An anti-reflection eye protection film and its preparation method

Abstract

The present invention relates to the field of film technology, and particularly to an anti-reflection eye protection film and a preparation method thereof. The anti-reflection eye protection film is obtained by coating a mixture of nano-hollow microspheres A and nano-hollow microspheres B on the surface of a glass substrate. The nano-hollow microspheres A are obtained by emulsion polymerization of methyl methacrylate, 2-hydroxyethyl methacrylate, and ethylene glycol dimethacrylate using an amphiphilic macromolecular RAFT reagent A as an emulsifier. The nano-hollow microspheres B are obtained by emulsion polymerization of methyl methacrylate, glycidyl methacrylate, and ethylene glycol dimethacrylate using an amphiphilic macromolecular RAFT reagent B as an emulsifier. The anti-reflection eye protection film prepared by the present invention has excellent light transmittance and extremely low reflectivity, and can maintain excellent optical properties for a long time during actual use. This stability makes it suitable for a variety of application scenarios, such as glasses, display screens, and other optical devices.

Description

Technical Field

[0001] The present invention relates to the field of film technology, and particularly to an anti-reflection eye protection film and a preparation method thereof. Background Art

[0002] Anti-reflection eye protection films play an important role in modern optical applications, especially in electronic display devices, spectacle lenses, and other optical devices that require reducing reflection and increasing light transmittance. With the progress of technology and the increasing demand for visual comfort, the development of anti-reflection films with excellent optical properties and durability has become a research hotspot.

[0003] The main function of an anti-reflection film is to reduce the reflection of light on the surface of a medium and increase the light transmittance, thereby enhancing visual clarity and brightness. Traditional anti-reflection films are usually achieved by coating one or more layers of materials with specific refractive indices on the surface of a substrate. These materials reduce the intensity of the reflected light through an interference effect. However, traditional methods have deficiencies in terms of abrasion resistance and long-term stability. Especially in the case of frequent use or cleaning, the film layer is prone to wear, resulting in a decline in optical performance. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide an anti-reflection eye protection film and a preparation method thereof to solve the problem that in the case of frequent use or cleaning, the film layer of a traditional anti-reflection film is prone to wear, resulting in a decline in optical performance.

[0005] Based on the above purpose, the present invention provides a preparation method of an anti-reflection eye protection film, including the following steps:

[0006] (1) Add methacrylic acid, methyl methacrylate, trithiocarbonate, 4,4'-azobis(4-cyanovaleric acid) to dioxane, heat up to 70 - 80 °C, carry out a polymerization reaction for 5 - 7 h, and perform rotary evaporation to obtain an amphiphilic macromolecular RAFT reagent A;

[0007] (2) Add methacrylic acid, methyl methacrylate, trithiocarbonate, 4,4'-azobis(4-cyanovaleric acid) to dioxane, heat up to 70 - 80 °C, carry out a polymerization reaction for 5 - 7 h, and perform rotary evaporation to obtain an amphiphilic macromolecular RAFT reagent B;

[0008] (3) Add the amphiphilic macromolecular RAFT reagent A to deionized water, adjust the pH to 7 - 8 with sodium hydroxide to obtain an aqueous phase, then mix methyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 20 - 40 min, then ultrasonicate for 15 - 25 min, and then heat up to 65 - 75 °C under a nitrogen atmosphere, react for 5 - 7 h, and finally perform vacuum drying to obtain nano-hollow microspheres A;

[0009] (4) Add the amphiphilic macromolecular RAFT reagent B to deionized water, adjust the pH to 7 - 8 with sodium hydroxide to obtain the aqueous phase. Then mix methyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 20 - 40 min, then sonicate for 30 - 50 min. Then, under a nitrogen atmosphere, heat up to 65 - 75 °C and react for 3 - 5 h. Finally, conduct vacuum drying to obtain nano - hollow microspheres B;

[0010] (5) Disperse nano - hollow microspheres A and nano - hollow microspheres B in deionized water, spin - coat them on the surface of a glass substrate, and conduct vacuum drying after spin - coating to obtain an anti - reflective and eye - protecting film.

[0011] Preferably, the addition amount of dioxane in step (1) is 2 - 5 times the total weight of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4 - cyanovaleric acid).

[0012] Preferably, the molar ratio of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4 - cyanovaleric acid) in step (1) is 15 - 20:10 - 14:0.8 - 1.2:0.05 - 0.15.

[0013] Preferably, the addition amount of dioxane in step (2) is 2 - 5 times the total weight of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4 - cyanovaleric acid).

