Anti-ultraviolet automobile film and preparation method thereof

Abstract

The invention discloses an anti-ultraviolet automobile film and a preparation method thereof, and belongs to the technical field of automobile films. The invention relates to a high-temperature-resistant coating which comprises the following components in parts by weight: 80-100 parts of polyethylene glycol terephthalate, 3-5 parts of polyimide, 5-8 parts of a plasticizer, 2-3 parts of a defoaming agent, 1-2 parts of a flatting agent and 20-30 parts of TiO2 / PDA / ZnO (at) MOF. TiO2 is wrapped by polydopamine, agglomeration of TiO2 is prevented, meanwhile, ZnO is wrapped on the outer layer more uniformly due to the adsorption effect on ZnO, and polydopamine also has the antibacterial and light absorption effects; the combination of TiO2 and ZnO can effectively improve the breadth and depth of ultraviolet protection. The prepared automobile film has high transmittance and ultraviolet absorptivity, and a pencil hardness test table has good mechanical properties and good antibacterial rate.

Description

Technical Field

[0001] The invention belongs to the technical field of automobile films, and in particular relates to an anti-ultraviolet automobile film and a preparation method thereof. Background Art

[0002] Car film is a thin film attached to the front and rear windshields, side windows and sunroof of a car. With global warming, increasing energy shortages and the widespread use of glass in the construction or automotive industry, functional protective films such as heat insulation, UV protection, explosion-proof and energy-saving protective films are increasingly attracting people's attention. In recent years, due to the continuous destruction of the ozone layer, the amount of ultraviolet radiation reaching the earth has continued to increase, affecting human health while also affecting the use of materials. Therefore, anti-ultraviolet materials have emerged. Among them, the more commonly used material is acrylic anti-ultraviolet paint. However, anti-ultraviolet paint has a corrosive effect, and it is urgent to develop a film material that can resist UV corrosion.

[0003] The patent application with publication number CN116199954A discloses an anti-ultraviolet film and a method for manufacturing the same. The film is a mixed film of low-density polyethylene and linear low-density polyethylene. The application adds modified nano zinc oxide powder and nano titanium dioxide powder to the system. Since the added nanoparticles have poor dispersibility, the transparency of the prepared material is poor. Therefore, it is urgent to study and prepare an automotive film with good light transmittance and strong anti-ultraviolet effect. Summary of the invention

[0004] The object of the present invention is to provide an anti-ultraviolet automobile film and a preparation method thereof, so as to improve the anti-ultraviolet performance of the automobile film.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An anti-ultraviolet automobile film comprises, by weight, 80-100 parts of polyethylene terephthalate, 3-5 parts of polyimide, 5-8 parts of plasticizer, 2-3 parts of defoamer, 1-2 parts of leveling agent and 20-30 parts of TiO2 / PDA / ZnO@MOF.

[0007] Furthermore, the plasticizer is one of dibutyl phthalate and dioctyl phthalate; the defoamer is BYK-024, and the leveling agent is BYK-381.

[0008] Furthermore, the TiO2 / PDA / ZnO@MOF is prepared by the following steps:

[0009] S1. Place nano-TiO2 and dopamine hydrochloride in a Tris buffer solution, stir, wash and dry to obtain TiO2 / PDA; disperse TiO2 / PDA and zinc acetate dihydrate in ethylene glycol, slowly add 1 mol / L NaOH solution, heat and stir; wash and dry to obtain nano-TiO2 / PDA / ZnO particles;

[0010] S2. Disperse nano-TiO2 / PDA / ZnO particles and benzophenone tetracarboxylic dianhydride in deionized water to obtain a dispersion; add copper acetate monohydrate and 4,4'-bipyridine to the dispersion and mix well, heat to react, wash and dry to obtain TiO2 / PDA / ZnO@MOF.

[0011] Furthermore, the nano-TiO2 crystal form is rutile, and the particle size is 50-80nm; the dosage ratio of the nano-TiO2, dopamine hydrochloride and Tris buffer is 3-6g:0.5-0.8g:250-350mL; the pH of the Tris buffer is 8.5; and the stirring time is 8-12h.

[0012] Furthermore, the dosage ratio of the TiO2 / PDA, zinc acetate dihydrate, ethylene glycol and NaOH solution is 4-8 g: 12-24 g: 500-600 mL: 50 mL-80 mL; and the heating and stirring is stirring at 110-120°C for 6-8 hours.

[0013] Furthermore, the usage ratio of the nano-TiO2 / PDA / ZnO particles, benzophenonetetracarboxylic dianhydride, deionized water, copper acetate monohydrate and 4,4'-bipyridine is 6-10g: 1-1.5g: 80-100mL: 1.5-2.5g: 1.2-1.5g.

