Rare earth heat shield automotive window film

Abstract

The application discloses a rare earth heat-insulating automobile window film and relates to the technical field of films.The prepared rare earth heat-insulating automobile window film is composed of a hardening layer, a magnetron sputtering film layer, a base material layer, a mounting adhesive layer and a release film layer in sequence and is integrated; the hardening layer is obtained by coating modified polyurethane on the magnetron sputtering film layer and solidifying; the modified polyurethane is obtained by mixing polyurethane prepolymer, modified lanthanum hexaboride and phosphorus-containing silane crosslinking agent; and the prepared rare earth heat-insulating automobile window film has good heat insulation, weather resistance and flame retardance.

Description

Technical Field

[0001] This invention relates to the field of membrane technology, specifically to a rare earth heat-insulating automotive window film. Background Technology

[0002] The production of automotive window films is mainly achieved through the composite of multiple functional materials. A typical structure includes a polyester film substrate layer, an adhesive layer, a metal or ceramic functional layer, and a scratch-resistant coating. Traditional heat insulation films rely on magnetron sputtering to deposit metal (such as silver or aluminum) or metal oxide (such as indium tin oxide) films, utilizing their reflection of infrared rays in the solar spectrum to block heat.

[0003] However, the metal layer is prone to oxidation, leading to performance degradation. While metal oxides are more stable than pure metals, they have inherent drawbacks such as insufficient infrared absorption and difficulty in balancing visible light transmittance and heat insulation efficiency. In particular, metal oxide films develop microcracks, optical distortion, and color drift under long-term ultraviolet radiation and humid conditions, and their insufficient weather resistance significantly shortens their service life. Furthermore, existing window films generally lack functional extensions. With increasing demands for driver and passenger health, ordinary films cannot inhibit bacterial growth on the window surface, and the flammable nature of polymer substrates poses safety hazards.

[0004] Against this backdrop, the introduction of rare earth elements has become a key technological breakthrough. Rare earth elements possess unique electronic transition energy levels, enabling them to efficiently absorb near-infrared heat energy in the 780-2500nm range while maintaining high visible light transmittance. Their atomic structure stability far exceeds that of conventional metal oxides. To meet the growing demand for functionalization, modern high-performance window film designs can incorporate additional functionality into their composite structures. For example, antibacterial needles can inhibit bacterial growth on window surfaces, achieving hygiene protection; and in terms of flame retardancy, imparting flame-retardant properties enhances driving safety. Summary of the Invention

[0005] The purpose of this invention is to provide a rare earth heat-insulating automotive window film to solve the problems existing in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A rare earth heat-insulating automotive window film is composed of a hardening layer, a magnetron sputtering film layer, a substrate layer, an installation adhesive layer, and a release film layer in sequence.

[0008] The hardened layer is obtained by coating a modified polyurethane onto a magnetron sputtered film and curing it.

[0009] The modified polyurethane is prepared as follows:

[0010] (1) The aldehyde monomer is obtained by reacting cyanuric chloride and 5-aldehyde-2-thiophene boric acid;

[0011] (2) The amino monomer precursor was obtained by reacting bis(4-aminophenyl)acetylene with diisopropyl sulfide xanthate; the amino monomer precursor was obtained by reacting nickel chloride hexahydrate with nickel chloride hexahydrate.

[0012] (3) Pretreated lanthanum hexaboride, aldehyde monomer, and amino monomer were reacted to obtain modified lanthanum hexaboride;

[0013] (4) Polycarbonate diol, isophorone diisocyanate and 1-allyl-1H-1,2,4-triazole-3-amine were reacted to obtain polyurethane prepolymer;

[0014] (5) Tris(hydroxymethyl)aminomethane hydrochloride and trichlorosilane are reacted to obtain aminosilane; aminosilane and phosphorus oxychloride are reacted to obtain phosphorus-containing silane crosslinking agent;

[0015] (6) The modified polyurethane is obtained by mixing polyurethane prepolymer, modified lanthanum hexaboride and phosphorus-containing silane crosslinking agent.

[0016] As an optimization, the preparation method of the aldehyde monomer in step (1) is as follows: cyanuric chloride and 5-aldehyde-2-thiophene boric acid are dissolved in 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride are added, and the mixture is heated to 70-80℃ and reacted for 6-8h to obtain the aldehyde monomer; the molar ratio of cyanuric chloride and 5-aldehyde-2-thiophene boric acid is 1:(3.1-3.2); the mass ratio of cyanuric chloride, 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride is 1:(5-6):(1.7-2.0):(0.04-0.06).

