A high-hardness resin lens and its preparation method

Abstract

This invention belongs to the field of resin lens technology, specifically relating to a high-hardness resin lens and its preparation method, comprising a lens substrate and an anti-abrasion film layer. By weight, the lens substrate comprises the following components: 50-60 parts bisphenol A epoxy acrylate, 3-5 parts modified nano-zirconia, 30-35 parts tripropylene glycol diacrylate, 0.5-1 part azobisisobutyronitrile (AIB) initiator, 1-1.5 parts release agent, and 3-3.5 parts ultraviolet absorber. By weight, the anti-abrasion film layer comprises the following components: 20-30 parts sulfobetaine methacrylate, 10-15 parts vinyltriethoxysilane, 3-8 parts 2-hydroxy-4-acryloyloxybenzophenone, and 0.3-0.5 parts azobisisobutyronitrile (AIB). In this invention, an anti-abrasion film is coated on the outside of the lens substrate, improving the bonding strength between the anti-abrasion film and the lens substrate.

Description

Technical Field

[0001] This invention belongs to the field of resin lens technology, specifically relating to a high-hardness resin lens and its preparation method. Background Technology

[0002] Eyeglasses, as "one of the most widely used optical treatments," primarily function through their lenses. Initially, lenses were made of ground glass, which was heavy, uncomfortable, and fragile, often causing eye injuries. Optical resin lenses, being lightweight and impact-resistant, were a good alternative to glass lenses. However, the biggest drawback of resin lenses is their low hardness, susceptibility to surface wear, and poor scratch resistance, which are fundamental problems limiting their lifespan.

[0003] To improve the hardness of resin lenses, existing technologies generally treat the surface of the resin lens material to form a high-hardness anti-wear film, thereby improving the wear resistance of the resin lens.

[0004] However, the adhesion between the anti-abrasion film and the lens resin substrate is a key factor in the functionality and lifespan of the anti-abrasion film. Poor adhesion between the anti-abrasion film and the substrate leads to a reduced lifespan of the anti-abrasion film and insufficient anti-abrasion effect. Summary of the Invention

[0005] The purpose of this invention is to provide a high-hardness resin lens and its preparation method to solve the above-mentioned technical problems.

[0006] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows:

[0007] A high-hardness resin lens includes a lens substrate and an anti-abrasion coating;

[0008] The lens matrix comprises the following components by weight: 50-60 parts of bisphenol A epoxy acrylate, 3-5 parts of modified nano-zirconia, 30-35 parts of tripropylene glycol diacrylate, 0.5-1 part of azobisisobutyronitrile initiator, 1-1.5 parts of release agent, and 3-3.5 parts of ultraviolet absorber.

[0009] The anti-wear film layer comprises the following components by weight: 20-30 parts of sulfobetaine methacrylate, 10-15 parts of vinyltriethoxysilane, 3-8 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.3-0.5 parts of azobisisobutyronitrile.

[0010] As a further improvement, the ultraviolet absorber is UV329 or UV326, and the release agent is glyceryl stearate or polyethylene wax.

[0011] This invention also provides a method for preparing high-hardness resin lenses, comprising the following steps:

[0012] S1. Preparation of the lens substrate;

[0013] Bisphenol A epoxy acrylate, modified nano-zirconia, tripropylene glycol diacrylate, mold release agent and ultraviolet absorber are mixed, and then the initiator azobisisobutyronitrile is added. The mixture is vacuumed at 30°C for 30-40 minutes, and the mixture is continuously shaken and mixed evenly to obtain a viscous prepolymer. The viscous prepolymer is then poured into a glass mold, cured once, and then the mold is opened, the edges are trimmed, and the mold is cleaned. A second curing is then performed to obtain the lens substrate.

[0014] S2. Sulfobetaine methacrylate, vinyltriethoxysilane and 2-hydroxy-4-acryloyloxybenzophenone were mixed and dissolved in anhydrous ethanol. Then, azobisisobutyronitrile (AIBN) was added and the mixture was deoxygenated with argon for 30 min. The mixture was reacted at 70-80 °C for 10-12 h. After the reaction was completed, the mixture was centrifuged at 3000 rpm for 15 min. After removing the supernatant, the precipitate was redispersed in anhydrous ethanol. The centrifugation was repeated 3 times. Finally, the precipitate was dried and dissolved in trifluoroethanol to obtain a solution.

