Efficient anti-fouling protective film for mobile phone and preparation method thereof

Abstract

The application relates to the technical field of protective films, in particular to a high-efficiency anti-fouling protective film for mobile phones and a preparation method thereof, which comprises a functional film layer, and the functional film layer is composed of the following raw materials in parts by weight: 80-100 parts of a base material, 8-10 parts of a first additive, 8-10 parts of a second additive, 3-5 parts of a third additive and 1-3 parts of a processing aid. In the application, the third additive is a fluorine-containing branched polyester, which migrates to the surface in processing, refines and encrypts the arrangement of fluorine atoms on the outermost layer, and under the multiple linkage mechanism, the surface of the protective film simultaneously has extremely low surface energy and suitable micro-nano roughness, remarkable synergistic effects are generated, and full protection is realized on water-based and oil-based stains.

Description

Technical Field

[0001] This invention relates to the field of protective film technology, specifically to a highly effective anti-fouling protective film for mobile phones and its preparation method. Background Technology

[0002] In today's consumer electronics market, screen protectors are widely used as an important mobile phone accessory. In addition to smartphones, they are also suitable for screen protection of devices such as tablets. With the continuous advancement of technology, screen protectors play an important role in improving screen protection performance, meeting consumers' various needs for screen scratch and dirt prevention, enabling mobile phone screens to maintain good working condition and extend their lifespan. Moreover, their manufacturing process is becoming increasingly mature, and the variety of products is rich and diverse, occupying an important position in the market.

[0003] In the existing technology, most of the mainstream antifouling technologies on the market rely on coating a layer of low surface energy fluorosilicone coating on the surface of the protective film. Although it can provide a certain hydrophobic and oleophobic effect in the early stage, it is very easy to wear or peel off due to friction and scratches in daily use, resulting in a rapid decline in antifouling performance. Summary of the Invention

[0004] The purpose of this invention is to provide a highly efficient anti-fouling protective film for mobile phones and its preparation method. The protective film prepared by this invention not only has good anti-fouling performance, but also excellent hardness performance.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a highly efficient anti-fouling protective film for mobile phones, comprising a functional film layer, wherein the functional film layer is composed of the following raw materials in parts by weight: 80-100 parts of base material, 8-10 parts of first additive, 8-10 parts of second additive, 3-5 parts of third additive, and 1-3 parts of processing aid. The raw materials for the first additive include octafluoropentanol, trimellitic anhydride, terephthalic acid, isophthalic acid, ethylene glycol, hydroxyl-terminated polybutadiene, and tetrabutyl titanate. The raw materials for the second additive include nano-silica, fluorinated polyetheramine, dimethyl 2,5-furandicarboxylate, 1,3-propanediol, tetrabutyl titanate, toluene, anhydrous ethanol, and acetic acid. The raw materials for the third additive include 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, maleic anhydride, neopentyl glycol, and p-toluenesulfonic acid.

[0006] Preferably, the preparation method of the first additive is as follows: octafluoropentanol, trimellitic anhydride and tetrabutyl titanate are added to a reaction vessel, and under nitrogen protection, the temperature is slowly raised to 160-180℃ and reacted for 2-3 hours to obtain a first intermediate. Then, terephthalic acid, isophthalic acid, ethylene glycol and hydroxyl-terminated polybutadiene are added, and the temperature is raised to 210-240℃ until the water output reaches more than 95% of the theoretical value. Then, the absolute pressure is adjusted to less than 100 Pa, the temperature is controlled at 240-280℃, and the reaction is carried out for 3-4 hours to obtain the first additive.

[0007] Preferably, the mass ratio of octafluoropentanol, trimellitic anhydride, tetrabutyl titanate, terephthalic acid, isophthalic acid, ethylene glycol, and hydroxyl-terminated polybutadiene is 100:60-80:0.5-1.5:70-90:20-30:40-50:50-70, and the molecular weight of the hydroxyl-terminated polybutadiene is 1000-3000.

[0008] Preferably, the preparation method of the second additive is as follows: nano-silica is dispersed in toluene, ultrasonically treated for 30 min, then fluorine-terminated polyetheramine is added, and the mixture is refluxed at 105-110℃ for 5-7 h. After the reaction, the precipitate is collected by centrifugation and washed with toluene 3-5 times to obtain the second intermediate. The second intermediate is then dispersed in toluene, and dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate are added sequentially. Under nitrogen protection, the temperature is raised to 180℃ and the reaction is continued for 4-5 h to obtain the third intermediate. The third intermediate is dispersed in anhydrous ethanol, tridecafluorooctyltriethoxysilane is added, the pH is adjusted to 4-5 with acetic acid, and the mixture is stirred at 100-300 r / min at 70℃ for 4 h. After the reaction, the solid is collected by centrifugation, washed with anhydrous ethanol 3-5 times, and vacuum dried at 80℃ for 8-10 h to obtain the second additive.