[0017] As an optimization, diisopropyl xanthate sulfide and m-xylene are mixed and heated to 120-130℃ for 20-24 h to obtain an amino monomer precursor; the molar ratio of bis(4-aminophenyl)acetylene, azobisisobutyronitrile, and diisopropyl xanthate sulfide is 1:(0.4-0.5):(1.1-1.2); the mass of m-xylene is 20-30 times that of bis(4-aminophenyl)acetylene; the amino monomer precursor is dissolved in tetrahydrofuran / water solution; tetramethylammonium hydroxide-methanol solution is added, and the mixture is stirred at room temperature for 3 hours. After 0-40 min, nickel chloride hexahydrate was added, and stirring was continued at room temperature for 10-12 h. Then iodine was added and stirred for 10-12 h to obtain the amino monomer. The molar ratio of the amino monomer precursor, tetramethylammonium hydroxide, nickel chloride hexahydrate, and iodine was 1:(2-2.5):(0.5-0.6):(0.5-0.6). The mass of tetrahydrofuran / water solution was 15-20 times that of the amino monomer precursor. The tetramethylammonium hydroxide-methanol solution was obtained by mixing tetramethylammonium hydroxide and methanol at a mass ratio of 1:(5-6).

[0018] As an optimization, the preparation method of the modified lanthanum hexaboride in step (3) is as follows: Lanthanum hexaboride is uniformly dispersed in ethanol / water solution, 3-aminopropyltrimethoxysilane is added, the pH of the solution is adjusted to 5-6 with dilute sulfuric acid, and the temperature is raised to 70-80℃ for 5-6 h to obtain pretreated lanthanum hexaboride; the mass ratio of lanthanum hexaboride, 3-aminopropyltrimethoxysilane and ethanol / water solution is 1:(0.3-0.5):(20-30); the pretreated lanthanum hexaboride, N,N-dimethylacetamide and acetic acid are ultrasonically mixed, aldehyde monomer and amino monomer are added, and the temperature is raised to 90-100℃ for 72 h to obtain modified lanthanum hexaboride; the mass ratio of pretreated lanthanum hexaboride, N,N-dimethylacetamide, acetic acid, aldehyde monomer and amino monomer is 1:(20-30):(10-12):(0.3-0.5):(0.2-0.3).

[0019] As an optimization, the preparation method of the polyurethane prepolymer in step (4) is as follows: polycarbonate diol and n-butyl acetate are mixed, isophorone diisocyanate and dibutyltin dilaurate are added at 50°C, the reaction is carried out for 3-4 hours, the temperature is raised to 65-75°C, 1-allyl-1H-1,2,4-triazole-3-amine is added and the reaction is continued for 3-4 hours to obtain the polyurethane prepolymer; the mass ratio of polycarbonate diol, n-butyl acetate, isophorone diisocyanate, dibutyltin dilaurate and 1-allyl-1H-1,2,4-triazole-3-amine is 1:(30-40):(0.8-1.0):(0.001-0.002):(0.4-0.6).

[0020] As an optimization, the preparation method of the phosphorus-containing silane crosslinking agent in step (5) is as follows: Tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and trichlorosilane are mixed in a molar ratio of 1:(1.1-1.3):(1.3-1.5), dissolved in 1,4-dioxane at 10-12 times the mass of tris(hydroxymethyl)aminomethane hydrochloride, and the mixture is heated to 70-80℃ and reacted for 6-8 hours to obtain aminosilane; aminosilane, triethylamine, and phosphorus oxychloride are mixed in a molar ratio of (3.1-3.2):(3.3-3.5):1, dissolved in diethanol dimethyl ether at 10-12 times the mass of aminosilane, and the mixture is heated to 95-105℃ and reacted for 5-6 hours to obtain the phosphorus-containing silane crosslinking agent.

[0021] As an optimization, the preparation method of the modified polyurethane in step (6) is as follows: the polyurethane prepolymer, modified lanthanum hexaboride, phosphorus-containing silane crosslinking agent, caster catalyst, and toluene are mixed in a mass ratio of 1:(0.2-0.3):(0.2-0.3):(0.005-0.01):(4-5) to obtain the modified polyurethane.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] The rare earth heat-insulating automotive window film prepared by this invention comprises a hardening layer, a magnetron sputtering film layer, a substrate layer, an adhesive layer, and a release film layer integrally formed; the hardening layer is obtained by coating modified polyurethane onto the magnetron sputtering film layer and curing it.

[0024] In the preparation of modified polyurethane, firstly, cyanuric chloride and 5-aldehyde-2-thiophene boric acid are used to prepare aldehyde monomers containing triazine, thiophene, and aldehyde groups through a Suzuki coupling reaction. Then, ligands containing thiodiene are prepared using bis(4-aminophenyl)acetylene and diisopropyl sulfide xanthate as raw materials and complexed with nickel to obtain tetraaldehyde monomers. Rare earth nanoparticles treated with aminosilane coupling agent have abundant amino groups on their surface. The aldehyde monomers and amino monomers are converted into conjugated polymers on the surface of lanthanum hexaboride through a Schiff base reaction.