[0015] S3. Place the lens substrate in the solution, let it stand for 5 minutes, then remove it and cure it with 365nm, 100w UV light for 30 minutes. After UV curing, place it at 115℃~120℃ for curing to obtain the resin lens.

[0016] As a further improvement, in step S1, the first curing process specifically involves: an initial temperature of 25~35℃, a temperature increase to 40~45℃ in 0.5h, a temperature increase to 45~50℃ in 2.5h, a temperature increase to 52~54℃ in 9h, a temperature increase to 65~70℃ in 3h, and a temperature increase to 75~80℃ in 2h; the second curing process specifically involves: a temperature increase to 120~125℃, and curing for 2~2.5h.

[0017] As a further improvement, in step S1, the preparation method of the modified nano-zirconia is as follows: weigh the dried nano-zirconia, add it to toluene, ultrasonically disperse it at 25°C for 40 min, then add 10% by mass of γ-methacryloxypropyltrimethoxysilane aqueous solution, ultrasonically disperse it for 10 min, and then react it at 80~85°C for 25~30 min. After the reaction is completed, cool it, then centrifuge it at 16000 rpm for 20 min, ultrasonically disperse it for 10 min, filter the solid material, wash and dry it to obtain the modified nano-zirconia.

[0018] As a further improvement, for every 2g of dried nano-zirconia added, the amount of γ-methacryloxypropyltrimethoxysilane aqueous solution used is 10mL.

[0019] As a further improvement, in step S2, the concentration of the precipitate in the solution is 2 g / mL.

[0020] Due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows:

[0021] The present invention provides a high-hardness resin lens and its preparation method. An anti-wear film is coated on the outside of the lens substrate. The 2-hydroxy-4-acryloyloxybenzophenone in the anti-wear film contains hydroxyl groups. During UV curing and high-temperature curing, the hydroxyl groups and the epoxy groups on the bisphenol A epoxy acrylate of the lens substrate form a β-hydroxy ether structure, which improves the bonding strength between the anti-wear film and the lens substrate.

[0022] Vinyltriethoxysilane is used in the anti-wear film. The presence of siloxane can improve the hardness of the anti-wear film and enhance its effectiveness.

[0023] In this invention, modified nano-zirconia is added to the lens substrate. The nano-zirconia can improve the hardness of the lens substrate, forming a high-hardness lens substrate. Furthermore, the nano-zirconia is modified by γ-methacryloxypropyltrimethoxysilane. γ-methacryloxypropyltrimethoxysilane forms hydrogen bonds with the nano-zirconia, which on the one hand inhibits the aggregation of nano-zirconia, and on the other hand, during the lens substrate curing process, the propylene groups on γ-methacryloxypropyltrimethoxysilane crosslink with bisphenol A epoxy acrylate and tripropylene glycol diacrylate, improving the dispersibility of nano-zirconia with optical resin and ensuring that the nano-zirconia is uniformly distributed in the lens substrate, resulting in uniform hardness of the lens substrate.

[0024] In this invention, sulfobetaine methacrylate is added to the anti-abrasion film. This substance is a strong hydrophilic material that can improve the anti-fogging effect of the lens substrate. It will not form a fog film on the lens when entering a warm room in cold winter, thus affecting the transparency performance. At the same time, sulfobetaine methacrylate and vinyltriethoxysilane crosslink to form an amphiphilic polymer. The hydrophilic segments give the coating hygroscopicity, while the hydrophobic segments can inhibit the swelling of the coating caused by excessive moisture absorption. This solves the problem that the anti-fogging effect of strong hydrophilic materials is poor due to moisture absorption and swelling. Attached Figure Description

[0025] Figure 1 These are images of the resin lenses prepared in Example 1;

[0026] Figure 2 The images are ATR-FTIR spectra of the resin lens and lens substrate in Example 1. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0028] Example 1 A high-hardness resin lens, comprising a lens substrate and an anti-abrasion coating.

