected from at least one of vinyltrimethoxysilane and vinyltriethoxysilane.

[0031] Further, the organic ultraviolet absorber B in step S2 is selected from at least one of 4-propenoxy-2-hydroxybenzophenone, 2-hydroxy-4-(methacryloyloxy)benzophenone and 2-hydroxy-4-acryloyloxyethoxybenzophenone.

[0032] Furthermore, the initiator in step S2 is azobisisobutyronitrile.

[0033] Furthermore, the reaction temperature in step S2 is 40-60℃, and the reaction time is 3-5h.

[0034] Furthermore, the preparation method of the functional layer includes the following steps: mixing waterborne polyurethane emulsion, functional compound, defoamer, and leveling agent evenly to obtain the final product.

[0035] Furthermore, the automotive glass protective film also includes a protective film layer disposed on the functional layer, and / or a release layer disposed under the adhesive layer.

[0036] Furthermore, the protective film layer is a PET film or a silicone protective film.

[0037] Furthermore, the release layer is a PET release film.

[0038] Furthermore, the substrate layer is a PET film.

[0039] Furthermore, the first adhesive layer and the second adhesive layer are each independently selected from either acrylic pressure-sensitive adhesive or polyurethane adhesive.

[0040] Furthermore, the mounting adhesive layer is an acrylic pressure-sensitive adhesive.

[0041] Furthermore, the thickness of the functional layer is 2-10µm.

[0042] Furthermore, the thickness of the first TPU film layer is 50-100µm.

[0043] Furthermore, the thickness of the first adhesive layer is 5-20µm.

[0044] Furthermore, the thickness of the substrate layer is 15-50µm.

[0045] Furthermore, the thickness of the second adhesive layer is 5-20µm.

[0046] Furthermore, the thickness of the second TPU film layer is 50-100µm.

[0047] Furthermore, the thickness of the mounting adhesive layer is 10-30µm.

[0048] Furthermore, the thickness of the protective film layer is 3-20µm.

[0049] Furthermore, the thickness of the release layer is 10-80µm.

[0050] This invention provides a method for preparing the above-mentioned automotive glass protective film, comprising the following steps: A first adhesive layer and a second adhesive layer are coated on the surface of the substrate layer, respectively. After drying, they are laminated to the first TPU film layer and the second TPU film layer on both sides, respectively. An installation adhesive layer is coated on the release surface of the release layer, and after drying, it is laminated to the second TPU film layer. A functional layer is coated on the first TPU film layer, and then laminated to the protective film layer to obtain the final product.

[0051] The present invention also provides the application of the above-mentioned automotive glass protective film in the rear side window glass or sunroof glass of an automobile.

[0052] Compared with the prior art, the present invention has the following beneficial effects: This invention uses a combination of polyethyleneimine-modified filler and cellulose aerogel loaded with ultraviolet absorbers as a functional composite, which significantly improves the UV resistance, heat insulation, explosion resistance and service life of automotive glass protective film. During the experiment, the inventors found that the key to this technical solution is: (1) the use of polyethyleneimine-modified hexagonal flake magnesium hydroxide and nano titanium dioxide, especially the use of polyethyleneimine and hexagonal flake magnesium hydroxide. Compared with the use of silane coupling agents and ordinary spherical magnesium hydroxide, the use of the hydrogen bonding between the amino group of polyethyleneimine and cellulose aerogel and waterborne polyurethane emulsion, as well as the interlocking stacking of hexagonal flake magnesium hydroxide and nano titanium dioxide, makes the filler uniformly dispersed in the polyurethane crosslinked network structure after curing. (1) The explosion-proof properties and service life of the automotive glass protective film are significantly improved; (2) The cellulose aerogel loaded with ultraviolet absorbers obtained by the present invention using a specific preparation method has different ultraviolet absorbers loaded inside and outside the cellulose aerogel: the porous and highly cross-linked network structure of the cellulose aerogel selectively absorbs and reflects infrared rays; loading different ultraviolet absorbers inside and outside the cellulose aerogel improves the migration resistance and ultraviolet blocking properties of the ultraviolet absorbers, thereby synergistically improving the ultraviolet blocking and heat insulation properties of the automotive glass protective film; (3) The synergistic effect of polyethyleneimine modified filler and cellulose aerogel loaded with ultraviolet absorbers makes the automotive glass protective film have excellent ultraviolet resistance, heat insulation, explosion-proof properties and service life. Attached Figure Description

[0053] Figure 1 This is a schematic diagram of the automotive glass protective film structure in Example 1. Detailed Implementation

[0054] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0055] Unless otherwise specified, the raw materials, reagents or apparatus used in the following examples and comparative examples are available from conventional commercial sources or can be obtained by existing known methods.