[0025] The preparation process of the amino monomer is illustrated below:

[0026]

[0027] Nickel-coordinated thiodiene structures exhibit characteristic absorption of near-infrared light. Introducing this structure into the polymer backbone via small-molecule polymerization can endow the polymer with excellent near-infrared absorption properties. Furthermore, the triazine group, as a strong electron-withdrawing group, and the thiophene group, as an electron-rich group, are connected via π-bridges. During polymer formation, these connections can further broaden the absorption spectral range and enhance the absorption intensity of the nickel-coordinated thiodiene structure, thereby further improving the infrared blocking performance of the material.

[0028] Secondly, tris(hydroxymethyl)aminomethane hydrochloride and trichlorosilane are reacted to generate stable tricage-like aminosilane; aminosilane and phosphorus oxychloride are linked by phosphoramide bonds to generate a crosslinking agent with three flame retardant elements: silicon, nitrogen, and phosphorus. The agent has a high content of effective flame retardant elements, and when applied to materials, it can effectively exert the synergistic flame retardant effect of each element, thereby reducing the amount of flame retardant used and improving the flame retardant effect.

[0029] Finally, diols and diisocyanates were polymerized and end-capped with 1-allyl-1H-1,2,4-triazole-3-amine to prepare polyurethane oligomers with terminal allyl triazole groups. In addition to acting as an end-capping agent, the triazole structure contained in 1-allyl-1H-1,2,4-triazole-3-amine can endow polyurethane with certain antibacterial properties. The polyurethane prepolymer, modified lanthanum hexaboride, and phosphorus-containing silane crosslinking agent were mixed and coated onto a magnetron sputtering film and cured to obtain a hardened layer. In the presence of a Castiglione catalyst, the ternary silane structure on the crosslinking agent and the terminal allyl groups of the polyurethane undergo hydrosilylation to initiate crosslinking and generate a network structure for curing.

[0030] The thiophene group, triazine group, and Schiff base functional group formed on the surface of lanthanum hexaboride, the triazole group on polyurethane, and the amide functional group in the crosslinking agent can all efficiently complex metal ions, forming a metal passivation layer on the magnetron sputtering film, blocking the corrosion of the magnetron sputtering film by the humid and hot environment, and extending the service life of the magnetron sputtering film. Attached Figure Description

[0031] The accompanying drawings are intended only to illustrate and explain the present invention and do not limit the scope of the invention.

[0032] Figure 1 The diagram shown is a structural schematic of a rare-earth heat-insulating automotive window film according to a specific embodiment of the present invention.

[0033] The components are, in sequence, a hardening layer (1), a magnetron sputtering film layer (2), a substrate layer (3), an adhesive layer (4), and a release film layer (5), which are combined into one unit. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] The polycarbonate diols described in the following examples and comparative examples have a molecular weight of 1000; the magnetron sputtering film is model SS35, purchased from Kangdexin; the substrate layer is a polyester film, model Toray U48, with a thickness of 23 μm; the mounting adhesive layer is an acrylic adhesive, model SAA1451, with a curing agent of SAC11, purchased from Xi'an Aerospace Sanwo Chemical Co., Ltd., with a thickness of 7 μm; the release film layer is a single-sided release film, a polyester film, with a thickness of 23 μm, purchased from Suzhou Longjian New Material Technology Co., Ltd.

[0036] Example 1:

[0037] A rare-earth heat-insulating automotive window film is composed of a hardening layer, a magnetron sputtering film layer, a substrate layer, an adhesive layer, and a release film layer, which are integrally formed. The hardening layer is formed by coating modified polyurethane onto the magnetron sputtering film layer and then curing it at 80°C. The thickness of the hardening layer is 5μm.

[0038] The polyurethane is prepared by:

[0039] (1) Under nitrogen protection, cyanuric chloride and 5-aldehyde-2-thiophene boric acid were dissolved in 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride were added, the temperature was raised to 80℃ and the reaction was carried out for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain the aldehyde monomer; the molar ratio of cyanuric chloride and 5-aldehyde-2-thiophene boric acid was 1:3.1; the mass ratio of cyanuric chloride, 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride was 1:5:1.7:0.04;

[0040] (2) Bis(4-aminophenyl)acetylene, azobisisobutyronitrile, diisopropyl sulfide xanthate, and m-xylene were mixed and reacted at 130°C for 24 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature and purified by column chromatography (eluent: n-hexane / ethyl acetate = 1 / 2 (V / V)) to obtain the amino monomer precursor. The molar ratio of bis(4-aminophenyl)acetylene, azobisisobutyronitrile, and diisopropyl sulfide xanthate was 1:0.4:1.1. The mass of m-xylene was 20 times that of bis(4-aminophenyl)acetylene. The amino monomer precursor was dissolved in tetrahydrofuran / water solution (tetrahydrofuran / water = 2 / 1). In a 0.5 (V / V) mixture, a tetramethylammonium hydroxide-methanol solution was added, and the mixture was stirred at room temperature for 40 min. Then, nickel chloride hexahydrate was added, and the mixture was stirred for another 12 h at room temperature. Iodine was then added and stirred for another 12 h. After the reaction was complete, the mixture was filtered, redissolved with dimethyl sulfoxide, precipitated with methanol, filtered again, and washed with methanol to obtain the amino monomer. The molar ratio of the amino monomer precursor, tetramethylammonium hydroxide, nickel chloride hexahydrate, and iodine was 1:2:0.5:0.5. The mass of the tetrahydrofuran / water solution was 15 times that of the amino monomer precursor. The tetramethylammonium hydroxide-methanol solution was obtained by mixing tetramethylammonium hydroxide and methanol at a mass ratio of 1:5.