[0029] By weight, the lens matrix comprises the following components: 50 parts bisphenol A epoxy acrylate, 3 parts modified nano zirconia, 30 parts tripropylene glycol diacrylate, 0.5 parts initiator azobisisobutyronitrile, 1 part release agent glyceryl stearate, and 3 parts ultraviolet absorber UV329.

[0030] By weight, the anti-wear film layer comprises the following components: 20 parts of sulfobetaine methacrylate, 10 parts of vinyltriethoxysilane, 3 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.3 parts of azobisisobutyronitrile.

[0031] This embodiment also provides a method for preparing the above-mentioned resin lens, which specifically includes the following steps:

[0032] S1, Preparation of modified nano-zirconia;

[0033] The nano-zirconia powder was dried at 60℃ for 6 hours to obtain the dried nano-zirconia powder.

[0034] Prepare a 10% (w / w) aqueous solution of γ-methacryloxypropyltrimethoxysilane.

[0035] Weigh 2g of dried nano-zirconia and add it to 15mL of toluene. Disperse it by sonication at 25℃ for 40min. Then add 10mL of 10% (w / w) aqueous solution of γ-methacryloxypropyltrimethoxysilane. Sonicate for 10min and react at 80℃ for 30min. After the reaction is complete, cool it and centrifuge at 16000rpm for 20min. Sonicate it again for 10min. Filter the solid material, wash it, and dry it at 100℃ for 5h to obtain modified nano-zirconia.

[0036] S2. Preparation of the lens substrate;

[0037] 5g of bisphenol A epoxy acrylate, 0.3g of modified nano-zirconia, 3g of tripropylene glycol diacrylate, 0.1g of glyceryl stearate, and 0.3g of UV329 were mixed, and then 0.05g of azobisisobutyronitrile (AIB) initiator was added. The mixture was vacuumed at 30°C for 30 minutes, and continuously shaken to mix evenly to obtain a viscous prepolymer. The viscous prepolymer was then poured into a glass mold and cured once. After the mold was opened, the edges were trimmed, and the mixture was cleaned. A second curing process was then performed to obtain the lens substrate. The first curing process was as follows: initial temperature 25°C, temperature increased to 40°C in 0.5h, temperature increased to 45°C in 2.5h, temperature increased to 52°C in 9h, temperature increased to 65°C in 3h, and temperature increased to 75°C in 2h. The second curing process was as follows: temperature increased to 120°C and cured for 2.5h. The mold opening, edge trimming, and cleaning processes used techniques commonly used in the preparation of resin lenses, which will not be described in detail here.

[0038] S3, Preparation of resin lenses;

[0039] 2g of sulfobetaine methacrylate, 1g of vinyltriethoxysilane and 0.3g of 2-hydroxy-4-acryloyloxybenzophenone were mixed and dissolved in 30mL of anhydrous ethanol. Then, 0.03g of initiator azobisisobutyronitrile was added and the mixture was deoxygenated with argon for 30min. The reaction was carried out at 70℃ for 12h. After the reaction was completed, the mixture was centrifuged at 3000rpm for 15min. After removing the supernatant, the precipitate was redispersed in anhydrous ethanol. The centrifugation was repeated 3 times. Finally, the precipitate was dried at 45℃ for 24h and then dissolved in trifluoroethanol to obtain a solution of 2g / mL.

[0040] The lens substrate is placed in the solution and left to stand for 5 minutes. Then it is removed and cured with 365nm, 100w UV light for 30 minutes. After UV curing, it is cured at 120℃ to obtain the resin lens.

[0041] like Figure 1 The image shown is a sample of the resin lens prepared in this embodiment.

[0042] Example 2 This example provides a high-hardness resin lens, including a lens substrate and an anti-abrasion coating.

[0043] By weight, the lens matrix comprises the following components: 60 parts bisphenol A epoxy acrylate, 5 parts modified nano zirconium oxide, 35 parts tripropylene glycol diacrylate, 1 part azobisisobutyronitrile initiator, 1.5 parts polyethylene wax release agent, and 3.5 parts UV326 ultraviolet absorber.