[0014] Furthermore, the temperature-raising reaction is carried out at 120-150° C. for 48-64 hours; and the drying is carried out at 500-600° C. for 2-3 hours.

[0015] A method for preparing an anti-ultraviolet automobile film comprises the following steps:

[0016] Polyethylene terephthalate, polyimide, plasticizer, defoamer, leveling agent, TiO2 / PDA / ZnO@MOF are uniformly mixed, extruded, and biaxially stretched before shaping to obtain an anti-ultraviolet automotive film.

[0017] Furthermore, the temperatures of various zones of the screw machine during the extrusion process are 160-170°C, 175-195°C, 200-210°C, 180-190°C, and 175-165°C.

[0018] Beneficial effects of the present invention:

[0019] (1) The present invention provides an anti-ultraviolet automobile film, which improves the anti-ultraviolet performance of the automobile film by adding anti-ultraviolet particles, wherein rutile TiO2 is wrapped by polydopamine, which can prevent the agglomeration of TiO2 and adsorb ZnO, so that ZnO is more evenly connected in the outer layer. In addition, polydopamine also has antibacterial and light absorbing effects; TiO2 wrapped by polydopamine has strong absorption of UVB, while the adsorbed ZnO has stronger absorption effect on UVA. The combined use of the two can effectively improve the breadth and depth of ultraviolet protection.

[0020] (2) The copper ion-based MOF material used in the present invention has a strong barrier capability against ultraviolet light in the metal ions in the metal organic framework material. On the other hand, the MOF material effectively protects the stability of TiO2 / PDA / ZnO. In addition, the benzophenone tetracarboxylic dianhydride in the MOF material can also form hydrogen bonds with polyethylene terephthalate, which is beneficial to enhancing the mechanical properties of the material. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0022] Example 1

[0023] This embodiment provides an anti-ultraviolet automobile film, which is prepared by the following steps:

[0024] S1. Place 4 g of rutile nano-TiO2 with a particle size of 60 nm and 0.6 g of dopamine hydrochloride in 300 mL of Tris buffer at pH = 8.5, stir for 10 h, wash and dry to obtain TiO2 / PDA; disperse 5 g of TiO2 / PDA and 20 g of zinc acetate dihydrate in 500 mL of ethylene glycol, slowly add 60 mL of 1 mol / L NaOH solution, stir at 110°C for 8 h; wash and dry to obtain nano-TiO2 / PDA / ZnO particles;

[0025] S2. Disperse 8 g of nano-TiO2 / PDA / ZnO particles and 1.25 g of benzophenone tetracarboxylic dianhydride in 100 mL of deionized water to obtain a dispersion; add 2 g of copper acetate monohydrate and 1.5 g of 4,4'-bipyridine to the dispersion, mix well, react at 130°C for 64 h, wash, and dry at 550°C for 2 h to obtain TiO2 / PDA / ZnO@MOF.

[0026] S3. 90 g polyethylene terephthalate, 4 g polyimide, 6 g dibutyl phthalate, 3 g BYK-024, 2 g BYK-381, and 25 g TiO2 / PDA / ZnO@MOF are mixed evenly and extruded. The temperatures of various zones of the screw machine are 165°C, 185°C, 205°C, 185°C, and 170°C. After biaxial stretching, the film is shaped to obtain an anti-ultraviolet automotive film.

[0027] Example 2

[0028] Compared with Example 1, the present embodiment is different in that "90g polyethylene terephthalate, 4g polyimide, 6g dibutyl phthalate, 3g BYK-024, 2g BYK-381, 25g TiO2 / PDA / ZnO@MOF" in S3 is changed to "100g polyethylene terephthalate, 4g polyimide, 7g dibutyl phthalate, 3g BYK-024, 2g BYK-381, 20g TiO2 / PDA / ZnO@MOF".

[0029] The remaining raw materials and preparation process remain the same as in Example 1.

[0030] Example 3

[0031] Compared with Example 1, the present embodiment is different in that "90g polyethylene terephthalate, 4g polyimide, 6g dibutyl phthalate, 3g BYK-024, 2g BYK-381, 25g TiO2 / PDA / ZnO@MOF" in S3 is changed to "80g polyethylene terephthalate, 4g polyimide, 5g dibutyl phthalate, 2g BYK-024, 2g BYK-381, 30g TiO2 / PDA / ZnO@MOF".

[0032] The remaining raw materials and preparation process remain the same as in Example 1.