[0009] Preferably, during the preparation of the second additive, after the reaction stage at 180°C, it is cooled to 100°C, then evacuated to an absolute pressure of 5-8 kPa and maintained for 30-60 min. The mass ratio of nano-silica to toluene is 1:10-20, the mass ratio of the second intermediate to toluene is 1:10-20, the mass ratio of the third intermediate to anhydrous ethanol is 1:10-20, the mass ratio of nano-silica to fluorinated polyetheramine is 1:0.2-0.3, the mass ratio of the second intermediate to dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate is 100:8-12:4-6:0.1-0.3, and the mass ratio of the third intermediate to tridecafluorooctyltriethoxysilane is 100:4-7.

[0010] Preferably, the preparation method of the third additive is as follows: 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride and p-toluenesulfonic acid are placed in a reaction vessel and reacted at 110-120℃ for 3-4 hours to obtain a fourth intermediate. The fourth intermediate, maleic anhydride and neopentyl glycol are added to the reaction vessel and reacted at 120℃ for 1 hour. Then the temperature is gradually increased to 160℃, 170℃, 180℃ and 190℃, and maintained for 1 hour at each stage. Finally, the reaction is carried out at 200℃ and vacuumed for 1 hour to complete the preparation of the third additive.

[0011] Preferably, the mass ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, p-toluenesulfonic acid, maleic anhydride and neopentyl glycol is 100:40-50:1-3:45-55:1-3.

[0012] Preferably, the base material is one or both of polyethylene terephthalate and polyethylene terephthalate-1,4-cyclohexanediol ester.

[0013] Preferably, the processing aid is composed of the following raw materials in parts by weight: 0.5-1.5 parts polyethylene wax, 0.3-0.8 parts antioxidant 1010, 0.3-0.8 parts ultraviolet absorber UV-531 and 0.2-0.6 parts zinc stearate.

[0014] A method for preparing a highly effective anti-fouling protective film for mobile phones includes the following steps: Step 1: Mix the base material, first additive, second additive, third additive, and processing aid in a high-speed mixer to obtain the first mixture; Step 2: The first mixture is passed through a twin-screw extruder and melt-blended, extruded, cooled, and pelletized within a temperature range of 230-260℃ to obtain the functional masterbatch; Step 3: The functional masterbatch is calendered to form a functional film layer. A release film is attached to one side of the functional film layer. A liquid optical adhesive is evenly coated on the other side of the functional film layer. After UV curing, a strong adhesive layer is formed. A release film is then laminated onto the adhesive surface of the cured adhesive layer to obtain a high-efficiency anti-fouling protective film for mobile phones.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, the first additive, as a fluorinated hyperbranched polyester, constructs a stable low surface energy network framework in the matrix. The second additive uses fluorinated polyether amine to pretreat nano-silica, giving it two key functions: the amine groups are firmly bonded to the nanoparticles to ensure dispersion stability, while the fluorocarbon chains interpenetrate and are compatible with the network of the first additive, achieving a high-strength interfacial bond between the inorganic nanoparticles and the matrix. The third additive, as a fluorinated branched polyester, migrates to the surface during processing to refine and densify the arrangement of the outermost fluorine atoms. Under the multiple linkage mechanisms, the protective film surface simultaneously possesses extremely low surface energy and suitable micro-nano roughness, resulting in a significant synergistic effect and achieving all-round protection against water-based and oil-based stains. 2. In this invention, the hydroxyl-terminated polybutadiene segments in the first additive introduce flexibility, and work together with the nano-silica modified with fluorine-terminated polyetheramine in the second additive. The latter, as a highly efficient nano-reinforcement, is uniformly dispersed in the matrix. Through physical cross-linking points and chemical bonding, it significantly improves the rigidity and scratch resistance of the material. At the same time, the branched structure of the third additive helps to reduce crystallization defects, and the good compatibility and interfacial bonding between the components effectively avoid light scattering caused by phase separation. Attached Figure Description

[0016] Figure 1 The present invention provides a flowchart of a highly efficient anti-fouling protective film for mobile phones and its preparation method. Detailed Implementation

[0017] 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.

[0018] It should be noted that the raw materials used in the following embodiments are all commercially available.

[0019] Example 1: A highly efficient anti-fouling protective film for mobile phones, comprising a functional film layer, the functional film layer being composed of the following raw materials in parts by weight: 80 parts base material, 8 parts first additive, 8 parts second additive, 3 parts third additive, and 1 part processing aid; The raw materials for the first additive include octafluoropentanol, trimellitic anhydride, terephthalic acid, isophthalic acid, ethylene glycol, hydroxyl-terminated polybutadiene, and tetrabutyl titanate. The raw materials for the second additive include nano-silica, fluorinated polyetheramine, dimethyl 2,5-furandicarboxylate, 1,3-propanediol, tetrabutyl titanate, toluene, anhydrous ethanol, and acetic acid. The raw materials for the third additive include 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, maleic anhydride, neopentyl glycol, and p-toluenesulfonic acid.