[0041] (3) Lanthanum hexaboride was uniformly dispersed in an ethanol / water solution (ethanol / water = 4:1 (v / v)), 3-aminopropyltrimethoxysilane was added, and the pH of the solution was adjusted to 6 using 20% ​​dilute sulfuric acid. After reacting at 80°C for 6 hours, the solution was filtered, washed, and dried to obtain pretreated lanthanum hexaboride. The mass ratio of lanthanum hexaboride, 3-aminopropyltrimethoxysilane, and ethanol / water solution was 1:0.3:20. Under nitrogen protection, pretreated lanthanum hexaboride, N,N-dimethylacetamide, and acetic acid were ultrasonically mixed, and aldehyde monomer and amino monomer were added. The solution was heated to 100°C and reacted for 72 hours under sealed conditions. After the reaction was completed, the solution was cooled to room temperature, filtered, washed, and dried to obtain modified lanthanum hexaboride. The mass ratio of pretreated lanthanum hexaboride, N,N-dimethylacetamide, acetic acid, aldehyde monomer, and amino monomer was 1:20:10:0.3:0.2.

[0042] (4) Mix polycarbonate diol and n-butyl acetate, add isophorone diisocyanate and dibutyltin dilaurate at 50°C under nitrogen protection, react for 4 hours, raise the temperature to 75°C and add 1-allyl-1H-1,2,4-triazole-3-amine to continue the reaction for 4 hours. After the reaction is completed, precipitate with anhydrous diethyl ether, filter, wash and dry to obtain polyurethane prepolymer; the mass ratio of polycarbonate diol, n-butyl acetate, isophorone diisocyanate, dibutyltin dilaurate and 1-allyl-1H-1,2,4-triazole-3-amine is 1:30:0.8:0.001:0.4;

[0043] (5) Mix tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and trichlorosilane in a molar ratio of 1:1.1:1.3, dissolve in 1,4-dioxane in 10 times the mass of tris(hydroxymethyl)aminomethane hydrochloride, heat to 80°C and react for 8 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain aminosilane; Mix aminosilane, triethylamine, and phosphorus oxychloride in a molar ratio of 3.1:3.3:1, dissolve in diethanol dimethyl ether in 11 times the mass of aminosilane, heat to 105°C and react for 6 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain phosphorus-containing silane crosslinking agent;

[0044] (6) The polyurethane prepolymer, modified lanthanum hexaboride, phosphorus-containing silane crosslinking agent, caster catalyst and toluene are mixed in a mass ratio of 1:0.2:0.2:0.005:4 to obtain the modified polyurethane.

[0045] Example 2:

[0046] A rare-earth heat-insulating automotive window film is composed of a hardening layer, a magnetron sputtering film layer, a substrate layer, an adhesive layer, and a release film layer, which are integrally formed. The modified hardening layer is formed by coating modified polyurethane onto the magnetron sputtering film layer and then curing it at 80°C. The thickness of the hardening layer is 6μm.

[0047] The modified polyurethane is prepared by:

[0048] (1) Under nitrogen protection, cyanuric chloride and 5-aldehyde-2-thiophene boric acid were dissolved in 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride were added, the temperature was raised to 75℃ and the reaction was carried out for 7 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain the aldehyde monomer; the molar ratio of cyanuric chloride and 5-aldehyde-2-thiophene boric acid was 1:3.15; the mass ratio of cyanuric chloride, 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride was 1:5.5:1.8:0.05;

[0049] (2) Bis(4-aminophenyl)acetylene, azobisisobutyronitrile, diisopropyl sulfide xanthate, and m-xylene were mixed and reacted at 125°C for 23 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature and purified by column chromatography (eluent: n-hexane / ethyl acetate = 1 / 2 (V / V)) to obtain the amino monomer precursor. The molar ratio of bis(4-aminophenyl)acetylene, azobisisobutyronitrile, and diisopropyl sulfide xanthate was 1:0.45:1.15. The mass of m-xylene was 25 times that of bis(4-aminophenyl)acetylene. The amino monomer precursor was dissolved in tetrahydrofuran / water solution (tetrahydrofuran / water = 2 / 1.5). In a (V / V) mixture, a tetramethylammonium hydroxide-methanol solution was added, and the mixture was stirred at room temperature for 35 min. Then, nickel chloride hexahydrate was added, and the mixture was stirred for another 11 h at room temperature. Iodine was then added and stirred for another 11 h. After the reaction was complete, the mixture was filtered, redissolved with dimethyl sulfoxide, precipitated with methanol, filtered again, and washed with methanol to obtain the amino monomer. The molar ratio of the amino monomer precursor, tetramethylammonium hydroxide, nickel chloride hexahydrate, and iodine was 1:2.3:0.55:0.55. The mass of the tetrahydrofuran / water solution was 17 times that of the amino monomer precursor. The tetramethylammonium hydroxide-methanol solution was obtained by mixing tetramethylammonium hydroxide and methanol at a mass ratio of 1:5.5.

