Weather-resistant colorful window film material based on nanocomposite technology and preparation method thereof

Abstract

This invention discloses a weather-resistant, colorful window film material based on nanocomposite technology and its preparation method, relating to the technical field of window film preparation. By combining a PP release film layer, a polyurethane adhesive layer, a composite polyester film layer, and a polypropylene wear-resistant layer, the resulting window film material exhibits excellent infrared and heat insulation properties, UV resistance, and flexibility. This significantly reduces the frequency of air conditioning use, conserves energy, and avoids light pollution and safety hazards. The visible light transmittance can be adjusted as needed to meet the requirements of different applications.

Description

Technical Field

[0001] The present invention relates to the technical field of window film preparation, and in particular to a weather-resistant colorful window film material based on nanocomposite technology and a preparation method thereof. Background Art

[0002] With the rapid development of new energy vehicles and green buildings, energy-saving technologies have become a research priority. The range of new energy vehicles is limited by battery capacity, while a large portion of building energy consumption is used for air conditioning and cooling. Reducing energy consumption and improving energy efficiency have become key to technological development. In this context, the development of effective energy-saving materials, especially those that reduce heat transfer, is crucial for promoting the development of new energy vehicles and green buildings.

[0003] There are two main types of solar thermal insulation window films on the market: thermal absorbing films and monometallic films. Thermal absorbing films reduce the amount of heat entering a room by absorbing heat from sunlight, but this can cause the film's temperature to rise, leading to secondary heat radiation into the room. Monometallic films have a certain reflectivity in the infrared region, but their reflectivity is higher in the visible light region, causing light pollution. The heat absorption of thermal absorbing films causes the temperature to rise, posing a risk of spontaneous glass explosion and a threat to personal safety. While monometallic films offer some insulation, their high visible light reflectivity does not meet national regulations and contributes to light pollution.

[0004] Therefore, the present invention proposes a weather-resistant colorful window film material based on nano-composite technology and a preparation method thereof, which can effectively prevent most infrared light from entering the car or indoors, thereby reducing the frequency of air conditioning use, saving energy, and avoiding light pollution and safety hazards. Summary of the Invention

[0005] The object of the present invention is to provide a weather-resistant colorful window film material based on nanocomposite technology and a preparation method thereof, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a weather-resistant colorful window film material based on nano-composite technology is formed by the following structures from top to bottom: a PP release film layer, a polyurethane adhesive layer, a composite polyester film layer and a polypropylene wear-resistant layer.

[0007] Furthermore, the thickness of the PP release film layer is 0.01 mm to 0.03 mm;

[0008] The thickness of the polypropylene wear-resistant layer is 0.03mm~0.06mm;

[0009] The thickness of the polyurethane adhesive layer is 0.01 mm to 0.02 mm.

[0010] Furthermore, the composite polyester film layer is prepared by the following process:

[0011] The modified polyester masterbatch and the double-bond anti-infrared heat-insulating compound are blended, melted, extruded, cast, drawn, shaped, and cooled to form a composite polyester film layer.

[0012] Furthermore, the mass ratio of the modified polyester masterbatch to the double-bond-containing anti-infrared heat-insulating composite is (90-95): (5-10).

[0013] Furthermore, the melting temperature is 230°C to 270°C.

[0014] Furthermore, the thickness of the composite polyester film layer is 0.05 mm.

[0015] Furthermore, the preparation process of the modified polyester masterbatch is as follows:

[0016] PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and initiator are mixed, melted, extruded and granulated under the protection of nitrogen atmosphere to obtain modified polyester masterbatch.

[0017] Furthermore, the double bonds in the double-bond branched polyester and the double-bond-containing anti-infrared heat-insulating composite are carbon-carbon unsaturated double bonds.

[0018] Furthermore, the mass ratio of the PET masterbatch, the double-bond branched polyester, the double-bond-containing anti-infrared heat-insulating composite and the initiator is 10: (3-8): (0.5-1.5): (0.01-0.05).

[0019] Furthermore, the melting temperature is 270°C to 290°C.

[0020] Furthermore, the initiator is one or both of benzoyl peroxide and azobisisobutyronitrile.

[0021] Furthermore, the double-bond branched polyester is obtained by reacting a terminal hydroxyl hyperbranched polyester with a benzophenone derivative, and the specific process is as follows:

[0022] The terminal hydroxyl hyperbranched polyester is mixed with N,N-dimethylformamide, stirred, heated to 100°C~140°C, and then tetra-n-butylammonium bromide and benzophenone derivative are added, reacted for 2h~4h, cooled, adjusted to pH 8~10, reacted for 4h~6h, and vacuum distilled and centrifuged to obtain a double-bond branched polyester.