[0033] Example 4

[0034] Compared with Example 1, the present embodiment is different in that "8g nano-TiO2 / PDA / ZnO particles, 1.25g benzophenonetetracarboxylic dianhydride", "2g cupric acetate monohydrate and 1.5g 4,4'-bipyridine" in S2 are changed to "10g nano-TiO2 / PDA / ZnO particles, 1g benzophenonetetracarboxylic dianhydride", "2.5g cupric acetate monohydrate and 1.5g 4,4'-bipyridine".

[0035] The remaining raw materials and preparation process remain the same as in Example 1.

[0036] Example 5

[0037] Compared with Example 1, the present embodiment is different in that "8g nano-TiO2 / PDA / ZnO particles, 1.25g benzophenonetetracarboxylic dianhydride", "2g cupric acetate monohydrate and 1.5g 4,4'-bipyridine" in S2 are changed to "6g nano-TiO2 / PDA / ZnO particles, 1.5g benzophenonetetracarboxylic dianhydride", "1.5g cupric acetate monohydrate and 1.2g 4,4'-bipyridine".

[0038] The remaining raw materials and preparation process remain the same as in Example 1.

[0039] Example 6

[0040] The present embodiment is different from the embodiment 1 in that "5 g TiO2 / PDA, 20 g zinc acetate dihydrate" in S1 is changed to "5 g TiO2 / PDA, 24 g zinc acetate dihydrate".

[0041] The remaining raw materials and preparation process remain the same as in Example 1.

[0042] Comparative Example 1

[0043] Compared with Example 1, this comparative example differs in that no MOF material is added, and the specific implementation steps are as follows:

[0044] S1. Place 4 g of rutile nano-TiO2 with a particle size of 60 nm and 0.6 g of dopamine hydrochloride in 300 mL of Tris buffer at pH = 8.5, stir for 10 h, wash and dry to obtain TiO2 / PDA; disperse 5 g of TiO2 / PDA and 20 g of zinc acetate dihydrate in 500 mL of ethylene glycol, slowly add 60 mL of 1 mol / L NaOH solution, stir at 110°C for 8 h; wash and dry to obtain nano-TiO2 / PDA / ZnO particles;

[0045] S2. 90 g of polyethylene terephthalate, 4 g of polyimide, 6 g of dibutyl phthalate, 3 g of BYK-024, 2 g of BYK-381, and 25 g of nano-TiO2 / PDA / ZnO particles are mixed evenly, and extruded. The temperatures of various zones of the screw machine are 165° C., 185° C., 205° C., 185° C., and 170° C. After biaxial stretching, the film is shaped to obtain an anti-ultraviolet automobile film.

[0046] The remaining raw materials and preparation process remain the same as in Example 1.

[0047] Comparative Example 2

[0048] Compared with Example 1, this comparative example differs in that polydopamine is not added, and the specific implementation steps are as follows:

[0049] S1. Disperse 4 g of rutile nano-TiO2 with a particle size of 60 nm and 20 g of zinc acetate dihydrate in 500 mL of ethylene glycol, slowly add 60 mL of 1 mol / L NaOH solution, and stir at 110° C. for 8 h; wash and dry to obtain nano-TiO2 / ZnO particles;

[0050] S2. Disperse 8 g of nano-TiO2 / ZnO particles and 1.25 g of benzophenone tetracarboxylic dianhydride in 100 mL of deionized water to obtain a dispersion; add 2 g of copper acetate monohydrate and 1.5 g of 4,4'-bipyridine to the dispersion, mix well, react at 130°C for 64 h, wash, and dry at 550°C for 2 h to obtain TiO2 / ZnO@MOF.

[0051] S3. Mix 90g polyethylene terephthalate, 4g polyimide, 6g dibutyl phthalate, 3g BYK-024, 2g BYK-381, and 25g TiO2 / ZnO@MOF evenly, extrude, and set the temperature of each zone of the screw machine at 165°C, 185°C, 205°C, 185°C, and 170°C. After biaxial stretching, the film is shaped to obtain an anti-ultraviolet automotive film.

[0052] The remaining raw materials and preparation process remain the same as in Example 1.

[0053] Comparative Example 3

[0054] Compared with Example 1, this comparative example differs in that ZnO is not added, and the specific implementation steps are as follows:

[0055] S1, 4 g of rutile nano-TiO2 with a particle size of 60 nm and 0.6 g of dopamine hydrochloride were placed in 300 mL of Tris buffer with a pH of 8.5, stirred for 10 h, washed and dried to obtain TiO2 / PDA;

[0056] S2. Disperse 8 g of nano-TiO2 / PDA particles and 1.25 g of benzophenone tetracarboxylic dianhydride in 100 mL of deionized water to obtain a dispersion; add 2 g of copper acetate monohydrate and 1.5 g of 4,4'-bipyridine to the dispersion, mix well, react at 130°C for 64 h, wash, and dry at 550°C for 2 h to obtain TiO2 / PDA@MOF.