[0020] The preparation method of the first additive is as follows: Octafluoropentanol, trimellitic anhydride and tetrabutyl titanate are added to the reaction vessel, and under nitrogen protection, the temperature is slowly raised to 160°C and reacted for 2 hours to obtain the first intermediate. Then, terephthalic acid, isophthalic acid, ethylene glycol and hydroxyl-terminated polybutadiene are added, and the temperature is raised to 210°C until the water output reaches more than 95% of the theoretical value. Then, the absolute pressure is adjusted to less than 100 Pa, the temperature is controlled at 240°C, and the reaction is carried out for 3 hours to obtain the first additive.

[0021] The mass ratio of octafluoropentanol, trimellitic anhydride, tetrabutyl titanate, terephthalic acid, isophthalic acid, ethylene glycol, and hydroxyl-terminated polybutadiene is 100:60:0.5:70:20:40:50, and the molecular weight of the hydroxyl-terminated polybutadiene is 1000.

[0022] The preparation method of the second additive is as follows: Nano-silica is dispersed in toluene, ultrasonically treated for 30 min, and then fluorinated polyetheramine is added. The mixture is refluxed at 105℃ for 5 h. After the reaction is completed, the precipitate is collected by centrifugation and washed three times with toluene to obtain the second intermediate. The second intermediate is then dispersed in toluene, and dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate are added sequentially. Under nitrogen protection, the temperature is raised to 180℃ and the reaction is continued for 4 h to obtain the third intermediate. The third intermediate is dispersed in anhydrous ethanol, and tridecafluorooctyltriethoxysilane is added. The pH is adjusted to 4 with acetic acid, and the mixture is stirred at 100-300 r / min at 70℃ for 4 h. After the reaction is completed, the solid is collected by centrifugation, washed three times with anhydrous ethanol, and vacuum dried at 80℃ for 8 h to obtain the second additive.

[0023] During the preparation of the second additive, after the reaction stage at 180°C, it is cooled to 100°C, then vacuumed to an absolute pressure of 5 kPa and maintained for 30 min. The mass ratio of nano-silica to toluene is 1:10, the mass ratio of the second intermediate to toluene is 1:10, the mass ratio of the third intermediate to anhydrous ethanol is 1:10, the mass ratio of nano-silica to fluorinated polyetheramine is 1:0.2, the mass ratio of the second intermediate to dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate is 100:8:4:0.1, and the mass ratio of the third intermediate to tridecafluorooctyltriethoxysilane is 100:4.

[0024] The preparation method of the third additive is as follows: 1H,1H,2H,2H-perfluoro-1-decanol, 1,2,4-benzenetricarboxylic anhydride and p-toluenesulfonic acid are placed in a reaction vessel and reacted at 115℃ for 3 hours to obtain the fourth intermediate. The fourth intermediate, maleic anhydride and neopentyl glycol are added to the reaction vessel and reacted at 120℃ for 1 hour. Then the temperature is gradually increased to 160℃, 170℃, 180℃ and 190℃, and maintained for 1 hour at each stage. Finally, the reaction is carried out at 200℃ and vacuumed for 1 hour to complete the preparation of the third additive.

[0025] The mass ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, p-toluenesulfonic acid, maleic anhydride and neopentyl glycol is 100:40:1:45:1.

[0026] The base material is polyethylene terephthalate.

[0027] The processing aid consists of the following raw materials in parts by weight: 0.5 parts polyethylene wax, 0.3 parts antioxidant 1010, 0.3 parts ultraviolet absorber UV-531 and 0.2 parts zinc stearate.

[0028] A method for preparing a highly effective anti-fouling protective film for mobile phones includes the following steps: Step 1: Mix the base material, first additive, second additive, third additive, and processing aid in a high-speed mixer to obtain the first mixture; Step 2: The first mixture is passed through a twin-screw extruder and melt-blended, extruded, cooled, and pelletized within a temperature range of 230-260℃ to obtain the functional masterbatch; Step 3: The functional masterbatch is calendered to form a functional film layer. A release film is attached to one side of the functional film layer. A liquid optical adhesive is evenly coated on the other side of the functional film layer. After UV curing, a strong adhesive layer is formed. A release film is then laminated onto the adhesive surface of the cured adhesive layer to obtain a high-efficiency anti-fouling protective film for mobile phones.