[0050] (3) Lanthanum hexaboride was uniformly dispersed in an ethanol / water solution (ethanol / water = 4:1 (v / v)), 3-aminopropyltrimethoxysilane was added, and the pH of the solution was adjusted to 5.5 with 20% dilute sulfuric acid. After the reaction was heated to 75°C for 5.5 h, the solution was filtered, washed and dried to obtain pretreated lanthanum hexaboride. The mass ratio of lanthanum hexaboride, 3-aminopropyltrimethoxysilane and ethanol / water solution was 1:0.4:25. Under nitrogen protection, pretreated lanthanum hexaboride, N,N-dimethylacetamide and acetic acid were ultrasonically mixed, and aldehyde monomer and amino monomer were added. The solution was heated to 100°C for 72 h under closed conditions. After the reaction was completed, the solution was cooled to room temperature, filtered, washed and dried to obtain modified lanthanum hexaboride. The mass ratio of pretreated lanthanum hexaboride, N,N-dimethylacetamide, acetic acid, aldehyde monomer and amino monomer was 1:25:11:0.4:0.25.

[0051] (4) Polycarbonate diol and n-butyl acetate were mixed, and isophorone diisocyanate and dibutyltin dilaurate were added under nitrogen protection at 50°C. The reaction was carried out for 3.5 h, and then 1-allyl-1H-1,2,4-triazole-3-amine was added at 60°C and the reaction was continued for 3.5 h. After the reaction was completed, the polyurethane prepolymer was obtained by precipitation with anhydrous diethyl ether, filtration, washing and drying. The mass ratio of polycarbonate diol, n-butyl acetate, isophorone diisocyanate, dibutyltin dilaurate and 1-allyl-1H-1,2,4-triazole-3-amine was 1:35:0.9:0.001:0.5.

[0052] (5) Mix tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and trichlorosilane in a molar ratio of 1:1.2:1.4, dissolve in 1,4-dioxane in 11 times the mass of tris(hydroxymethyl)aminomethane hydrochloride, heat to 75°C and react for 7 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain aminosilane; Mix aminosilane, triethylamine, and phosphorus oxychloride in a molar ratio of 3.15:3.4:1, dissolve in diethanol dimethyl ether in 11 times the mass of aminosilane, heat to 100°C and react for 5.5 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain phosphorus-containing silane crosslinking agent;

[0053] (6) The polyurethane prepolymer, modified lanthanum hexaboride, phosphorus-containing silane crosslinking agent, cassiterite catalyst and toluene are mixed in a mass ratio of 1:0.25:0.25:0.007:4.5 to obtain the modified polyurethane.

[0054] Example 3:

[0055] A rare-earth heat-insulating automotive window film is composed of a hardening layer, a magnetron sputtering film layer, a substrate layer, an adhesive layer, and a release film layer, which are integrally formed. The hardening layer is formed by coating modified polyurethane onto the magnetron sputtering film layer and then curing it at 80°C. The thickness of the hardening layer is 5μm.

[0056] The polyurethane is prepared by:

[0057] (1) Under nitrogen protection, cyanuric chloride and 5-aldehyde-2-thiophene boric acid were dissolved in 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride were added, the temperature was raised to 70℃ and the reaction was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain the aldehyde monomer; the molar ratio of cyanuric chloride and 5-aldehyde-2-thiophene boric acid was 1:3.2; the mass ratio of cyanuric chloride, 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride was 1:6:2.0:0.06;

[0058] (2) Bis(4-aminophenyl)acetylene, azobisisobutyronitrile, diisopropyl sulfide xanthate, and m-xylene were mixed and reacted at 120°C for 20 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature and purified by column chromatography (eluent: n-hexane / ethyl acetate = 1 / 2 (V / V)) to obtain the amino monomer precursor. The molar ratio of bis(4-aminophenyl)acetylene, azobisisobutyronitrile, and diisopropyl sulfide xanthate was 1:0.5:1.2. The mass of m-xylene was 30 times that of bis(4-aminophenyl)acetylene. The amino monomer precursor was dissolved in tetrahydrofuran / water solution (tetrahydrofuran / water = 2 / 1). In a 5 (V / V) mixture, a tetramethylammonium hydroxide-methanol solution was added, and the mixture was stirred at room temperature for 30 min. Then, nickel chloride hexahydrate was added, and the mixture was stirred for another 10 h at room temperature. Iodine was then added and stirred for another 10 h. After the reaction was complete, the mixture was filtered, redissolved with dimethyl sulfoxide, precipitated with methanol, filtered again, and washed with methanol to obtain the amino monomer. The molar ratio of the amino monomer precursor, tetramethylammonium hydroxide, nickel chloride hexahydrate, and iodine was 1:2.5:0.6:0.6. The mass of the tetrahydrofuran / water solution was 20 times that of the amino monomer precursor. The tetramethylammonium hydroxide-methanol solution was obtained by mixing tetramethylammonium hydroxide and methanol at a mass ratio of 1:6.