[0057] S3, 90g polyethylene terephthalate, 4g polyimide, 6g dibutyl phthalate, 3g BYK-024, 2g BYK-381, 25g TiO2 / PDA@MOF were mixed evenly, extruded, and the temperatures of various regions of the screw machine were 165℃, 185℃, 205℃, 185℃, 170℃, and shaped after biaxial stretching to obtain an anti-ultraviolet automotive film. .

[0058] The remaining raw materials and preparation process remain the same as in Example 1.

[0059] Comparative Example 4

[0060] Compared with Example 1, this comparative example differs in that polydopamine and MOF material are not added at the same time, and the specific implementation steps are as follows:

[0061] S1. Disperse 4 g of rutile nano-TiO2 with a particle size of 60 nm and 20 g of zinc acetate dihydrate in 500 mL of ethylene glycol, slowly add 60 mL of 1 mol / L NaOH solution, and stir at 110° C. for 8 h; wash and dry to obtain nano-TiO2 / ZnO particles;

[0062] S2. 90 g of polyethylene terephthalate, 4 g of polyimide, 6 g of dibutyl phthalate, 3 g of BYK-024, 2 g of BYK-381, and 25 g of TiO2 / ZnO are mixed evenly, and extruded. The temperatures of various zones of the screw machine are 165° C., 185° C., 205° C., 185° C., and 170° C. After biaxial stretching, the film is shaped to obtain an anti-ultraviolet automotive film.

[0063] The remaining raw materials and preparation process remain the same as in Example 1.

[0064] Comparative Example 5

[0065] Compared with Example 1, this comparative example differs in that ZnO and MOF materials are not added at the same time, and the specific implementation steps are as follows:

[0066] S1, 4 g of rutile nano-TiO2 with a particle size of 60 nm and 0.6 g of dopamine hydrochloride were placed in 300 mL of Tris buffer with a pH of 8.5, stirred for 10 h, washed and dried to obtain TiO2 / PDA;

[0067] S3. 90 g of polyethylene terephthalate, 4 g of polyimide, 6 g of dibutyl phthalate, 3 g of BYK-024, 2 g of BYK-381, and 25 g of TiO2 / PDA are mixed evenly and extruded. The temperatures of various zones of the screw machine are 165° C., 185° C., 205° C., 185° C., and 170° C. After biaxial stretching, the film is shaped to obtain an anti-ultraviolet automotive film.

[0068] The remaining raw materials and preparation process remain the same as in Example 1.

[0069] Comparative Example 6

[0070] The difference between this comparative example and Example 1 is that the "500 mL of ethylene glycol" in S1 is replaced by "500 mL of deionized water".

[0071] The remaining raw materials and preparation process remain the same as in Example 1.

[0072] Performance Testing:

[0073] According to GB / T 2410-2008, the light transmittance of the anti-ultraviolet automobile films obtained in various embodiments and comparative examples of the present application was tested;

[0074] According to GB / T 2680-2021, the UV absorption rate of the anti-ultraviolet automotive film obtained in each embodiment and comparative example of the present application was tested (wavelength 290-400nm);

[0075] The anti-ultraviolet automotive films obtained in various embodiments and comparative examples of the present application were subjected to a pencil hardness test according to GB / T 6739-2022;

[0076] According to GB / T 31402-2023, the anti-ultraviolet car films obtained in various embodiments and comparative examples of the present application were tested for antibacterial properties (taking Staphylococcus aureus as an example);

[0077] The results are shown in Table 1:

[0078] Table 1

[0079]

[0080]

[0081] It can be seen from Table 1 that the only difference between Examples 2 to 6 and Example 1 is that the raw material ratio is changed within a reasonable range. From the results, the prepared anti-ultraviolet automotive films have good light transmittance, ultraviolet absorption rate, pencil hardness and antibacterial rate.