[0029] Among them, the average particle size of the nano-silica is 10nm, and the purity is greater than 99.8%. The fluorine-terminated polyetheramine has a molecular weight of 800, a fluorine content of 15%, and an amine value of 1.8 mmol / g.

[0030] A highly effective anti-fouling screen protector for mobile phones includes a functional film layer, which is composed of the following raw materials in parts by weight: 90 parts base material, 9 parts first additive, 9 parts second additive, 4 parts third additive, and 2 parts processing aid. The raw materials for the first additive include octafluoropentanol, trimellitic anhydride, terephthalic acid, isophthalic acid, ethylene glycol, hydroxyl-terminated polybutadiene, and tetrabutyl titanate. The raw materials for the second additive include nano-silica, fluorinated polyetheramine, dimethyl 2,5-furandicarboxylate, 1,3-propanediol, tetrabutyl titanate, toluene, anhydrous ethanol, and acetic acid. The raw materials for the third additive include 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, maleic anhydride, neopentyl glycol, and p-toluenesulfonic acid.

[0031] The preparation method of the first additive is as follows: Octafluoropentanol, trimellitic anhydride and tetrabutyl titanate are added to the reaction vessel, and under nitrogen protection, the temperature is slowly raised to 170°C and reacted for 2.5 h to obtain the first intermediate. Then, terephthalic acid, isophthalic acid, ethylene glycol and hydroxyl-terminated polybutadiene are added, and the temperature is raised to 220°C until the water output reaches more than 95% of the theoretical value. Then, the absolute pressure is adjusted to less than 100 Pa, the temperature is controlled at 260°C, and the reaction is carried out for 3.5 h to obtain the first additive.

[0032] The mass ratio of octafluoropentanol, trimellitic anhydride, tetrabutyl titanate, terephthalic acid, isophthalic acid, ethylene glycol, and hydroxyl-terminated polybutadiene is 100:70:1:80:25:45:60, and the molecular weight of the hydroxyl-terminated polybutadiene is 2000.

[0033] The preparation method of the second additive is as follows: Nano-silica is dispersed in toluene, ultrasonically treated for 30 min, and then fluorinated polyetheramine is added. The mixture is refluxed at 108 °C for 6 h. After the reaction is completed, the precipitate is collected by centrifugation and washed four times with toluene to obtain the second intermediate. The second intermediate is then dispersed in toluene, and dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate are added sequentially. Under nitrogen protection, the temperature is raised to 180 °C and the reaction is continued for 4.5 h to obtain the third intermediate. The third intermediate is dispersed in anhydrous ethanol, and tridecafluorooctyltriethoxysilane is added. The pH is adjusted to 4 with acetic acid, and the mixture is stirred at 70 °C at 200 r / min for 4 h. After the reaction is completed, the solid is collected by centrifugation, washed four times with anhydrous ethanol, and vacuum dried at 80 °C for 9 h to obtain the second additive.

[0034] During the preparation of the second additive, after the reaction stage at 180°C, it is cooled to 100°C, then evacuated to an absolute pressure of 6 kPa and maintained for 40 min. The mass ratio of nano-silica to toluene is 1:15, the mass ratio of the second intermediate to toluene is 1:15, the mass ratio of the third intermediate to anhydrous ethanol is 1:15, the mass ratio of nano-silica to fluorinated polyetheramine is 1:0.25, the mass ratio of the second intermediate to dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate is 100:10:5:0.2, and the mass ratio of the third intermediate to tridecafluorooctyltriethoxysilane is 100:6.

[0035] The preparation method of the third additive is as follows: 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride and p-toluenesulfonic acid are placed in a reaction vessel and reacted at 115℃ for 3.5h to obtain the fourth intermediate. The fourth intermediate, maleic anhydride and neopentyl glycol are added to the reaction vessel and reacted at 120℃ for 1h. Then the temperature is gradually increased to 160℃, 170℃, 180℃ and 190℃, and maintained for 1h at each stage. Finally, the reaction is carried out at 200℃ and vacuumed for 1h to complete the preparation of the third additive.

[0036] The mass ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, p-toluenesulfonic acid, maleic anhydride and neopentyl glycol is 100:45:2:50:2.

[0037] The base material is a combination of two materials: polyethylene terephthalate and polyethylene terephthalate-1,4-cyclohexanediol ester.

[0038] The processing aid consists of the following raw materials in parts by weight: 1 part polyethylene wax, 0.6 parts antioxidant 1010, 0.6 parts ultraviolet absorber UV-531 and 0.4 parts zinc stearate.