[0023] Furthermore, the mass ratio of the terminal hydroxyl hyperbranched polyester, N,N-dimethylformamide, tetra-n-butylammonium bromide, and benzophenone derivative is 1: (0.5-1.5): (0.01-0.05): (0.5-1.5).

[0024] Furthermore, the centrifugal process conditions are: rotation speed 1000r / min~3000r / min, time 1min~3min.

[0025] Furthermore, the terminal hydroxyl hyperbranched polyester is a mixture of one or more of H102, H101, and H103.

[0026] Furthermore, the benzophenone derivative contains an epoxy group and a double bond, and the specific preparation process is as follows:

[0027] S1: Mix polyethylene glycol diglycidyl ether and dichloromethane, heat the mixture to react, then add 2,4-dihydroxybenzophenone, stir the mixture to react, and evaporate under reduced pressure to obtain an epoxy-containing benzophenone derivative;

[0028] S2: Mix the epoxy-containing benzophenone derivative, tetrahydrofuran and triethylamine, stir evenly, then add acryloyl chloride, react at 0°C~10°C for 6h~8h, precipitate, filter and obtain the benzophenone derivative.

[0029] Furthermore, in S1, the mass ratio of polyethylene glycol diglycidyl ether, dichloromethane and 2,4-dihydroxybenzophenone is (1~2):(4~6):1.

[0030] Furthermore, in S1, the process conditions of the temperature-raising reaction are: temperature 65°C to 75°C, time 1h to 2h.

[0031] Furthermore, in S1, the stirring reaction process conditions are: temperature 65°C~75°C, time 3h~5h.

[0032] Furthermore, in S2, the ratio of epoxy benzophenone derivative, tetrahydrofuran, triethylamine and acryloyl chloride is 10 g: (20~40) mL: (5~7) mL: (4~6) mL.

[0033] Furthermore, the anti-infrared heat-insulating composite material containing double bonds is prepared by the following process:

[0034] Step 1, taking tin tetrachloride pentahydrate, antimony trichloride, and hydrochloric acid, mixing them, then adding cesium carbonate and a chelating agent, stirring them evenly to obtain a mixed solution, then adding ammonia water, precipitating, filtering, washing, grinding, and calcining to obtain antimony-cesium doped tin oxide;

[0035] Step 2: Mix vinyltriethoxysilane and ethanol aqueous solution, adjust the pH to 3-5, let it stand for 1 hour, add antimony-cesium doped tin oxide and nano-titanium dioxide, heat under reflux in a water bath, centrifuge, collect the precipitate, wash, and dry to obtain an anti-infrared heat-insulating composite containing a double bond.

[0036] Furthermore, in step 1, the mass ratio of tin tetrachloride pentahydrate, antimony trichloride, hydrochloric acid, cesium carbonate and chelating agent is 10: (4-12): (40-80): (0.01-0.1): (0.01-0.1);

[0037] The mass ratio of the mixed solution to ammonia water is 10:(0.01~0.05).

[0038] Furthermore, in step 1, the hydrochloric acid is added in the form of a solution with a concentration of 1.5 mol / L to 3.5 mol / L;

[0039] The concentration of the ammonia solution is 0.4 mol / L to 1.0 mol / L;

[0040] The chelating agent is a mixture of one or more of diethylenetriaminepentaacetic acid, tartaric acid, gluconic acid and ethylenediaminetetraacetic acid.

[0041] Furthermore, in step 1, the calcination process conditions are: temperature 400° C. to 800° C., and time 1 h to 3 h.

[0042] Furthermore, in step 2, the ratio of vinyltriethoxysilane, ethanol aqueous solution, antimony-cesium doped tin oxide and nano-titanium dioxide is (1-5) mg: (4-10) mL: (2-4) g: (0.5-1.5) mg.

[0043] Furthermore, in step 2, the process conditions for the water bath heating reflux reaction are: temperature 60°C~80°C, reflux time 3h~5h.

[0044] Furthermore, in step 2, the centrifugal process conditions are: rotation speed 8000r / min~10000r / min; time 10min~30min.

[0045] Furthermore, in step 2, the drying process conditions are: temperature 40°C to 60°C, and time 8h to 12h.

[0046] Furthermore, in step 2, the volume ratio of ethanol to water in the ethanol aqueous solution is 10:1.