[0056] Preparation Example 1: Functional Complex The functional composite is a cellulose aerogel consisting of a polyethyleneimine-modified filler and a UV absorber loaded in a mass ratio of 12:6.

[0057] The preparation method of the polyethyleneimine modified filler includes the following steps: dissolving polyethyleneimine in ethanol, heating to 50°C, adding filler while stirring, continuing to stir for 12 hours, washing, and drying to obtain the filler.

[0058] The mass ratio of polyethyleneimine, ethanol and filler is 1:8:6.

[0059] The viscosity of the polyethyleneimine is 8200-8600 mPa·s at 25°C. (Source: Gongbike New Material Technology (Shanghai) Co., Ltd.: GBK-PEI7550).

[0060] The filler is hexagonal sheet magnesium hydroxide and nano titanium dioxide in a mass ratio of 1:1.

[0061] The hexagonal flake magnesium hydroxide has an average particle size of 2µm, Luoyang Zhongchao New Material Co., Ltd.: MH-01.

[0062] The average particle size of the nano-titanium dioxide is 20nm. Nanjing Tianxing New Materials Co., Ltd.: TTP-R80.

[0063] The method for preparing the cellulose aerogel loaded with ultraviolet absorber includes the following steps: S1. Disperse bacterial cellulose in water to obtain a bacterial cellulose solution. Add organic ultraviolet absorber A to the bacterial cellulose solution and stir at 300 rpm for 3 hours at 25°C. After stirring, freeze dry under vacuum at -80°C for 24 hours to obtain a cellulose aerogel intermediate. S2. Disperse the cellulose aerogel intermediate in ethanol, add vinyl silane coupling agent, organic ultraviolet absorber B and initiator, react at 50°C for 4 hours, centrifuge, wash and dry after the reaction to obtain cellulose aerogel loaded with ultraviolet absorber.

[0064] The mass ratio of bacterial cellulose, organic ultraviolet absorber A, and water in step S1 is 3:1:100.

[0065] The bacterial cellulose described in step S1 has a diameter of 50-100 nm. (Shenzhen Qihong New Materials Co., Ltd.)

[0066] The organic ultraviolet absorber A mentioned in step S1 is UV327.

[0067] The mass ratio of the cellulose aerogel intermediate, vinyl silane coupling agent, organic ultraviolet absorber B, initiator and ethanol in step S2 is 50:0.2:1.5:0.3:100.

[0068] The vinyl silane coupling agent mentioned in step S2 is vinyltrimethoxysilane.

[0069] The organic ultraviolet absorber B mentioned in step S2 is 4-propenoxy-2-hydroxybenzophenone.

[0070] The initiator mentioned in step S2 is azobisisobutyronitrile.

[0071] Preparation Example 2: Functional Complex The only difference from Preparation Example 1 is that the hexagonal flake magnesium hydroxide is replaced with an equal mass of ordinary magnesium hydroxide with an average particle size of 1.6-1.9µm (Luoyang Zhongchao New Material Co., Ltd.: AH-01); all other aspects are the same.

[0072] Preparation Example 3: Functional Complex The only difference from Preparation Example 1 is that the polyethyleneimine modified filler is replaced with an equal mass of silane coupling agent modified filler, that is, the polyethyleneimine is replaced with an equal mass of KH550; all other aspects are the same.

[0073] Preparation Example 4: Functional Complex The only difference from Preparation Example 1 is that the cellulose aerogel loaded with ultraviolet absorber is replaced with an equal mass of cellulose aerogel. The preparation method of the cellulose aerogel includes the following steps: S1, dispersing bacterial cellulose in water to obtain a bacterial cellulose solution, stirring at 300 rpm for 3 hours at 25°C, and then freeze-drying under vacuum at -80°C for 24 hours after stirring to obtain cellulose aerogel. The mass ratio of bacterial cellulose to water is 3:100; all other steps are the same.

[0074] Preparation Example 5 The only difference from the preparation example is that the method for preparing the cellulose aerogel loaded with ultraviolet absorber includes the following steps: Bacterial cellulose was dispersed in water to obtain a bacterial cellulose solution. Organic ultraviolet absorber A was added to the bacterial cellulose solution, and the mixture was stirred at 300 rpm for 3 hours at 25°C. After stirring, the mixture was freeze-dried under vacuum at -80°C for 24 hours to obtain the final product. The rest of the process was the same.

[0075] Preparation Example 6 The only difference from Preparation Example 1 is that the method for preparing the cellulose aerogel loaded with ultraviolet absorber includes the following steps: S1. Disperse bacterial cellulose in water to obtain a bacterial cellulose solution. Stir at 300 rpm for 3 hours at 25°C. After stirring, freeze dry under vacuum at -80°C for 24 hours to obtain a cellulose aerogel intermediate. S2. Disperse the cellulose aerogel intermediate in ethanol, add vinyl silane coupling agent, organic ultraviolet absorber B and initiator, react at 50°C for 4 hours, centrifuge, wash and dry after the reaction to obtain cellulose aerogel loaded with ultraviolet absorber. The mass ratio of bacterial cellulose to water in step S1 is 3:100; all other ratios are the same.