[0039] A method for preparing a highly effective anti-fouling protective film for mobile phones includes the following steps: Step 1: Mix the base material, first additive, second additive, third additive, and processing aid in a high-speed mixer to obtain the first mixture; Step 2: The first mixture is passed through a twin-screw extruder and melt-blended, extruded, cooled, and pelletized within a temperature range of 230-260℃ to obtain the functional masterbatch; Step 3: The functional masterbatch is calendered to form a functional film layer. A release film is attached to one side of the functional film layer. A liquid optical adhesive is evenly coated on the other side of the functional film layer. After UV curing, a strong adhesive layer is formed. A release film is then laminated onto the adhesive surface of the cured adhesive layer to obtain a high-efficiency anti-fouling protective film for mobile phones.

[0040] Among them, the average particle size of the nano-silica is 20nm, and the purity is greater than 99.8%. The molecular weight of the fluorinated polyetheramine is 1500, the fluorine content is 25%, and the amine value is 2 mmol / g; Example

[0041] A highly effective anti-fouling screen protector for mobile phones includes a functional film layer, which is composed of the following raw materials in parts by weight: 100 parts base material, 10 parts first additive, 10 parts second additive, 5 parts third additive, and 3 parts processing aid. The raw materials for the first additive include octafluoropentanol, trimellitic anhydride, terephthalic acid, isophthalic acid, ethylene glycol, hydroxyl-terminated polybutadiene, and tetrabutyl titanate. The raw materials for the second additive include nano-silica, fluorinated polyetheramine, dimethyl 2,5-furandicarboxylate, 1,3-propanediol, tetrabutyl titanate, toluene, anhydrous ethanol, and acetic acid. The raw materials for the third additive include 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, maleic anhydride, neopentyl glycol, and p-toluenesulfonic acid.

[0042] The preparation method of the first additive is as follows: Octafluoropentanol, trimellitic anhydride and tetrabutyl titanate are added to the reaction vessel, and under nitrogen protection, the temperature is slowly raised to 180°C and reacted for 3 hours to obtain the first intermediate. Then, terephthalic acid, isophthalic acid, ethylene glycol and hydroxyl-terminated polybutadiene are added, and the temperature is raised to 240°C until the water output reaches more than 95% of the theoretical value. Then, the absolute pressure is adjusted to be less than 100 Pa, the temperature is controlled at 280°C, and the reaction is carried out for 4 hours to obtain the first additive.

[0043] The mass ratio of octafluoropentanol, trimellitic anhydride, tetrabutyl titanate, terephthalic acid, isophthalic acid, ethylene glycol, and hydroxyl-terminated polybutadiene is 100:80:1.5:90:30:50:70, and the molecular weight of the hydroxyl-terminated polybutadiene is 3000.

[0044] The preparation method of the second additive is as follows: Nano-silica is dispersed in toluene, ultrasonically treated for 30 min, and then fluorinated polyetheramine is added. The mixture is refluxed at 110 °C for 7 h. After the reaction is completed, the precipitate is collected by centrifugation and washed 5 times with toluene to obtain the second intermediate. The second intermediate is then dispersed in toluene, and dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate are added sequentially. Under nitrogen protection, the temperature is raised to 180 °C and the reaction is continued for 5 h to obtain the third intermediate. The third intermediate is dispersed in anhydrous ethanol, and tridecafluorooctyltriethoxysilane is added. The pH is adjusted to 5 with acetic acid, and the mixture is stirred at 300 r / min at 70 °C for 4 h. After the reaction is completed, the solid is collected by centrifugation, washed 5 times with anhydrous ethanol, and vacuum dried at 80 °C for 10 h to obtain the second additive.

[0045] During the preparation of the second additive, after the reaction stage at 180°C, it is cooled to 100°C, then evacuated to an absolute pressure of 8 kPa and maintained for 60 min. The mass ratio of nano-silica to toluene is 1:20, the mass ratio of the second intermediate to toluene is 1:20, the mass ratio of the third intermediate to anhydrous ethanol is 1:20, the mass ratio of nano-silica to fluorinated polyetheramine is 1:0.3, the mass ratio of the second intermediate to dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate is 100:12:6:0.3, and the mass ratio of the third intermediate to tridecafluorooctyltriethoxysilane is 100:7.

[0046] The preparation method of the third additive is as follows: 1H,1H,2H,2H-perfluoro-1-decanol, 1,2,4-benzenetricarboxylic anhydride and p-toluenesulfonic acid are placed in a reaction vessel and reacted at 120℃ for 4 hours to obtain the fourth intermediate. The fourth intermediate, maleic anhydride and neopentyl glycol are added to the reaction vessel and reacted at 120℃ for 1 hour. Then the temperature is gradually increased to 160℃, 170℃, 180℃ and 190℃, and maintained for 1 hour at each stage. Finally, the reaction is carried out at 200℃ and vacuumed for 1 hour to complete the preparation of the third additive.

[0047] The mass ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, p-toluenesulfonic acid, maleic anhydride and neopentyl glycol is 100:50:3:55:3.

[0048] The base material is polyethylene terephthalate.