[0014] Preferably, the molar ratio of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4 - cyanovaleric acid) in step (2) is 20 - 28:3 - 9:0.8 - 1.2:0.05 - 0.15.

[0015] Preferably, the power of sonication in step (3) is 400 - 600 w.

[0016] Preferably, the weight ratio of the amphiphilic macromolecular RAFT reagent A, deionized water, methyl methacrylate, 2 - hydroxyethyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile in step (3) is 15 - 25:50 - 110:20 - 28:10 - 16:4 - 8:15 - 25:0.1 - 0.3.

[0017] Preferably, the weight ratio of the amphiphilic macromolecular RAFT reagent B, deionized water, methyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile in step (4) is 3 - 7:15 - 25:4 - 8:2.5 - 4.5:1 - 2:2 - 8:0.02 - 0.1.

[0018] Preferably, the power of the ultrasonic wave in step (4) is 800-1200w.

[0019] Preferably, the addition amount of deionized water in step (5) is 15-30 times the total weight of nano-hollow microspheres A and nano-hollow microspheres B.

[0020] Preferably, the weight ratio of nano-hollow microspheres A and nano-hollow microspheres B in step (5) is 2:0.5-1.5.

[0021] Furthermore, the present invention also provides an anti-reflection eye protection film obtained by the preparation method of the anti-reflection eye protection film.

[0022] Advantages of the present invention:

[0023] The anti-reflection eye protection film of the present invention exhibits excellent optical properties and durability. The film has excellent light transmittance and extremely low reflectance in the initial state, ensuring clear visual effects and comfortable use experiences. More importantly, even after being polished, the film still maintains a high light transmittance and a low reflectance, indicating that it can maintain excellent optical properties for a long time during actual use. This stability makes it suitable for a variety of application scenarios, such as glasses, display screens, and other optical devices.

[0024] By regulating the lengths of the hydrophilic segment and the hydrophobic segment of the amphiphilic macromolecular RAFT reagent, the present invention can effectively adjust the light transmittance and reflectance of the film. This is because different segment lengths can adjust the particle sizes of nano-hollow microspheres A and B, enabling the small-sized microspheres B to fill the stacking gaps of microspheres A, reducing scattering and refraction, thereby increasing the light transmittance and decreasing the reflectance.

[0025] The dosages of nano-hollow microspheres A and B in the present invention also have a significant impact on the optical properties of the film. Appropriate dosages can significantly reduce the average reflectance, which is crucial for achieving broadband anti-reflection. However, using only one of the microspheres alone will lead to a decline in wear resistance because the adhesion force between the microspheres in the coating formed by a single microsphere is low and it is easy to fall off during the polishing process. Therefore, a reasonable combination and dosage of microspheres are the key to ensuring the film performance. Specific embodiments

[0026] To make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the following further elaborates on the present invention in conjunction with specific embodiments.

[0027] Example 1:

[0028] (1) Add 12.9 g of methacrylic acid, 10 g of methyl methacrylate, 2.9 g of trithiocarbonate, and 0.14 g of 4,4'-azobis(4-cyanovaleric acid) to 52 g of dioxane, heat up to 70 °C, carry out polymerization reaction for 5 h, and perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent A;

[0029] (2) Add 17.3 g of methacrylic acid, 3 g of methyl methacrylate, 2.9 g of trithiocarbonate, and 0.14 g of 4,4'-azobis(4-cyanovaleric acid) to 47 g of dioxane, heat up to 70 °C, carry out polymerization reaction for 5 h, and perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent B;

[0030] (3) Add 15 g of amphiphilic macromolecular RAFT reagent A to 50 g of deionized water, adjust the pH to 7.1 with sodium hydroxide to obtain the aqueous phase. Then mix 20 g of methyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 4 g of ethylene glycol dimethacrylate, 15 g of paraffin wax, and 0.1 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 20 min, then ultrasonicate at a power of 400 w for 15 min. Then, under a nitrogen atmosphere, heat up to 65 °C and react for 5 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0031] (4) Add 3 g of amphiphilic macromolecular RAFT reagent B to 15 g of deionized water, adjust the pH to 7.2 with sodium hydroxide to obtain the aqueous phase. Then mix 4 g of methyl methacrylate, 2.5 g of glycidyl methacrylate, 1 g of ethylene glycol dimethacrylate, 2 g of paraffin wax, and 0.02 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 20 min, then ultrasonicate at a power of 800 w for 30 min. Then, under a nitrogen atmosphere, heat up to 65 °C and react for 3 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0032] (5) Disperse 20 g of nano-hollow microspheres A and 5 g of nano-hollow microspheres B in 375 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h after spin-coating to obtain an anti-reflection and eye-protecting film.