[0047] Furthermore, a colorful metal layer is provided on the surface of the composite polyester film layer close to the polypropylene wear-resistant layer. The specific preparation method is as follows:

[0048] A composite polyester film layer is sputtered with indium tin oxide in an argon and oxygen atmosphere to form a colorful metal layer.

[0049] Furthermore, the gas flow rates of the argon and oxygen are 10 mL / s to 20 mL / s, and the flow ratio of the argon and oxygen is 1:1.

[0050] Furthermore, the sputtering method is vacuum ion sputtering, and the sputtering process conditions are: current 10A~20A, deflection voltage 100V~150V, temperature 100℃~160℃;

[0051] The thickness of the colorful metal layer is 20nm~60nm.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] 1. Tin oxide itself has the ability to absorb infrared light, but the carrier concentration is low and the absorption capacity is limited. Therefore, by doping with antimony and cesium, the carrier concentration is increased, thereby improving the absorption efficiency of infrared light. On the other hand, single tin oxide mainly absorbs infrared energy, causing the material to overheat, increasing the overall temperature of the window film and conducting secondary radiation into the room. Tin oxide doped with antimony and cesium can achieve a synergistic effect of absorbing and reflecting infrared light. Doped titanium dioxide can increase the specific surface area of ​​the anti-infrared heat-insulating composite, forming a porous skeleton, providing more infrared reflection sites, reducing heat conduction, and lowering the indoor temperature without affecting the visible light transmittance. Unsaturated double bonds are introduced into antimony-cesium doped tin oxide to obtain an anti-infrared heat-insulating composite containing double bonds.

[0054] The epoxy group of polyethylene glycol diglycidyl ether reacts with the 4-hydroxyl group of 2,4-dihydroxybenzophenone to obtain a benzophenone derivative containing an epoxy group. The 2-hydroxyl group of 2,4-dihydroxybenzophenone then reacts with the acyl chloride group of acryloyl chloride to obtain a benzophenone derivative containing both an epoxy group and a double bond. The epoxy group on the benzophenone derivative reacts with the hydroxyl group of a hydroxyl-terminated hyperbranched polyester to obtain a double-bond branched polyester. After a series of reactions, the molecular chain of the double-bond branched polyester contains benzophenone groups, double bonds, and polyethylene glycol flexible chain segments, giving it UV resistance and good flexibility. The double bonds can form a cross-linked structure with the double-bond anti-infrared heat-insulating composite, reducing precipitation, so that the obtained modified polyester masterbatch has UV resistance, infrared heat-insulating properties, and good flexibility.

[0055] Double-bond branched polyester can also undergo ester exchange reaction with PET during the melting process, reducing the regularity and crystallinity of the molecular chain, and further improving the impact resistance of the modified polyester masterbatch.

[0056] 2. A portion of the double-bond anti-infrared heat-insulating compound is first blended with PET and double-bond branched polyester to prepare a modified polyester masterbatch, and then co-extruded with the remaining double-bond anti-infrared heat-insulating compound. Compared with adding the anti-infrared heat-insulating compound at one time, the cross-linking density of the composite polyester film layer can be increased, the tensile strength of the film layer can be further improved, and the anti-infrared heat-insulating compound can be more evenly dispersed in the polyester network, thereby improving the anti-infrared and heat-insulating capabilities.

[0057] 3. Sputtering indium tin oxide on the composite PET film layer can form a gradient refraction structure and produce a colorful effect. Indium tin oxide has low reflectivity and good optical properties, which can avoid glare and improve driving safety.

[0058] 4. The weather-resistant colorful window film material obtained in the present invention can reduce the frequency of air conditioning use, save energy, avoid light pollution and safety hazards, comply with national regulations, and can adjust the visible light transmittance according to needs to meet the use requirements of different occasions. DETAILED DESCRIPTION

[0059] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0060] In the following specific embodiments,

[0061] PET masterbatch, model number XB-PET01DM;

[0062] The initiator is azobisisobutyronitrile;

[0063] Hydroxyl-terminated hyperbranched polyester, model H102;

[0064] The chelating agent is ethylenediaminetetraacetic acid;

[0065] Nano-titanium dioxide, particle size 5nm;

[0066] Indium tin oxide, 99.95% purity;

[0067] PP release film layer, thickness 0.03mm, raw materials from Dongguan Huibai Plastic Raw Materials Co., Ltd.

[0068] Polypropylene wear-resistant layer, thickness 0.06mm, raw materials from Suzhou Guanyawang Electronic Materials Co., Ltd.