[0049] The processing aid consists of the following raw materials in parts by weight: 1.5 parts polyethylene wax, 0.8 parts antioxidant 1010, 0.8 parts ultraviolet absorber UV-531 and 0.6 parts zinc stearate.

[0050] A method for preparing a highly effective anti-fouling protective film for mobile phones includes the following steps: Step 1: Mix the base material, first additive, second additive, third additive, and processing aid in a high-speed mixer to obtain the first mixture; Step 2: The first mixture is passed through a twin-screw extruder and melt-blended, extruded, cooled, and pelletized within a temperature range of 230-260℃ to obtain the functional masterbatch; Step 3: The functional masterbatch is calendered to form a functional film layer. A release film is attached to one side of the functional film layer. A liquid optical adhesive is evenly coated on the other side of the functional film layer. After UV curing, a strong adhesive layer is formed. A release film is then laminated onto the adhesive surface of the cured adhesive layer to obtain a high-efficiency anti-fouling protective film for mobile phones.

[0051] Among them, the average particle size of the nano-silica is 30nm, and the purity is greater than 99.8%. The fluorine-terminated polyetheramine has a molecular weight of 3000, a fluorine content of 45%, and an amine value of 2.2 mmol / g. In Examples 1-3, during the melt blending process, the temperature of the twin-screw extruder from the feed inlet to the die head is set as follows: Zone 1 230°C, Zone 2 240°C, Zone 3 250°C, and Die head 260°C. The screw speed is 300 r / min, and vacuum exhaust is performed at -0.08 MPa during the extrusion process. Comparative Example 1: The difference between this comparative example and Example 1 is that this comparative example does not contain the first additive.

[0052] Comparative Example 2 differs from Example 1 in that it does not contain a second additive.

[0053] Comparative Example 3 differs from Example 1 in that it does not contain a third additive.

[0054] Performance testing: The high-efficiency anti-fouling protective films for mobile phones prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance testing, and the test data are recorded in the table below: Transmittance and haze testing: Refer to national standard GB / T 2410-2008. Turn on the color haze meter. After the self-test is completed, preheat the lamp source for 15 minutes. After preheating, press the OK button to open the sample chamber. Then test the total transmittance and haze of the blank sample. The blank sample should have a transmittance of 100% and a haze of 0%. Close the sample chamber, cut the sample to completely cover the light-transmitting hole, and start the measurement. Record the data. Measure at least two different positions for each sample. When the transmittance is ≥90% and the haze is ≤0.8% in each experiment, the optical performance is considered qualified. Pencil Hardness: Referring to the national standard GB / T 6739-2022, a 1H (6H) pencil (MITSUBISHI-UNI test pencil) was used. The wooden part of the pencil was shaved off with a pencil sharpener, exposing about 6mm of the lead in a cylindrical shape. Then, a piece of 400-grit sandpaper was placed on a hard surface, and the lead was held vertically against the sandpaper and rubbed in circles, slowly grinding until the pencil tip was ground to a 90-degree flat surface with a sharp edge. The edge should be free of debris and nicks, resulting in a smooth, flat circular cross-section. The sharpened pencil was then placed on a dedicated pencil hardness tester (the load applied to the pencil tip was 1kg, and the angle between the pencil and the horizontal plane was 45°). The pencil was pushed forward 10mm on the test sample surface at a speed of 0.5mm / s, and the pencil lead was used to scratch the sample surface. The pencil position was changed after each scratch, for a total of 5 scratches. The pencil tip was re-sharpened after each scratch before reuse. Finally, erase the pencil marks with an eraser. The following criteria are met: the protective film must not be broken after the test, the surface of the protective film must not have any scratches, slight scratches are allowed within 2mm of the starting position, and there must be no scratches when the hardness is 1000g / 2H. Fingerprint resistance test: Prepare artificial fingerprint solution (weight ratio: myristic acid: glycerin: oleic acid: cholesterol: squalene: water = 5:5:5:1:1:83). Use a fingerprint mold to evenly imprint 0.2 mL of fingerprint solution onto the sample surface. After standing at room temperature for 10 minutes, wipe 10 times unidirectionally with a microfiber cloth (soaked in a small amount of isopropanol) under a 1 kg load. Observe and rate: Grade 5 - No residue at all, original shine; Grade 4 - Very slight visible residue; Grade 3 - Visible residue, but the outline is blurred; Grade 2 - Clear fingerprint outline; Grade 1 - Severe fingerprint residue, difficult to wipe off. Water contact angle and oil contact angle were tested according to the national standard GB / T 30447-2013 "Method for Measurement of Contact Angle of Nanofilms". A contact angle measuring instrument was used, and the test solution was deionized water and diiodomethane. At room temperature, 2μL of test solution was dropped onto the sample surface using a microsyringe. The instrument automatically took pictures and calculated the average value of the left and right contact angles. Five different points were tested for each sample and the average value was taken.