[0033] Example 2:

[0034] (1) Add 15.5 g of methacrylic acid, 12 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out polymerization reaction for 6 h, and perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent A;

[0035] (2) 20.7 g of methacrylic acid, 6 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) were added to 100 g of dioxane, heated to 75 °C, and subjected to a polymerization reaction for 6 h. After rotary evaporation, an amphiphilic macromolecular RAFT reagent B was obtained.

[0036] (3) 20 g of amphiphilic macromolecular RAFT reagent A was added to 80 g of deionized water, and the pH was adjusted to 7.5 with sodium hydroxide to obtain an aqueous phase. Then, 24 g of methyl methacrylate, 13.1 g of 2-hydroxyethyl methacrylate, 5.9 g of ethylene glycol dimethacrylate, 20 g of paraffin wax, and 0.2 g of azobisisobutyronitrile were mixed to obtain an oil phase. The aqueous phase and the oil phase were mixed, stirred for 30 min, then sonicated at a power of 500 w for 20 min, and then heated to 70 °C under a nitrogen atmosphere and reacted for 6 h. Finally, the paraffin wax and unreacted residual monomers were removed by vacuum drying to obtain nano-hollow microspheres A.

[0037] (4) 5 g of amphiphilic macromolecular RAFT reagent B was added to 20 g of deionized water, and the pH was adjusted to 7.5 with sodium hydroxide to obtain an aqueous phase. Then, 6 g of methyl methacrylate, 3.6 g of glycidyl methacrylate, 1.5 g of ethylene glycol dimethacrylate, 5 g of paraffin wax, and 0.05 g of azobisisobutyronitrile were mixed to obtain an oil phase. The aqueous phase and the oil phase were mixed, stirred for 30 min, then sonicated at a power of 1000 w for 40 min, and then heated to 70 °C under a nitrogen atmosphere and reacted for 4 h. Finally, the paraffin wax and unreacted residual monomers were removed by vacuum drying to obtain nano-hollow microspheres B.

[0038] (5) 20 g of nano-hollow microspheres A and 10 g of nano-hollow microspheres B were dispersed in 600 g of deionized water, spin-coated on the surface of a glass substrate, and vacuum dried for 6 h after spin-coating to obtain an anti-reflective and eye-protecting film.

[0039] Example 3:

[0040] (1) 17.2 g of methacrylic acid, 14 g of methyl methacrylate, 4.3 g of trithiocarbonate, and 0.42 g of 4,4'-azobis(4-cyanovaleric acid) were added to 180 g of dioxane, heated to 80 °C, and subjected to a polymerization reaction for 7 h. After rotary evaporation, an amphiphilic macromolecular RAFT reagent A was obtained.

[0041] (2) 24.1 g of methacrylic acid, 9 g of methyl methacrylate, 4.3 g of trithiocarbonate, and 0.42 g of 4,4'-azobis(4-cyanovaleric acid) were added to 190 g of dioxane, heated to 80 °C, and subjected to a polymerization reaction for 7 h. After rotary evaporation, an amphiphilic macromolecular RAFT reagent B was obtained.

[0042] (3) Add 25 g of amphiphilic macromolecular RAFT reagent A to 110 g of deionized water, adjust the pH to 7.8 with sodium hydroxide to obtain the aqueous phase. Then mix 28 g of methyl methacrylate, 16 g of 2-hydroxyethyl methacrylate, 8 g of ethylene glycol dimethacrylate, 25 g of paraffin wax, and 0.3 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 40 min, then ultrasonicate at a power of 600 w for 30 min. Then, under a nitrogen atmosphere, heat up to 75 °C and react for 7 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0043] (4) Add 7 g of amphiphilic macromolecular RAFT reagent B to 25 g of deionized water, adjust the pH to 8.0 with sodium hydroxide to obtain the aqueous phase. Then mix 8 g of methyl methacrylate, 4.5 g of glycidyl methacrylate, 2 g of ethylene glycol dimethacrylate, 8 g of paraffin wax, and 0.1 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 40 min, then ultrasonicate at a power of 1200 w for 50 min. Then, under a nitrogen atmosphere, heat up to 75 °C and react for 5 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0044] (5) Disperse 20 g of nano-hollow microspheres A and 15 g of nano-hollow microspheres B in 1050 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h to obtain an anti-reflection and eye-protecting film.