[0069] Polyurethane, model number JD-7810;

[0070] Tin dioxide, particle size 50 nm;

[0071] Glass substrate, thickness 20mm, length 0.7m, width 0.5m;

[0072] Prepare ethanol-water solution: mix ethanol and water in a volume ratio of 10:1 to obtain ethanol-water solution.

[0073] Example 1: A method for preparing a weather-resistant colorful window film material based on nanocomposite technology, comprising the following steps:

[0074] (1) Preparation of anti-infrared heat-insulating composites containing double bonds:

[0075] Step 1: Mix tin tetrachloride pentahydrate with antimony trichloride and hydrochloric acid solution, stir evenly, then add cesium carbonate and ethylenediaminetetraacetic acid, stir evenly to obtain a mixed solution, then add ammonia water, precipitate, filter, wash, grind, and calcine to obtain antimony-cesium doped tin oxide. Step 2: Mix vinyltriethoxysilane and ethanol aqueous solution, adjust the pH to 5, let stand for 1 hour, add antimony-cesium doped tin oxide and nano-titanium dioxide, heat under reflux in a water bath, centrifuge, collect the precipitate, wash, and dry to obtain a double-bond anti-infrared heat-insulating composite. In step 1, the mass ratio of tin tetrachloride pentahydrate, antimony trichloride, hydrochloric acid solution, cesium carbonate, and ethylenediaminetetraacetic acid is 10:12:80:0.1:0. 1; the mass ratio of the mixed solution to ammonia water is 10:0.05; the concentration of the hydrochloric acid solution is 3.5 mol / L; the concentration of the ammonia water is 1.0 mol / L; in step 1, the process conditions for calcination are: temperature 800°C, time 3 hours; in step 2, the ratio of vinyltriethoxysilane, ethanol aqueous solution, antimony-cesium-doped tin oxide and nano-titanium dioxide is 5 mg:10 mL:4 g:1.5 mg; in step 2, the process conditions for water bath heating reflux reaction are: temperature 80°C, reflux time 5 hours; in step 2, the process conditions for centrifugation are: speed 10000 r / min, time 30 minutes; in step 2, the process conditions for drying are: temperature 60°C, time 12 hours;

[0076] (2) Preparation of double bond branched polyester:

[0077] S1: Mix polyethylene glycol diglycidyl ether and dichloromethane, heat to 75°C and react for 2 hours, then add 2,4-dihydroxybenzophenone, stir and react, and evaporate under reduced pressure to obtain an epoxy-containing benzophenone derivative; S2: Mix the epoxy-containing benzophenone derivative, tetrahydrofuran and triethylamine, stir evenly, then add acryloyl chloride, react at 0°C for 6 hours, precipitate, and filter to obtain a benzophenone derivative; in S1, the mass ratio of polyethylene glycol diglycidyl ether, dichloromethane and 2,4-dihydroxybenzophenone is 2:6:1; in S1, the process conditions for the stirring reaction are: temperature 75°C, time 5 hours; in S2, the ratio of the epoxy-containing benzophenone derivative, tetrahydrofuran, triethylamine and acryloyl chloride is 10g:40mL:7mL:6mL;

[0078] The terminal hydroxyl hyperbranched polyester H102 was mixed with N,N-dimethylformamide, stirred, heated to 140°C, and then tetra-n-butylammonium bromide and a benzophenone derivative were added, reacted for 4 hours, cooled, adjusted to a pH of 10, reacted for 6 hours, and distilled under reduced pressure and centrifuged at 3000 r / min for 3 minutes to obtain a double-bond branched polyester; the mass ratio of the terminal hydroxyl hyperbranched polyester H102, N,N-dimethylformamide, tetra-n-butylammonium bromide, and the benzophenone derivative was 1:1.5:0.05:1.5;

[0079] (3) Preparation of modified polyester masterbatch:

[0080] PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile were mixed, melted, extruded and granulated at 290°C under nitrogen atmosphere to obtain modified polyester masterbatch; the mass ratio of PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile was 10:8:1.5:0.05;

[0081] (4) Preparation of weather-resistant colorful window film materials:

[0082] The modified polyester masterbatch and the double-bond anti-infrared heat-insulating compound are blended in a mass ratio of 95:5, heated to 270°C for melting, extruded, cast, drawn, shaped, and cooled to form a composite polyester film layer with a thickness of 0.05 mm;

[0083] Polyurethane was coated on the side of the composite polyester film layer near the PP release film layer and dried to form a 0.02mm thick polyurethane adhesive layer. Indium tin oxide was sputtered on the side of the composite polyester film layer near the polypropylene wear-resistant layer in an argon and oxygen atmosphere to form a 60nm thick colorful metal layer. The argon and oxygen gas flow rates were 20mL / s, and the argon to oxygen flow ratio was 1:1. The sputtering process conditions were: current 20A, deflection voltage 150V, and temperature 160°C.