[0055] Table 1. Protective Film Performance Test Table In Table 1, the contact angle data are expressed as "mean ± standard deviation". The superior performance of Examples 1-3 is due to the molecular synergy of the three additives. The first additive, as a fluorinated hyperbranched polyester backbone, constructs a low surface energy network in the matrix. The second additive, through fluorinated polyetheramine modification of nano-silica, achieves a dual function: its amine groups are firmly bonded to nano-silica, while the fluorocarbon chains are compatible with the network of the first additive. The nanoparticles simultaneously construct a micro-nano rough structure. The third additive, as a fluorinated branched polyester, migrates to the surface during processing, further densifying the fluorine atom arrangement. The synergy of these three additives precisely achieves the combination of low surface energy chemical composition and micro-nano rough physical structure, thereby obtaining high contact angle and excellent fingerprint resistance.

[0056] In Comparative Example 1, the absence of the first additive led to a fundamental defect in the entire system. The first additive is the basic framework for constructing a continuous fluorinated polymer network. Its absence caused the system to lose its main low surface energy matrix. Although the second additive provided roughness and some fluorine atoms, and the third additive was mobile, the fluorine atoms could not form a dense and continuous chemical cross-linked network, resulting in a significant increase in surface energy. According to the data, its water contact angle was only 98°, its fingerprint resistance was level 2, and its standard deviation was the largest, proving that the surface chemical modification was extremely uneven and incomplete, and the synergistic effect was completely destroyed. Comparative Example 2 lacks the second additive, resulting in the loss of key physical structure reinforcement and fluorine atom anchoring centers. The nano-silica without fluorine-terminated polyetheramine modification relies solely on the chemical modification of the first and third additives, lacking the necessary micro-nano roughness to amplify the hydrophobic and oleophobic effects. At the same time, the lack of fluorine-terminated polyetheramine significantly reduces the effective anchor point density of fluorine atoms on the surface. Although its water contact angle and oil contact angle are better than those of Comparative Example 1, they are far inferior to those of the Example, and its fingerprint resistance is average, proving that the lack of rough structure reinforcement is the performance bottleneck. Comparative Example 3 lacked a third additive, resulting in insufficient final modification and optimization of the fluorine atom arrangement on the surface. While the first and second additives provided the basic fluorinated network and rough structure, the absence of the third additive meant that these molecular structures were more prone to migrating to the fluorinated branched polymers at the interface, leading to insufficient fluorine atom density and order on the outermost surface. Although the water contact angle was acceptable, the oil contact angle and anti-fingerprint properties significantly decreased. This reflects the crucial role of the third additive in optimizing surface energy, particularly improving oleophobicity and anti-fingerprint performance. The surface fluorocarbon chains exhibited insufficient packing order. By comparing and analyzing the relevant data in the table, it can be seen that the protective film for mobile phones treated with the high-efficiency anti-fouling film of this invention not only has good anti-fouling performance but also excellent hardness. This indicates that the high-efficiency anti-fouling mobile phone protective film provided by this invention has a broader market prospect and is more suitable for promotion.

[0057] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0058] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A highly effective anti-fouling screen protector for mobile phones, characterized in that: It includes a functional membrane layer, which is composed of the following raw materials in parts by weight: 80-100 parts of base material, 8-10 parts of first additive, 8-10 parts of second additive, 3-5 parts of third additive, and 1-3 parts of processing aid. The raw materials for the first additive include octafluoropentanol, trimellitic anhydride, terephthalic acid, isophthalic acid, ethylene glycol, hydroxyl-terminated polybutadiene, and tetrabutyl titanate. The raw materials for the second additive include nano-silica, fluorinated polyetheramine, dimethyl 2,5-furandicarboxylate, 1,3-propanediol, tetrabutyl titanate, toluene, anhydrous ethanol, and acetic acid. The raw materials for the third additive include 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, maleic anhydride, neopentyl glycol, and p-toluenesulfonic acid.

2. The high-efficiency anti-fouling protective film for mobile phones according to claim 1, characterized in that, The preparation method of the first additive is as follows: Octafluoropentanol, trimellitic anhydride and tetrabutyl titanate are added to a reaction vessel, and under nitrogen protection, the temperature is slowly raised to 160-180℃ and reacted for 2-3 hours to obtain the first intermediate. Then, terephthalic acid, isophthalic acid, ethylene glycol and hydroxyl-terminated polybutadiene are added, and the temperature is raised to 210-240℃ until the water output reaches more than 95% of the theoretical value. Then, the absolute pressure is adjusted to less than 100 Pa, the temperature is controlled at 240-280℃, and the reaction is carried out for 3-4 hours to obtain the first additive.