[0045] Comparative Example 1:

[0046] The difference between Comparative Example 1 and Example 2 is that the amphiphilic macromolecular RAFT reagent A in step (3) is replaced by amphiphilic macromolecular RAFT reagent B;

[0047] The specific steps are as follows:

[0048] (1) Add 20.7 g of methacrylic acid, 6 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, and carry out a polymerization reaction for 6 h. Then perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent B;

[0049] (2) Add 20 g of amphiphilic macromolecular RAFT reagent B to 80 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain an aqueous phase. Then mix 24 g of methyl methacrylate, 13.1 g of 2-hydroxyethyl methacrylate, 5.9 g of ethylene dimethacrylate, 20 g of paraffin wax, and 0.2 g of azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 500 w for 20 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 6 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0050] (3) Add 5 g of amphiphilic macromolecular RAFT reagent B to 20 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain an aqueous phase. Then mix 6 g of methyl methacrylate, 3.6 g of glycidyl methacrylate, 1.5 g of ethylene dimethacrylate, 5 g of paraffin wax, and 0.05 g of azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 1000 w for 40 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 4 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0051] (4) Disperse 20 g of nano-hollow microspheres A and 10 g of nano-hollow microspheres B in 600 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h after spin-coating to obtain an eye protection film.

[0052] Comparative Example 2:

[0053] The difference between Comparative Example 2 and Example 2 is that: in step (4), amphiphilic macromolecular RAFT reagent B is replaced with amphiphilic macromolecular RAFT reagent A;

[0054] The specific steps are as follows:

[0055] (1) Add 15.5 g of methacrylic acid, 12 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out a polymerization reaction for 6 h, and rotary evaporate to obtain amphiphilic macromolecular RAFT reagent A;

[0056] (2) Add 20 g of amphiphilic macromolecular RAFT reagent A to 80 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain the aqueous phase. Then mix 24 g of methyl methacrylate, 13.1 g of 2-hydroxyethyl methacrylate, 5.9 g of ethylene dimethacrylate, 20 g of paraffin wax, and 0.2 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 500 w for 20 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 6 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0057] (3) Add 5 g of amphiphilic macromolecular RAFT reagent A to 20 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain the aqueous phase. Then mix 6 g of methyl methacrylate, 3.6 g of glycidyl methacrylate, 1.5 g of ethylene dimethacrylate, 5 g of paraffin wax, and 0.05 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 1000 w for 40 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 4 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0058] (4) Disperse 20 g of nano-hollow microspheres A and 10 g of nano-hollow microspheres B in 600 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h to obtain an eye protection film.

[0059] Comparative Example 3:

[0060] The difference between Comparative Example 3 and Example 2 is that: in step (5), the amount of nano-hollow microspheres A is 10 g, and the amount of nano-hollow microspheres B is 20 g;

[0061] The specific steps are as follows:

[0062] (1) Add 15.5 g of methacrylic acid, 12 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out a polymerization reaction for 6 h, and rotary evaporate to obtain amphiphilic macromolecular RAFT reagent A;

[0063] (2) Add 20.7 g of methacrylic acid, 6 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out a polymerization reaction for 6 h, and rotary evaporate to obtain amphiphilic macromolecular RAFT reagent B;

[0064] (3) Add 20 g of amphiphilic macromolecular RAFT reagent A to 80 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain an aqueous phase. Then mix 24 g of methyl methacrylate, 13.1 g of 2-hydroxyethyl methacrylate, 5.9 g of ethylene glycol dimethacrylate, 20 g of paraffin wax, and 0.2 g of azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 500 w for 20 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 6 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0065] (4) Add 5 g of amphiphilic macromolecular RAFT reagent B to 20 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain an aqueous phase. Then mix 6 g of methyl methacrylate, 3.6 g of glycidyl methacrylate, 1.5 g of ethylene glycol dimethacrylate, 5 g of paraffin wax, and 0.05 g of azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 1000 w for 40 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 4 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0066] (5) Disperse 10 g of nano-hollow microspheres A and 20 g of nano-hollow microspheres B in 600 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h after spin-coating to obtain an eye protection film.