[0084] The PP release film layer, polyurethane adhesive layer, composite polyester film layer, colorful metal layer and polypropylene wear-resistant layer are stacked from top to bottom and hot rolled to obtain a weather-resistant colorful window film material; the hot rolling process conditions are: temperature 200°C, time 3.5s, roller speed 100m / s.

[0085] Example 2: A method for preparing a weather-resistant colorful window film material based on nanocomposite technology, comprising the following steps:

[0086] (1) Preparation of anti-infrared heat-insulating composites containing double bonds:

[0087] Step 1: Mix tin tetrachloride pentahydrate with antimony trichloride and hydrochloric acid solution, stir evenly, then add cesium carbonate and ethylenediaminetetraacetic acid, stir evenly to obtain a mixed solution, then add ammonia water, precipitate, filter, wash, grind, and calcine to obtain antimony-cesium doped tin oxide; Step 2: Mix vinyltriethoxysilane and ethanol aqueous solution, adjust the pH to 4, let stand for 1 hour, add antimony-cesium doped tin oxide and nano-titanium dioxide, heat in a water bath and reflux reaction, centrifuge, collect precipitate, wash, and dry to obtain a double-bond anti-infrared heat-insulating composite; in step 1, the mass ratio of tin tetrachloride pentahydrate, antimony trichloride, hydrochloric acid solution, cesium carbonate and ethylenediaminetetraacetic acid is 10:8:60:0.05:0 .05; the mass ratio of the mixed solution to ammonia water is 10:0.03; the concentration of the hydrochloric acid solution is 2.5 mol / L; the concentration of the ammonia water is 0.7 mol / L; in step 1, the process conditions for calcination are: temperature 600°C, time 2h; in step 2, the ratio of vinyltriethoxysilane, ethanol aqueous solution, antimony-cesium doped tin oxide and nano-titanium dioxide is 3mg:7mL:3g:1.0mg; in step 2, the process conditions for water bath heating reflux reaction are: temperature 70°C, reflux time 4h; in step 2, the process conditions for centrifugation are: speed 9000r / min; time 20min; in step 2, the process conditions for drying are: temperature 50°C, time 10h;

[0088] (2) Preparation of double bond branched polyester:

[0089] S1: Mix polyethylene glycol diglycidyl ether and dichloromethane, heat to 70°C and react for 1.5 hours, then add 2,4-dihydroxybenzophenone, stir and react, and evaporate under reduced pressure to obtain an epoxy-containing benzophenone derivative; S2: Mix the epoxy-containing benzophenone derivative, tetrahydrofuran and triethylamine, stir evenly, then add acryloyl chloride, react at 5°C for 7 hours, precipitate, and filter to obtain a benzophenone derivative; in S1, the mass ratio of polyethylene glycol diglycidyl ether, dichloromethane and 2,4-dihydroxybenzophenone is 1:5:1; in S1, the stirring reaction process conditions are: temperature 70°C, time 4 hours; in S2, the ratio of epoxy-containing benzophenone derivative, tetrahydrofuran, triethylamine and acryloyl chloride is 10g:30mL:6mL:5mL;

[0090] The terminal hydroxyl hyperbranched polyester H102 was mixed with N,N-dimethylformamide, stirred, heated to 120°C, and then tetra-n-butylammonium bromide and a benzophenone derivative were added, reacted for 3 hours, cooled, adjusted to pH 9, reacted for 5 hours, and distilled under reduced pressure and centrifuged at 2000 r / min for 2 minutes to obtain a double-bond branched polyester; the mass ratio of the terminal hydroxyl hyperbranched polyester H102, N,N-dimethylformamide, tetra-n-butylammonium bromide, and the benzophenone derivative was 1:1.0:0.03:1.0;

[0091] (3) Preparation of modified polyester masterbatch:

[0092] PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile were mixed, melted, extruded and granulated at 280°C under nitrogen atmosphere to obtain modified polyester masterbatch; the mass ratio of PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile was 10:5:1.0:0.03;

[0093] (4) Preparation of weather-resistant colorful window film materials:

[0094] The modified polyester masterbatch and the double-bond anti-infrared heat-insulating compound are blended in a mass ratio of 93:7, heated to 250°C for melting, extruded, cast, drawn, shaped, and cooled to form a composite polyester film layer with a thickness of 0.05 mm;

[0095] Polyurethane was coated on the side of the composite polyester film layer near the PP release film layer and dried to form a polyurethane adhesive layer with a thickness of 0.02 mm. In an argon and oxygen atmosphere, indium tin oxide was sputtered on the side of the composite polyester film layer near the polypropylene wear-resistant layer to form a colorful metallic layer with a thickness of 40 nm. The gas flow rate of argon and oxygen was 15 mL / s, and the flow ratio of argon to oxygen was 1:1. The sputtering process conditions were: current 15 A, deflection voltage 130 V, and temperature 130°C.