3. The high-efficiency anti-fouling protective film for mobile phones according to claim 1, characterized in that, The mass ratio of octafluoropentanol, trimellitic anhydride, tetrabutyl titanate, terephthalic acid, isophthalic acid, ethylene glycol, and hydroxyl-terminated polybutadiene is 100:60-80:0.5-1.5:70-90:20-30:40-50:50-70, and the molecular weight of the hydroxyl-terminated polybutadiene is 1000-3000.

4. The high-efficiency anti-fouling protective film for mobile phones according to claim 1, characterized in that, The preparation method of the second additive is as follows: nano-silica is dispersed in toluene, ultrasonically treated for 30 min, then fluorine-terminated polyetheramine is added, and the mixture is refluxed at 105-110℃ for 5-7 h. After the reaction is completed, the precipitate is collected by centrifugation and washed with toluene 3-5 times to obtain the second intermediate. The second intermediate is then dispersed in toluene, and dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate are added sequentially. Under nitrogen protection, the temperature is raised to 180℃ and the reaction is continued for 4-5 h to obtain the third intermediate. The third intermediate is dispersed in anhydrous ethanol, tridecafluorooctyltriethoxysilane is added, the pH is adjusted to 4-5 with acetic acid, and the mixture is stirred at 100-300 r / min at 70℃ for 4 h. After the reaction is completed, the solid is collected by centrifugation, washed with anhydrous ethanol 3-5 times, and vacuum dried at 80℃ for 8-10 h to obtain the second additive.

5. The high-efficiency anti-fouling protective film for mobile phones according to claim 1, characterized in that, During the preparation of the second additive, after the reaction stage at 180°C, it is cooled to 100°C, then evacuated to an absolute pressure of 5-8 kPa and maintained for 30-60 minutes. The mass ratio of nano-silica to toluene is 1:10-20, the mass ratio of the second intermediate to toluene is 1:10-20, the mass ratio of the third intermediate to anhydrous ethanol is 1:10-20, the mass ratio of nano-silica to fluorinated polyetheramine is 1:0.2-0.3, the mass ratio of the second intermediate to dimethyl 2,5-furandicarboxylate, 1,3-propanediol and tetrabutyl titanate is 100:8-12:4-6:0.1-0.3, and the mass ratio of the third intermediate to tridecafluorooctyltriethoxysilane is 100:4-7.

6. The highly efficient anti-fouling protective film for mobile phones according to claim 1, characterized in that, The preparation method of the third additive is as follows: 1H,1H,2H,2H-perfluoro-1-decanol, 1,2,4-benzenetricarboxylic anhydride and p-toluenesulfonic acid are placed in a reaction vessel and reacted at 110-120℃ for 3-4 hours to obtain a fourth intermediate. The fourth intermediate, maleic anhydride and neopentyl glycol are added to the reaction vessel and reacted at 120℃ for 1 hour. Then the temperature is gradually increased to 160℃, 170℃, 180℃ and 190℃, and maintained for 1 hour at each stage. Finally, the reaction is carried out at 200℃ and vacuumed for 1 hour to complete the preparation of the third additive.

7. The highly efficient anti-fouling protective film for mobile phones according to claim 1, characterized in that, The mass ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol, 1,2,4-benzenetricarboxylic anhydride, p-toluenesulfonic acid, maleic anhydride and neopentyl glycol is 100:40-50:1-3:45-55:1-3.

8. The highly efficient anti-fouling protective film for mobile phones according to claim 1, characterized in that, The base material is one or both of polyethylene terephthalate and polyethylene terephthalate-1,4-cyclohexanediol ester.

9. The highly efficient anti-fouling protective film for mobile phones according to claim 1, characterized in that, The processing aid is composed of the following raw materials in parts by weight: 0.5-1.5 parts polyethylene wax, 0.3-0.8 parts antioxidant 1010, 0.3-0.8 parts ultraviolet absorber UV-531 and 0.2-0.6 parts zinc stearate.

10. A method for preparing a highly efficient anti-fouling protective film for mobile phones according to any one of claims 1 to 9, characterized in that, Includes the following steps: Step 1: Mix the base material, first additive, second additive, third additive, and processing aid in a high-speed mixer to obtain the first mixture; Step 2: The first mixture is passed through a twin-screw extruder and melt-blended, extruded, cooled, and pelletized within a temperature range of 230-260℃ to obtain the functional masterbatch; Step 3: The functional masterbatch is calendered to form a functional film layer. A release film is attached to one side of the functional film layer. A liquid optical adhesive is evenly coated on the other side of the functional film layer. After UV curing, a strong adhesive layer is formed. A release film is then laminated onto the adhesive surface of the cured adhesive layer to obtain a high-efficiency anti-fouling protective film for mobile phones.

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