[0059] (3) Lanthanum hexaboride was uniformly dispersed in an ethanol / water solution (ethanol / water = 4:1 (v / v)), 3-aminopropyltrimethoxysilane was added, and the pH of the solution was adjusted to 5 with 20% dilute sulfuric acid. After the reaction was heated to 70℃ for 5 h, the solution was filtered, washed and dried to obtain pretreated lanthanum hexaboride. The mass ratio of lanthanum hexaboride, 3-aminopropyltrimethoxysilane and ethanol / water solution was 1:0.5:30. Under nitrogen protection, pretreated lanthanum hexaboride, N,N-dimethylacetamide and acetic acid were ultrasonically mixed, and aldehyde monomer and amino monomer were added. The solution was heated to 90-100℃ under closed conditions for 72 h. After the reaction was completed, the solution was cooled to room temperature, filtered, washed and dried to obtain modified lanthanum hexaboride. The mass ratio of pretreated lanthanum hexaboride, N,N-dimethylacetamide, acetic acid, aldehyde monomer and amino monomer was 1:30:12:0.5:0.3.

[0060] (4) Mix polycarbonate diol and n-butyl acetate, add isophorone diisocyanate and dibutyltin dilaurate at 50°C under nitrogen protection, react for 3 hours, raise the temperature to 65°C and add 1-allyl-1H-1,2,4-triazole-3-amine and continue to react for 3 hours. After the reaction is completed, precipitate with anhydrous diethyl ether, filter, wash and dry to obtain polyurethane prepolymer; the mass ratio of polycarbonate diol, n-butyl acetate, isophorone diisocyanate, dibutyltin dilaurate and 1-allyl-1H-1,2,4-triazole-3-amine is 1:40:1.0:0.002:0.6;

[0061] (5) Mix tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and trichlorosilane in a molar ratio of 1:1.3:1.5, dissolve in 1,4-dioxane in 12 times the mass of tris(hydroxymethyl)aminomethane hydrochloride, heat to 70°C and react for 6 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain aminosilane; Mix aminosilane, triethylamine, and phosphorus oxychloride in a molar ratio of 3.2:3.5:1, dissolve in diethanol dimethyl ether in 12 times the mass of aminosilane, heat to 95°C and react for 5 hours. Filter while hot, redissolve in pure water, adjust the pH to 8 with triethylamine, filter again, wash and dry to obtain phosphorus-containing silane crosslinking agent;

[0062] (6) The polyurethane prepolymer, modified lanthanum hexaboride, phosphorus-containing silane crosslinking agent, caster catalyst and toluene are mixed in a mass ratio of 1:0.3:0.3:0.01:5 to obtain the modified polyurethane.

[0063] Comparative Example 1:

[0064] The difference between the preparation method of the rare earth heat-insulating automotive window film in Comparative Example 1 and Example 2 is that it does not contain a phosphosilicate crosslinking agent; specifically, it does not include step (5), and step (6) is modified to: mixing polyurethane prepolymer, modified lanthanum hexaboride, and toluene at a mass ratio of 1:0.25:4.5 to obtain modified polyurethane. The remaining steps are the same as in Example 2.

[0065] Comparative Example 2:

[0066] The difference between the preparation method of the rare earth heat-insulating automotive window film in Comparative Example 2 and Example 2 is that it does not contain modified lanthanum hexaboride, specifically steps (1) to (3) are omitted, and step (6) is modified as follows: polyurethane prepolymer, phosphorus-containing silane crosslinking agent, cassiterite catalyst, and toluene are mixed at a mass ratio of 1:0.25:0.007:4.5 to obtain modified polyurethane. The remaining steps are the same as in Example 2.

[0067] Comparative Example 3:

[0068] The difference between the preparation method of the rare earth heat-insulating automotive window film in Comparative Example 3 and Example 2 is that the lanthanum hexaboride is not modified. Specifically, steps (1) to (3) are omitted, and step (6) is modified as follows: the polyurethane prepolymer, lanthanum hexaboride, phosphorus-containing silane crosslinking agent, cassiterite catalyst, and toluene are mixed in a mass ratio of 1:0.25:0.25:0.007:4.5 to obtain the modified polyurethane. The remaining steps are the same as in Example 2.