[0096] The PP release film layer, polyurethane adhesive layer, composite polyester film layer, colorful metal layer and polypropylene wear-resistant layer are stacked from top to bottom and hot-rolled to obtain a weather-resistant colorful window film material; the hot-rolling process conditions are: temperature 190°C, time 2.5s, and roller speed 90m / s.

[0097] Example 3: A method for preparing a weather-resistant colorful window film material based on nanocomposite technology, comprising the following steps:

[0098] (1) Preparation of anti-infrared heat-insulating composites containing double bonds:

[0099] Step 1: Mix tin tetrachloride pentahydrate with antimony trichloride and hydrochloric acid solution, stir evenly, then add cesium carbonate and ethylenediaminetetraacetic acid, stir evenly to obtain a mixed solution, then add ammonia water, precipitate, filter, wash, grind, and calcine to obtain antimony-cesium doped tin oxide; Step 2: Mix vinyltriethoxysilane and ethanol aqueous solution, adjust the pH to 3, let stand for 1 hour, add antimony-cesium doped tin oxide and nano-titanium dioxide, heat in a water bath and reflux reaction, centrifuge, collect precipitate, wash, and dry to obtain a double-bond anti-infrared heat-insulating composite; in step 1, the mass ratio of tin tetrachloride pentahydrate, antimony trichloride, hydrochloric acid solution, cesium carbonate and ethylenediaminetetraacetic acid is 10:4:40:0.01:0 .01; the mass ratio of the mixed solution to ammonia water is 10:0.01; the concentration of the hydrochloric acid solution is 1.5 mol / L; the concentration of the ammonia water is 0.4 mol / L; in step 1, the process conditions for calcination are: temperature 400°C, time 1h; in step 2, the ratio of vinyltriethoxysilane, ethanol aqueous solution, antimony-cesium doped tin oxide and nano-titanium dioxide is 1mg:4mL:2g:0.5mg; in step 2, the process conditions for water bath heating reflux reaction are: temperature 60°C, reflux time 3h; in step 2, the process conditions for centrifugation are: speed 8000r / min; time 10min; in step 2, the process conditions for drying are: temperature 40°C, time 8h;

[0100] (2) Preparation of double bond branched polyester:

[0101] S1: Mix polyethylene glycol diglycidyl ether and dichloromethane, heat to 65°C and react for 1 hour, then add 2,4-dihydroxybenzophenone, stir and react, and evaporate under reduced pressure to obtain an epoxy-containing benzophenone derivative; S2: Mix the epoxy-containing benzophenone derivative, tetrahydrofuran and triethylamine, stir evenly, then add acryloyl chloride, react at 10°C for 6 hours, precipitate, and filter to obtain a benzophenone derivative; in S1, the mass ratio of polyethylene glycol diglycidyl ether, dichloromethane and 2,4-dihydroxybenzophenone is 1:4:1; in S1, the stirring reaction process conditions are: temperature 65°C, time 3 hours; in S2, the ratio of epoxy-containing benzophenone derivative, tetrahydrofuran, triethylamine and acryloyl chloride is 10g:20mL:5mL:4mL;

[0102] The terminal hydroxyl hyperbranched polyester H102 was mixed with N,N-dimethylformamide, stirred, heated to 100°C, and then tetra-n-butylammonium bromide and a benzophenone derivative were added, reacted for 2 hours, cooled, adjusted to pH 8, reacted for 4 hours, and distilled under reduced pressure and centrifuged at 1000 r / min for 1 minute to obtain a double-bond branched polyester; the mass ratio of the terminal hydroxyl hyperbranched polyester H102, N,N-dimethylformamide, tetra-n-butylammonium bromide, and the benzophenone derivative was 1:0.5:0.01:0.5;

[0103] (3) Preparation of modified polyester masterbatch:

[0104] PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile were mixed, melted, extruded and granulated at 270°C under nitrogen atmosphere to obtain modified polyester masterbatch; the mass ratio of PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and azobisisobutyronitrile was 10:3:0.5:0.01;