[0076] Example 1 Figure 1 As shown: An automotive glass protective film comprises, from top to bottom, a protective film layer, a functional layer, a first TPU film layer, a first adhesive layer, a substrate layer, a second adhesive layer, a second TPU film layer, an installation adhesive layer, and a release layer.

[0077] The protective film layer is a PET film.

[0078] The raw materials of the functional layer, by weight, include 80 parts of waterborne polyurethane emulsion, 10 parts of functional composite, 0.6 parts of defoamer, and 0.6 parts of leveling agent.

[0079] The aqueous polyurethane emulsion is an aqueous aliphatic polyurethane emulsion, and the aqueous aliphatic polyurethane emulsion is SEAPUR 50K15 from Guangdong Xidun New Material Technology Co., Ltd.

[0080] The functional complex is the same as the functional complex prepared in Example 1.

[0081] The defoamer is BYK024.

[0082] The leveling agent is BYK306.

[0083] The method for preparing the functional layer includes the following steps: mixing waterborne polyurethane emulsion, functional compound, defoamer, and leveling agent evenly.

[0084] Both the first adhesive layer and the second adhesive layer are acrylic pressure-sensitive adhesives, Changxing Chemical SF08.

[0085] The substrate layer is a PET film.

[0086] The mounting adhesive layer is a polyurethane adhesive.

[0087] The release layer is a PET release film.

[0088] The thickness of the protective film is 10µm.

[0089] The thickness of the functional layer is 5µm.

[0090] The thickness of the first TPU film is 60µm.

[0091] The thickness of the first adhesive layer is 8µm.

[0092] The thickness of the substrate layer is 30µm.

[0093] The thickness of the second adhesive layer is 8µm.

[0094] The thickness of the second TPU film is 60µm.

[0095] The thickness of the mounting adhesive layer is 15µm.

[0096] The thickness of the release layer is 30µm.

[0097] The above-mentioned method for preparing automotive glass protective film includes the following steps: coating a first adhesive layer and a second adhesive layer on the surface of a substrate layer respectively, drying them, and then laminating them on both sides with a first TPU film layer and a second TPU film layer respectively; coating an installation adhesive layer on the release surface of the release layer, drying it, and then laminating it with the second TPU film layer; coating a functional layer on the first TPU film layer, and then laminating it with the protective film layer to obtain the final product.

[0098] Example 2 The only difference from Example 1 is that the functional complex is the same as that in Preparation Example 2; otherwise, they are the same.

[0099] Example 3 The only difference from Example 1 is that the functional complex is the same as that in Preparation Example 3; otherwise, they are the same.

[0100] Example 4 The only difference from Example 1 is that the functional complex is the same as that in Preparation Example 4; otherwise, they are the same.

[0101] Example 5 The only difference from Example 1 is that the functional complex is the same as that in Preparation Example 5; otherwise, they are the same.

[0102] Example 6 The only difference from Example 1 is that the functional complex is the same as that in Preparation Example 6; otherwise, they are the same.

[0103] I. Performance Testing Performance Test 1 UV blocking performance and heat insulation performance: According to GB / T 2680-2021, UV transmittance and solar transmittance are tested. UV transmittance represents UV blocking performance; the smaller the value, the better the UV blocking performance. Solar transmittance represents heat insulation performance; the smaller the value, the better the heat insulation performance. Performance Test 2 Mechanical properties: The maximum tensile force and elongation at break are tested according to QC / T 1170-2022. The higher the value, the better the explosion-proof performance.

[0104] Performance Test 3 Aging resistance performance: According to QC / T 1170-2022, the appearance, the difference in ultraviolet transmittance before and after the test, and the difference in solar transmittance before and after the test are tested. The test time is 1200h. The appearance is considered qualified if there is no obvious discoloration, bubbles, delamination or other significant defects. The difference in ultraviolet transmittance before and after the test is ≤1% and the difference in solar transmittance before and after the test is ≤3%.