[0044] By weight, the anti-wear film layer comprises the following components: 30 parts of sulfobetaine methacrylate, 15 parts of vinyltriethoxysilane, 8 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.5 parts of azobisisobutyronitrile.

[0045] This embodiment also provides a method for preparing the above-mentioned resin lens, which specifically includes the following steps:

[0046] S1, Preparation of modified nano-zirconia;

[0047] The nano-zirconia powder was dried at 60℃ for 6 hours to obtain the dried nano-zirconia powder.

[0048] Prepare a 10% (w / w) aqueous solution of γ-methacryloxypropyltrimethoxysilane.

[0049] Weigh 4g of dried nano-zirconia and add it to 30mL of toluene. Disperse it by sonication at 25℃ for 40min. Then add 20mL of 10% (w / w) aqueous solution of γ-methacryloyloxypropyltrimethoxysilane. Sonicate for 10min and react at 85℃ for 25min. After the reaction is complete, cool it and centrifuge it at 16000rpm for 20min. Sonicate it again for 10min. Filter the solid material, wash it, and dry it at 100℃ for 5h to obtain modified nano-zirconia.

[0050] S2. Preparation of the lens substrate;

[0051] 6g of bisphenol A epoxy acrylate, 0.5g of modified nano-zirconia, 3.5g of tripropylene glycol diacrylate, 0.15g of polyethylene wax, and 0.35g of UV326 were mixed, and then 0.1g of azobisisobutyronitrile (AIBN) initiator was added. The mixture was vacuumed at 30℃ for 40 minutes, and continuously shaken to mix evenly to obtain a viscous prepolymer. The viscous prepolymer was then poured into a glass mold and cured once. After the mold was opened, the edges were trimmed, and the mold was cleaned. A second curing process was then performed to obtain the lens substrate. The first curing process was as follows: initial temperature 35℃, temperature increased to 45℃ in 0.5h, temperature increased to 50℃ in 2.5h, temperature increased to 54℃ in 9h, temperature increased to 70℃ in 3h, and temperature increased to 80℃ in 2h. The second curing process was as follows: temperature increased to 125℃ and cured for 2h.

[0052] S3, Preparation of resin lenses;

[0053] 3g of sulfobetaine methacrylate, 1.5g of vinyltriethoxysilane and 0.8g of 2-hydroxy-4-acryloyloxybenzophenone were mixed and dissolved in 40mL of anhydrous ethanol. Then, 0.05g of initiator azobisisobutyronitrile was added and the mixture was deoxygenated with argon for 30min. The reaction was carried out at 80℃ for 10h. After the reaction was completed, the mixture was centrifuged at 3000rpm for 15min. After removing the supernatant, the precipitate was redispersed in anhydrous ethanol. The centrifugation was repeated 3 times. Finally, the precipitate was dried at 45℃ for 24h and then dissolved in trifluoroethanol to obtain a solution with a concentration of 2g / mL.

[0054] The lens substrate is placed in the solution and left to stand for 5 minutes. Then it is removed and cured with 365nm, 100w UV light for 30 minutes. After UV curing, it is cured at 115℃ to obtain the resin lens.

[0055] Example 3 This example provides a high-hardness resin lens, including a lens substrate and an anti-abrasion coating.

[0056] By weight, the lens matrix comprises the following components: 55 parts bisphenol A epoxy acrylate, 4 parts modified nano zirconium oxide, 33 parts tripropylene glycol diacrylate, 0.8 parts azobisisobutyronitrile initiator, 1.3 parts glyceryl stearate release agent, and 3.3 parts UV329 ultraviolet absorber.

[0057] By weight, the anti-wear film layer comprises the following components: 25 parts of sulfobetaine methacrylate, 13 parts of vinyltriethoxysilane, 5 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.4 parts of azobisisobutyronitrile.

[0058] This embodiment also provides a method for preparing the above-mentioned resin lens, which specifically includes the following steps:

[0059] S1, Preparation of modified nano-zirconia;

[0060] The nano-zirconia powder was dried at 60℃ for 6 hours to obtain the dried nano-zirconia powder.

[0061] Prepare a 10% (w / w) aqueous solution of γ-methacryloxypropyltrimethoxysilane.