[0082] Compared with Example 1, the difference between Comparative Examples 1, 3 and 5 lies mainly in whether ZnO and MOF components are contained. The results show that the performance of the membrane is more obviously reduced when ZnO and MOF are not added at the same time than when any single component is not added. This is because the metal ions in the metal organic framework material have a strong barrier ability to ultraviolet light and have the effect of improving the dispersibility and stability of ZnO; in addition, the combination of TiO2 and ZnO will expand the ultraviolet absorption range of the membrane, and its use is more extensive; Compared with Example 1, Comparative Examples 1, 2, and 4 have the effect of improving the dispersibility of polydopamine and MOF materials. effect, which will affect the light transmittance of the material; polydopamine also has antibacterial and light absorbing effects, and MOF materials can also form hydrogen bonds, which is beneficial to enhancing the mechanical properties of the material. Therefore, when polydopamine and MOF materials are not added, the ultraviolet absorption rate, pencil hardness and antibacterial rate of the material are reduced accordingly; Example 6 Compared with Example 1, the size of ZnO prepared by ethylene glycol as a solvent in the material is more uniform and stable than that of ZnO prepared by deionized water, thereby making the TiO2 / PDA / ZnO@MOF morphology more uniform and stable, and better improving the performance of the anti-ultraviolet automotive film.

[0083] In summary, the present invention provides an anti-ultraviolet automobile film and a preparation method thereof. The prepared automobile film has high transmittance and ultraviolet absorption rate. The pencil hardness test shows that it has good mechanical properties and good antibacterial rate, and has good application prospects in the field of automobile film technology.

[0084] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0085] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An anti-ultraviolet film for automobiles, characterized in that: By weight, it includes 80-100 parts of polyethylene terephthalate, 3-5 parts of polyimide, 5-8 parts of plasticizer, 2-3 parts of defoamer, 1-2 parts of leveling agent, and 20-30 parts of TiO2 / PDA / ZnO@MOF.

2. The anti-ultraviolet automobile film according to claim 1, characterized in that: The plasticizer is one of dibutyl phthalate and dioctyl phthalate; the defoamer is BYK-024, and the leveling agent is BYK-381.

3. The anti-ultraviolet automobile film according to claim 1, characterized in that: The TiO2 / PDA / ZnO@MOF is prepared by the following steps: S1. Place nano-TiO2 and dopamine hydrochloride in a Tris buffer solution, stir, wash and dry to obtain TiO2 / PDA; disperse TiO2 / PDA and zinc acetate dihydrate in ethylene glycol, slowly add 1 mol / L NaOH solution, and heat and stir; Washing and drying to obtain nano-TiO2 / PDA / ZnO particles; S2, dispersing nano-TiO2 / PDA / ZnO particles and benzophenone tetracarboxylic dianhydride in deionized water to obtain a dispersion; Copper acetate monohydrate and 4,4'-bipyridine are added to the dispersion and mixed evenly, the temperature is raised to react, and the mixture is washed and dried to obtain TiO2 / PDA / ZnO@MOF.

4. The anti-ultraviolet automobile film according to claim 3, characterized in that: The nano-TiO2 crystal form is rutile type, and the particle size is 50-80nm; the dosage ratio of the nano-TiO2, dopamine hydrochloride and Tris buffer is 3-6g:0.5-0.8g:250-350mL; the pH of the Tris buffer is 8.5; and the stirring time is 8-12h.

5. The anti-ultraviolet automobile film according to claim 3, characterized in that: The dosage ratio of the TiO2 / PDA, zinc acetate dihydrate, ethylene glycol and NaOH solution is 4-8g:12-24g:500-600mL:50mL-80mL; the heating and stirring is stirring at 110-120°C for 6-8h.

6. The anti-ultraviolet automobile film according to claim 3, characterized in that: The dosage ratio of the nano-TiO2 / PDA / ZnO particles, benzophenone tetracarboxylic dianhydride, deionized water, copper acetate monohydrate and 4,4'-bipyridine is 6-10g: 1-1.5g: 80-100mL: 1.5-2.5g: 1.2-1.5g.

7. The anti-ultraviolet automobile film according to claim 3, characterized in that: The temperature-raising reaction is carried out at 120-150° C. for 48-64 hours; and the drying is carried out at 500-600° C. for 2-3 hours.

8. A method for preparing an anti-ultraviolet automobile film according to any one of claims 1 to 7, characterized in that: The following steps are involved: Polyethylene terephthalate, polyimide, plasticizer, defoamer, leveling agent, TiO2 / PDA / ZnO@MOF are uniformly mixed, extruded, and biaxially stretched before shaping to obtain an anti-ultraviolet automotive film.

9. The method for preparing an anti-ultraviolet automobile film according to claim 8, characterized in that: The temperatures of various zones of the screw machine during the extrusion process are 160-170°C, 175-195°C, 200-210°C, 180-190°C, and 175-165°C.

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