[0105] II. Performance Test Results Table 1 As can be seen from Table 1: The functional composite of Example 1 is a cellulose aerogel with polyethyleneimine modified filler and loaded with ultraviolet absorber. The resulting automotive glass protective film has excellent ultraviolet blocking, heat insulation, explosion-proof and long service life. In Example 2, when the hexagonal flake magnesium hydroxide in the functional compound was replaced with ordinary magnesium hydroxide, the UV blocking and heat insulation properties of the resulting automotive glass protective film remained largely unchanged, but the explosion-proof properties and service life were significantly reduced. In Example 3, the polyethyleneimine modified filler in the functional compound was replaced with a silane coupling agent modified filler. The resulting automotive glass protective film showed little change in UV blocking and heat insulation properties, but its explosion-proof properties and service life were significantly reduced. In Example 4, the cellulose aerogel loaded with ultraviolet absorbers in the functional compound was replaced with cellulose aerogel. The explosion-proof properties and long service life of the resulting automotive glass protective film did not change much, but the ultraviolet blocking and heat insulation properties decreased significantly. In Example 5, the cellulose aerogel loaded with UV absorbers in the functional composite only loaded UV absorber A; in Example 6, the cellulose aerogel loaded with UV absorbers in the functional composite only loaded UV absorber B. The explosion-proof properties of the resulting automotive glass protective film did not change much, but the UV blocking properties, heat insulation properties, and service life decreased significantly.

[0106] The external test results of the explosion-proof properties of the automotive glass protective film of Example 1 are shown in Tables 2, 3 and 4 below.

[0107] Table 2 Table 3 Table 4 As can be seen from Table 4, the automotive glass protective film of Embodiment 1 of the present invention also has excellent temperature resistance.

[0108] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A car window protector, characterized in that, From top to bottom, it includes a functional layer, a first TPU film layer, a first adhesive layer, a substrate layer, a second adhesive layer, a second TPU film layer, and an mounting adhesive layer; The raw materials for the functional layer include waterborne polyurethane emulsion, functional compound, defoamer, and leveling agent; The functional composite comprises polyethyleneimine-modified filler and cellulose aerogel loaded with ultraviolet absorbers; The filler comprises hexagonal sheet magnesium hydroxide and nano-titanium dioxide.

2. The automotive glass protective film according to claim 1, characterized in that, The raw materials of the functional layer, by weight, include 80-100 parts of waterborne polyurethane emulsion, 10-25 parts of functional composite, 0.5-1.5 parts of defoamer, and 0.5-1.5 parts of leveling agent.

3. The automotive glass protective film according to claim 2, characterized in that, The mass ratio of the polyethyleneimine-modified filler to the cellulose aerogel loaded with ultraviolet absorbers is 5-15:5-10; the mass ratio of the hexagonal sheet magnesium hydroxide to nano titanium dioxide is 1-2:

1.

4. The automotive glass protective film according to claim 3, characterized in that, The preparation method of the polyethyleneimine modified filler includes the following steps: dissolving polyethyleneimine in ethanol, adding filler while stirring, continuing to stir, washing, and drying to obtain the filler.

5. The automotive glass protective film according to claim 4, characterized in that, The method for preparing the cellulose aerogel loaded with ultraviolet absorber includes the following steps: S1. Disperse bacterial cellulose in water to obtain a bacterial cellulose solution. Add organic ultraviolet absorber A to the bacterial cellulose solution and stir. After stirring, perform vacuum freeze-drying to obtain a cellulose aerogel intermediate. S2. Disperse the cellulose aerogel intermediate in ethanol, add vinyl silane coupling agent, organic ultraviolet absorber B and initiator, react, centrifuge, wash and dry after the reaction to obtain cellulose aerogel loaded with ultraviolet absorber.

6. The automotive glass protective film according to claim 5, characterized in that, The organic ultraviolet absorber A mentioned in step S1 is a benzotriazole ultraviolet absorber; the organic ultraviolet absorber B mentioned in step S2 is selected from at least one of 4-propenoxy-2-hydroxybenzophenone, 2-hydroxy-4-(methacryloyloxy)benzophenone and 2-hydroxy-4-acryloyloxyethoxybenzophenone.

7. The automotive glass protective film according to any one of claims 1-6, characterized in that, The automotive glass protective film also includes a protective film layer disposed on the functional layer, and / or a release layer disposed under the adhesive layer.

8. The automotive glass protective film according to claim 7, characterized in that, The protective film layer is a PET film or a silicone protective film; the release layer is a PET release film; the first adhesive layer and the second adhesive layer are each independently selected from either acrylic pressure-sensitive adhesive or polyurethane adhesive; the mounting adhesive layer is an acrylic pressure-sensitive adhesive.

9. The method for preparing the automotive glass protective film according to any one of claims 1-8, characterized in that, Includes the following steps: A first adhesive layer and a second adhesive layer are coated on the surface of the substrate layer, respectively. After drying, they are laminated to the first TPU film layer and the second TPU film layer on both sides, respectively. An installation adhesive layer is coated on the release surface of the release layer, and after drying, it is laminated to the second TPU film layer. A functional layer is coated on the first TPU film layer, and then laminated to the protective film layer to obtain the final product.

10. The application of the automotive glass protective film according to any one of claims 1-8 in the rear side window glass or sunroof glass of an automobile.

Images