[0067] Comparative Example 4:

[0068] The difference between Comparative Example 4 and Example 2 is that in step (5), only nano-hollow microspheres A are added;

[0069] The specific steps are as follows:

[0070] (1) Add 15.5 g of methacrylic acid, 12 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out a polymerization reaction for 6 h, and rotary evaporate to obtain amphiphilic macromolecular RAFT reagent A;

[0071] (2) Add 20 g of amphiphilic macromolecular RAFT reagent A to 80 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain the aqueous phase. Then mix 24 g of methyl methacrylate, 13.1 g of 2-hydroxyethyl methacrylate, 5.9 g of ethylene glycol dimethacrylate, 20 g of paraffin wax, and 0.2 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 500 w for 20 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 6 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres A;

[0072] (3) Disperse 30 g of nano-hollow microspheres A in 600 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h to obtain an eye protection film.

[0073] Comparative Example 5:

[0074] The difference between Comparative Example 5 and Example 2 is that: only nano-hollow microspheres B are added in step (5);

[0075] The specific steps are as follows:

[0076] (1) Add 20.7 g of methacrylic acid, 6 g of methyl methacrylate, 3.6 g of trithiocarbonate, and 0.28 g of 4,4'-azobis(4-cyanovaleric acid) to 100 g of dioxane, heat up to 75 °C, carry out a polymerization reaction for 6 h, and rotary evaporate to obtain amphiphilic macromolecular RAFT reagent B;

[0077] (2) Add 5 g of amphiphilic macromolecular RAFT reagent B to 20 g of deionized water, adjust the pH to 7.5 with sodium hydroxide to obtain the aqueous phase. Then mix 6 g of methyl methacrylate, 3.6 g of glycidyl methacrylate, 1.5 g of ethylene glycol dimethacrylate, 5 g of paraffin wax, and 0.05 g of azobisisobutyronitrile to obtain the oil phase. Mix the aqueous phase and the oil phase, stir for 30 min, then ultrasonicate at a power of 1000 w for 40 min. Then, under a nitrogen atmosphere, heat up to 70 °C and react for 4 h. Finally, remove the paraffin wax and unreacted residual monomers by vacuum drying to obtain nano-hollow microspheres B;

[0078] (3) Disperse 30 g of nano-hollow microspheres B in 600 g of deionized water, spin-coat on the surface of a glass substrate, and vacuum dry for 6 h to obtain an eye protection film.

[0079] Performance test:

[0080] Reflectivity: Measure the average reflectivity in the wavelength range of 200 - 700 nm with a spectrophotometer, and the results are shown in Table 1;

[0081] Light transmittance: The maximum light transmittance in the wavelength range of 200 - 700 nm was measured with a spectrophotometer, and the results are shown in Table 1;

[0082] Abrasion resistance: Tested with a reciprocating linear abrasion tester, the load was 1 kg / cm 2 , the friction medium was flannel cloth, the abrasion rate was 40 cycles / min, and the abrasion time was 5 min. The average reflectance and maximum light transmittance of the film after abrasion in the wavelength range of 200 - 700 nm were measured, and the results are shown in Table 1.

[0083] Table 1 Performance test results

[0084]

[0085] Data analysis:

[0086] From the data of Examples 1 - 3 in Table 1, it can be seen that the anti - reflective and eye - protecting film prepared by the present invention has excellent light transmittance and extremely low reflectance. Most importantly, after abrasion, it still has a high light transmittance and a low reflectance, which indicates that this anti - reflective and eye - protecting film not only performs well in the initial state but also can maintain its excellent optical properties for a long time during use, and is suitable for a variety of actual application scenarios.

[0087] From the data of Example 2 and Comparative Examples 1 - 2 in Table 1, it can be known that the lengths of the hydrophilic chain segment and the hydrophobic chain segment in the amphiphilic macromolecular RAFT reagent can effectively regulate the light transmittance and reflectance of the anti - reflective and eye - protecting film. This is mainly because the lengths of the hydrophilic chain segment and the hydrophobic chain segment can effectively adjust the particle sizes of nano - hollow microspheres A and nano - hollow microspheres B, so that the small - particle - size nano - hollow microspheres B are filled in the stacking gaps of nano - hollow microspheres A, reducing the scattering and refraction caused by the stacking gaps, increasing the light transmittance, and reducing the reflectance.

[0088] From the data of Example 2 and Comparative Example 3 in Table 1, it can be seen that the dosages of nano - hollow microspheres A and nano - hollow microspheres B can regulate the light transmittance of the anti - reflective and eye - protecting film, and appropriate dosages can significantly reduce the average reflectance, which is crucial for broadband anti - reflection.