[0069] Test Example 1:

[0070] Weather resistance testing:

[0071] Test method: A cross-shaped scratch, 25 mm in length and width, was made on the window film using a diamond cutter. The window film was then immersed in a 5 wt% sodium chloride solution at 85°C for 600 hours. The scratched areas were observed for blistering and discoloration. Results are shown in Table 1.

[0072]

[0073] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 1 shows that the material prepared by the present invention has good weather resistance.

[0074] The weather resistance of Examples 1-3 is better than that of the comparative examples. This is because the thiophene group, triazine group, and Schiff base functional group formed on the surface of lanthanum hexaboride, the triazole group on the polyurethane, and the amide functional group in the crosslinking agent can all efficiently complex metal ions, forming a metal passivation layer on the magnetron sputtering film, blocking the corrosion of the magnetron sputtering film by the humid and hot environment, and extending the service life of the magnetron sputtering film.

[0075] Test Example 2:

[0076] Flame retardant performance testing:

[0077] Test method: The polyurethanes prepared in the examples and comparative examples were cured into films in a mold at 80°C. After demolding, 120mm×6mm×4m specimens were prepared, and the limiting oxygen index was tested according to GB / T 2406.1—2008. The results are shown in Table 2:

[0078]

[0079] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 2 shows that the material prepared by the present invention has good flame retardant properties.

[0080] The flame retardant properties of Examples 1-3 are superior to those of the comparative examples because the reaction of tris(hydroxymethyl)aminomethane hydrochloride and trichlorosilane produces a stable tricage-like aminosilane; the aminosilane and phosphorus oxychloride are linked by phosphoramide bonds to form a crosslinking agent containing three flame retardant elements: silicon, nitrogen, and phosphorus. This agent has a high content of effective flame retardant elements, and when applied to materials, it can effectively exert the synergistic flame retardant effect of each element, thereby reducing the amount of flame retardant used and improving the flame retardant effect.

[0081] Test Example 3:

[0082] Thermal insulation performance testing:

[0083] Test Method: The release film layer of the automotive window films prepared in the examples and comparative examples was peeled off and laminated with clean 3mm flat glass. Referring to QC / T 1170-2022 "Functional Films for Automotive Glass", the incident ratio and reflectance were recorded in the near-infrared band (1400nm-2500nm) of the solar spectrum using a Hitachi U-4100 UV-Vis-NIR spectrophotometer, and the infrared blocking rate was calculated. The results are shown in Table 3.

[0084]

[0085] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 3 shows that the material prepared by the present invention has good thermal insulation performance.

[0086] The superior thermal insulation performance of Examples 1-3 compared to the comparative example is due to the characteristic absorption of near-infrared light inherent in the nickel-coordinated thiodiene structure. Introducing this structure into the polymer backbone via small-molecule polymerization imparts excellent near-infrared absorption properties to the polymer. Furthermore, the triazine group, as a strong electron-withdrawing group, and the thiophene group, as an electron-rich group, are connected via π-bridges, which can further broaden the nickel-coordinated thiodiene structure during polymer formation.