[0105] (4) Preparation of weather-resistant colorful window film materials:

[0106] The modified polyester masterbatch and the double-bond anti-infrared heat-insulating compound are blended in a mass ratio of 90:10, heated to 230°C for melting, extruded, cast, drawn, shaped, and cooled to form a composite polyester film layer with a thickness of 0.05 mm;

[0107] Polyurethane was coated on the side of the composite polyester film layer near the PP release film layer and dried to form a polyurethane adhesive layer with a thickness of 0.01 mm. In an argon and oxygen atmosphere, indium tin oxide was sputtered on the side of the composite polyester film layer near the polypropylene wear-resistant layer to form a colorful metal layer with a thickness of 20 nm. The gas flow rate of argon and oxygen was 10 mL / s, and the flow ratio of argon to oxygen was 1:1. The sputtering process conditions were: current 10 A, deflection voltage 100 V, and temperature 100°C.

[0108] The PP release film layer, polyurethane adhesive layer, composite polyester film layer, colorful metal layer and polypropylene wear-resistant layer are stacked from top to bottom and hot-rolled to obtain a weather-resistant colorful window film material; the hot rolling process conditions are: temperature 180°C, time 1.5s, and roller speed 80m / s.

[0109] Comparative Example 1: Using Example 1 as a comparison, no double bond was introduced into the anti-infrared heat-insulating composite, and other conditions remained unchanged.

[0110] Comparative Example 2: Using Example 1 as a comparison, the benzophenone derivative was replaced with 2,4-dihydroxybenzophenone, and the other conditions remained unchanged.

[0111] Comparative Example 3: Using Example 1 as a comparison, the double-bond-containing anti-infrared heat-insulating composite was blended and extruded with the PET masterbatch and the double-bond branched polyester at one time without preparing the modified polyester masterbatch in batches. Other conditions remained unchanged.

[0112] Comparative Example 4: Taking Example 1 as a comparison, no double bond is introduced into the anti-infrared heat-insulating composite, and the benzophenone derivative is replaced with 2,4-dihydroxybenzophenone, while other conditions remain unchanged.

[0113] Experiment: The weather-resistant colorful window film materials obtained in the examples and comparative examples were tested for various properties;

[0114] Infrared blocking rate, ultraviolet blocking rate, and visible light transmittance: Refer to GB / T 2680-2021 to test the infrared blocking rate, ultraviolet blocking rate, and visible light transmittance of window film materials;

[0115] Tensile strength: Refer to GB / T 1040.3-2006, and test window film materials that have not been exposed to UV and IR radiation, and those that have been exposed to IR radiation;

[0116] According to ISO 4892-3-2016, the window film material was subjected to ultraviolet accelerated aging test. The test conditions are: light source: UVA-340, radiation energy: 0.8W / (m 2 nm), temperature: 65℃, light on for 5 hours, turn off the light source for 1 hour, and cycle test 10 times.

[0117] Table 1 Test results of infrared and ultraviolet blocking rates of weather-resistant colorful window film materials

[0118]

[0119] Table 2 Weather resistance test results of colorful window film materials

[0120]

[0121] Based on the data in the above table, we can draw the following conclusions:

[0122] Compared with Example 1, in Comparative Example 1, no double bond was introduced into the anti-infrared heat-insulating composite, and the infrared blocking rate of the window film material decreased. The reason is that the anti-infrared heat-insulating composite cannot be cross-linked with the double-bond branched polyester, resulting in uneven distribution and reduced infrared blocking rate.

[0123] Compared with Example 1, Comparative Example 2 replaces the benzophenone derivative with 2,4-dihydroxybenzophenone. The UV blocking rate and tensile strength of the window film material decrease. The reason is that the benzophenone derivative contains epoxy groups, double bonds and polyethylene glycol flexible chain segments. The epoxy groups react with the hydroxyl groups of the terminal hydroxyl hyperbranched polyester. The double bonds can form a cross-linked structure with the double-bond-containing anti-infrared heat-insulating composite. The polyethylene glycol gives the material good flexibility.

[0124] Compared with Example 1, in Comparative Example 3, the anti-infrared and heat-insulating composite containing double bonds was co-blended with PET masterbatch and double-bond branched polyester at one time and extruded. The various properties of the window film material were reduced. The reason is that the anti-infrared and heat-insulating composite was added in batches, compared with adding the anti-infrared and heat-insulating composite all at once, which can increase the cross-linking density of the composite polyester film layer, further improve the tensile strength of the film layer, and also make the anti-infrared and heat-insulating composite more evenly dispersed in the polyester network, thereby improving the anti-infrared and heat-insulating capabilities.