[0089] From the data of Example 2 and Comparative Examples 4 - 5 in Table 1, it can be seen that using nano - hollow microspheres A or nano - hollow microspheres B alone will cause a decrease in abrasion resistance. This is mainly because the adhesion force between nano - hollow microspheres in the coating formed by using nano - hollow microspheres A or nano - hollow microspheres B alone is relatively low, and it is easy to fall off during the abrasion process, forming an uneven surface or directly exposing the glass substrate.

[0090] Those of ordinary skill in the art should understand that: The discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples; Under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, and they are not provided in detail for the sake of brevity.

Claims

1. A preparation method of an anti-reflection and eye-protecting film, characterized in that, It includes the following steps: (1) Add methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4-cyanovaleric acid) into dioxane, heat up to 70 - 80 °C, carry out polymerization reaction for 5 - 7 h, and perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent A; (2) Add methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4-cyanovaleric acid) into dioxane, heat up to 70 - 80 °C, carry out polymerization reaction for 5 - 7 h, and perform rotary evaporation to obtain amphiphilic macromolecular RAFT reagent B; (3) Add amphiphilic macromolecular RAFT reagent A into deionized water, adjust the pH to 7 - 8 with sodium hydroxide to obtain an aqueous phase. Then mix methyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 20 - 40 min, then ultrasonicate for 15 - 25 min. Then, under a nitrogen atmosphere, heat up to 65 - 75 °C and react for 5 - 7 h. Finally, perform vacuum drying to obtain nano - hollow microspheres A; (4) Add amphiphilic macromolecular RAFT reagent B into deionized water, adjust the pH to 7 - 8 with sodium hydroxide to obtain an aqueous phase. Then mix methyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile to obtain an oil phase. Mix the aqueous phase and the oil phase, stir for 20 - 40 min, then ultrasonicate for 30 - 50 min. Then, under a nitrogen atmosphere, heat up to 65 - 75 °C and react for 3 - 5 h. Finally, perform vacuum drying to obtain nano - hollow microspheres B; (5) Disperse nano - hollow microspheres A and nano - hollow microspheres B in deionized water, spin - coat them on the surface of a glass substrate, and perform vacuum drying after spin - coating to obtain an anti - reflective and eye - protecting film; In the step (1), the molar ratio of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4-cyanovaleric acid) is 15 - 20:10 - 14:0.8 - 1.2:0.05 - 0.15; In the step (2), the molar ratio of methacrylic acid, methyl methacrylate, trithiocarbonate, and 4,4'-azobis(4-cyanovaleric acid) is 20 - 28:3 - 9:0.8 - 1.2:0.05 - 0.15; In the step (3), the weight ratio of amphiphilic macromolecular RAFT reagent A, deionized water, methyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile is 15 - 25:50 - 110:20 - 28:10 - 16:4 - 8:15 - 25:0.1 - 0.3; In the step (4), the weight ratio of amphiphilic macromolecular RAFT reagent B, deionized water, methyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, paraffin, and azobisisobutyronitrile is 3 - 7:15 - 25:4 - 8:2.5 - 4.5:1 - 2:2 - 8:0.02 - 0.1; In the step (5), the weight ratio of nano - hollow microspheres A and nano - hollow microspheres B is 2:0.5 - 1.

5.

2. The preparation method of the anti-reflection eye protection film according to claim 1, characterized in that, The addition amount of dioxane in the step (1) is 2-5 times the total weight of methacrylic acid, methyl methacrylate, trithiocarbonate and 4,4'-azobis(4-cyanovaleric acid).

3. The preparation method of the anti-reflection eye protection film according to claim 1, wherein, The addition amount of dioxane in the step (2) is 2-5 times the total weight of methacrylic acid, methyl methacrylate, trithiocarbonate and 4,4'-azobis(4-cyanovaleric acid).

4. The preparation method of the anti-reflection eye protection film according to claim 1, wherein The power of ultrasonic wave in the step (3) is 400-600 w.

5. The preparation method of the anti-reflection eye protection film according to claim 1, characterized in that, The power of ultrasonic wave in the step (4) is 800-1200 w.

6. The preparation method of the anti-reflection eye protection film according to claim 1, wherein The addition amount of deionized water in the step (5) is 15-30 times the total weight of nano-hollow microsphere A and nano-hollow microsphere B.

7. An anti-reflection eye protection film, characterized in that, Obtained by the preparation method of the anti-reflection eye protection film according to any one of claims 1-6.

Images