[0087] 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 implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A rare-earth heat-insulating automotive window film, comprising, in sequence, a hardening layer, a magnetron sputtering film layer, a substrate layer, an adhesive layer, and a release film layer, integrally formed; characterized in that, The hardened layer is obtained by coating a modified polyurethane onto a magnetron sputtered film and curing it. The modified polyurethane is prepared as follows: (1) The aldehyde monomer is obtained by reacting cyanuric chloride and 5-aldehyde-2-thiophene boric acid; (2) The amino monomer precursor was obtained by reacting bis(4-aminophenyl)acetylene with diisopropyl sulfide xanthate; the amino monomer precursor was obtained by reacting nickel chloride hexahydrate with nickel chloride hexahydrate. (3) Pretreated lanthanum hexaboride, aldehyde monomer, and amino monomer were reacted to obtain modified lanthanum hexaboride; (4) Polycarbonate diol, isophorone diisocyanate and 1-allyl-1H-1,2,4-triazole-3-amine were reacted to obtain polyurethane prepolymer; (5) Tris(hydroxymethyl)aminomethane hydrochloride and trichlorosilane are reacted to obtain aminosilane; aminosilane and phosphorus oxychloride are reacted to obtain phosphorus-containing silane crosslinking agent; (6) The modified polyurethane is obtained by mixing polyurethane prepolymer, modified lanthanum hexaboride, and phosphorus-containing silane crosslinking agent; The preparation method of the pretreated lanthanum hexaboride is as follows: Lanthanum hexaboride is uniformly dispersed in an ethanol / water solution, 3-aminopropyltrimethoxysilane is added, the pH of the solution is adjusted to 5-6 with dilute sulfuric acid, and the temperature is raised to 70-80℃ for 5-6 hours to obtain pretreated lanthanum hexaboride; the mass ratio of lanthanum hexaboride, 3-aminopropyltrimethoxysilane, and ethanol / water solution is 1:(0.3-0.5):(20-30); The aldehyde monomer is prepared by dissolving cyanuric chloride and 5-aldehyde-2-thiophene boric acid in 1,4-dioxane, adding 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride, and heating to 70-80℃ for 6-8 hours to obtain the aldehyde monomer; the molar ratio of cyanuric chloride and 5-aldehyde-2-thiophene boric acid is 1:(3.1-3.2); the mass ratio of cyanuric chloride, 1,4-dioxane, 1M potassium carbonate aqueous solution and bis(triphenylphosphine)palladium dichloride is 1:(5-6):(1.7-2.0):(0.04-0.06); The amino monomer is prepared by mixing bis(4-aminophenyl)acetylene, azobisisobutyronitrile, diisopropyl sulfide xanthate, and m-xylene, and reacting at 120-130℃ for 20-24 h to obtain the amino monomer precursor; the molar ratio of bis(4-aminophenyl)acetylene, azobisisobutyronitrile, and diisopropyl sulfide xanthate is 1:(0.4-0.5):(1.1-1.2); the mass of m-xylene is 20-30 times that of bis(4-aminophenyl)acetylene; the amino monomer precursor is dissolved in tetrahydrofuran / aqueous solution; tetramethyl hydroxide is added. An ammonium-methanol solution is stirred at room temperature for 30-40 min, then nickel chloride hexahydrate is added, and the mixture is stirred for another 10-12 h at room temperature. Iodine is then added and stirred for another 10-12 h to obtain an amino monomer. The molar ratio of the amino monomer precursor, tetramethylammonium hydroxide, nickel chloride hexahydrate, and iodine is 1:(2-2.5):(0.5-0.6):(0.5-0.6). The mass of the tetrahydrofuran / water solution is 15-20 times that of the amino monomer precursor. The tetramethylammonium hydroxide-methanol solution is obtained by mixing tetramethylammonium hydroxide and methanol at a mass ratio of 1:(5-6).

2. The rare earth heat-insulating automotive window film according to claim 1, characterized in that, The preparation method of the modified lanthanum hexaboride in step (3) is as follows: pretreated lanthanum hexaboride, N,N-dimethylacetamide, and acetic acid are ultrasonically mixed, aldehyde monomer and amino monomer are added, and the mixture is heated to 90-100℃ and reacted for 72h to obtain modified lanthanum hexaboride; the mass ratio of pretreated lanthanum hexaboride, N,N-dimethylacetamide, acetic acid, aldehyde monomer and amino monomer is 1:(20-30):(10-12):(0.3-0.5):(0.2-0.3).

3. The rare earth heat-insulating automotive window film according to claim 1, characterized in that, The preparation method of the polyurethane prepolymer in step (4) is as follows: polycarbonate diol and n-butyl acetate are mixed, isophorone diisocyanate and dibutyltin dilaurate are added at 50°C, and the reaction is carried out for 3-4 hours. The temperature is raised to 65-75°C and 1-allyl-1H-1,2,4-triazole-3-amine is added and the reaction is continued for 3-4 hours to obtain the polyurethane prepolymer. The mass ratio of polycarbonate diol, n-butyl acetate, isophorone diisocyanate, dibutyltin dilaurate and 1-allyl-1H-1,2,4-triazole-3-amine is 1:(30-40):(0.8-1.0):(0.001-0.002):(0.4-0.6).

4. The rare earth heat-insulating automotive window film according to claim 1, characterized in that, The preparation method of the phosphorus-containing silane crosslinking agent in step (5) is as follows: Tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and trichlorosilane are mixed in a molar ratio of 1:(1.1-1.3):(1.3-1.5), dissolved in 1,4-dioxane at 10-12 times the mass of tris(hydroxymethyl)aminomethane hydrochloride, and reacted at 70-80℃ for 6-8h to obtain aminosilane; aminosilane, triethylamine, and phosphorus oxychloride are mixed in a molar ratio of (3.1-3.2):(3.3-3.5):1, dissolved in diethanol dimethyl ether at 10-12 times the mass of aminosilane, and reacted at 95-105℃ for 5-6h to obtain phosphorus-containing silane crosslinking agent.

5. The rare earth heat-insulating automotive window film according to claim 1, characterized in that, The modified polyurethane in step (6) is prepared by mixing polyurethane prepolymer, modified lanthanum hexaboride, phosphorus-containing silane crosslinking agent, caster catalyst, and toluene in a mass ratio of 1:(0.2-0.3):(0.2-0.3):(0.005-0.01):(4-5) to obtain modified polyurethane.

6. The rare earth heat-insulating automotive window film according to claim 1, characterized in that, The hardened layer has a thickness of 5-7 μm; the magnetron sputtered film is a metal oxide film; the substrate layer is a polyester film; the mounting adhesive layer is an acrylic adhesive; and the release film layer is a polyester film.

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