[0125] Compared with Example 1, Comparative Example 4 neither introduces a double bond into the anti-infrared heat-insulating composite nor replaces the benzophenone derivative with 2,4-dihydroxybenzophenone, and the performance of the window film material is reduced.

[0126] In summary, it is shown that the setting of materials and process conditions in the present invention can promote the comprehensive improvement of the ultraviolet and infrared blocking rates and weather resistance of the obtained window film material.

[0127] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A method for preparing a weather-resistant colorful window film material based on nanocomposite technology, characterized in that: From top to bottom, it is composed of the following structures: PP release film layer, polyurethane adhesive layer, composite polyester film layer and polypropylene wear-resistant layer; The composite polyester film layer is prepared by the following process: The modified polyester masterbatch and the double-bond anti-infrared heat-insulating compound are blended, melted, extruded, cast, drawn, shaped, and cooled to form a composite polyester film layer; The preparation process of the modified polyester masterbatch is as follows: The PET masterbatch, double-bond branched polyester, double-bond anti-infrared heat-insulating compound and initiator are mixed, melted, extruded and granulated under nitrogen atmosphere to obtain modified polyester masterbatch; The double-bond branched polyester is obtained by reacting a terminal hydroxyl hyperbranched polyester with a benzophenone derivative, and the specific process is as follows: The hydroxyl-terminated hyperbranched polyester is mixed with N,N-dimethylformamide, stirred, heated to 100°C-140°C, and then tetra-n-butylammonium bromide and a benzophenone derivative are added, reacted for 2h-4h, cooled, adjusted to a pH of 8-10, reacted for 4h-6h, and vacuum distilled and centrifuged to obtain a double-bond branched polyester; The benzophenone derivative contains an epoxy group and a double bond, and the specific preparation process is as follows: S1: Mix polyethylene glycol diglycidyl ether and dichloromethane, heat the mixture, add 2,4-dihydroxybenzophenone, stir the mixture, and evaporate under reduced pressure to obtain an epoxy-containing benzophenone derivative; S2: Mixing an epoxy group-containing benzophenone derivative, tetrahydrofuran, and triethylamine, stirring evenly, adding acryloyl chloride, reacting at low temperature, precipitating, and filtering to obtain a benzophenone derivative; The double-bond anti-infrared heat-insulating composite is prepared by the following process: Step 1, taking tin tetrachloride pentahydrate, antimony trichloride, and hydrochloric acid, mixing them, then adding cesium carbonate and a chelating agent, stirring them evenly to obtain a mixed solution, then adding ammonia water, precipitating, filtering, washing, grinding, and calcining to obtain antimony-cesium doped tin oxide; Step 2: vinyl triethoxysilane and ethanol aqueous solution are mixed, the pH is adjusted to 3-5, and the mixture is allowed to stand for 1 hour. Antimony-cesium doped tin oxide and nano-titanium dioxide are added, and the mixture is heated in a water bath for reflux reaction, centrifuged, and the precipitate is collected, washed, and dried to obtain an infrared-resistant heat-insulating composite containing a double bond; The composite polyester film layer is provided with a colorful metal layer on the side close to the polypropylene wear-resistant layer. The specific preparation method is as follows: A composite polyester film layer is sputtered with indium tin oxide in an argon and oxygen atmosphere to form a colorful metal layer.

2. The method for preparing a weather-resistant colorful window film material based on nanocomposite technology according to claim 1, characterized in that: The mass ratio of the modified polyester masterbatch to the double-bond-containing anti-infrared heat-insulating composite is (90-95): (5-10).

3. The method for preparing a weather-resistant colorful window film material based on nanocomposite technology according to claim 1, characterized in that: The mass ratio of the PET masterbatch, the double-bond branched polyester, the double-bond-containing anti-infrared heat-insulating composite and the initiator is 10: (3-8): (0.5-1.5): (0.01-0.05).

4. The method for preparing a weather-resistant colorful window film material based on nanocomposite technology according to claim 1, characterized in that: The mass ratio of the terminal hydroxyl hyperbranched polyester, N,N-dimethylformamide, tetra-n-butylammonium bromide and benzophenone derivative is 1: (0.5-1.5): (0.01-0.05): (0.5-1.5).

5. Weather-resistant colorful window film material based on nanocomposite technology, characterized by: Obtained according to the preparation method according to any one of claims 1 to 4.

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