[0062] Weigh 2g of dried nano-zirconia and add it to 15mL of toluene. Disperse it by sonication at 25℃ for 40min. Then add 10mL of 10% (w / w) aqueous solution of γ-methacryloyloxypropyltrimethoxysilane. Sonicate for 10min and react at 85℃ for 25min. After the reaction is complete, cool it and centrifuge it at 16000rpm for 20min. Sonicate it again for 10min. Filter the solid material, wash it, and dry it at 100℃ for 5h to obtain modified nano-zirconia.

[0063] S2. Preparation of the lens substrate;

[0064] 5.5g of bisphenol A epoxy acrylate, 0.4g of modified nano-zirconia, 3.3g of tripropylene glycol diacrylate, 0.13g of polyethylene wax, and 0.33g of UV326 were mixed, and then 0.08g of azobisisobutyronitrile (AIBN) initiator was added. The mixture was vacuumed at 30℃ for 35 minutes, and continuously shaken and mixed until homogeneous to obtain a viscous prepolymer. The viscous prepolymer was then poured into a glass mold and cured once. After the mold was opened, the edges were trimmed, and the mold was cleaned. A second curing process was then performed to obtain the lens substrate. The first curing process was as follows: initial temperature 30℃, temperature increased to 43℃ in 0.5h, temperature increased to 48℃ in 2.5h, temperature increased to 53℃ in 9h, temperature increased to 68℃ in 3h, and temperature increased to 78℃ in 2h. The second curing process was as follows: temperature increased to 123℃ and cured for 2.3h.

[0065] S3, Preparation of resin lenses;

[0066] 2.5 g of sulfobetaine methacrylate, 1.3 g of vinyltriethoxysilane and 0.5 g of 2-hydroxy-4-acryloyloxybenzophenone were mixed and dissolved in 35 mL of anhydrous ethanol. Then, 0.04 g of initiator azobisisobutyronitrile was added and the mixture was deoxygenated with argon for 30 min. The reaction was carried out at 75 °C for 11 h. After the reaction was completed, the mixture was centrifuged at 3000 rpm for 15 min. After removing the supernatant, the precipitate was redispersed in anhydrous ethanol. The centrifugation was repeated 3 times. Finally, the precipitate was dried at 45 °C for 24 h and then dissolved in trifluoroethanol to obtain a solution with a concentration of 2 g / mL.

[0067] The lens substrate is placed in the solution and left to stand for 5 minutes. Then it is removed and cured with 365nm, 100w UV light for 30 minutes. After UV curing, it is cured at 118℃ to obtain the resin lens.

[0068] The present invention characterized the lens substrate and the resin lens with anti-abrasion coating prepared in Example 1 by ATR-FTIR, and the results are as follows: Figure 2 As shown, a is the ATR-FTIR spectrum of the lens matrix, and b is the ATR-FTIR spectrum of the resin lens. Figure 2It can be seen that the absorption curve of the lens matrix is ​​at 980cm. -1 The characteristic absorption peak of Si-O-Zr is present, and it is at 1250 cm⁻¹. -1 The characteristic absorption peak of asymmetric epoxy groups is present at 1250 cm⁻¹, while in the ATR-FTIR spectrum of the resin lens, the peak is at 1250 cm⁻¹. -1 The characteristic absorption peak of the epoxy group disappears at 1050 cm⁻¹. -1 The characteristic absorption peak of COC appears at 3300 cm⁻¹, and at 3300 cm⁻¹... -1 The presence of a characteristic absorption peak for hydroxyl groups indicates that, in this invention, the hydroxyl groups on the 2-hydroxy-4-acryloyloxybenzophenone in the anti-wear film form a β-hydroxy ether structure with the epoxy groups on the bisphenol A epoxy acrylate of the lens substrate during UV curing and high-temperature curing.

[0069] Comparative Example 1 This comparative example provides a resin lens and its preparation method.

[0070] In this comparative example, the resin lens includes the lens matrix, which, by weight, comprises: 50 parts of bisphenol A epoxy acrylate, 30 parts of tripropylene glycol diacrylate, 0.5 parts of azobisisobutyronitrile (AIO) initiator, 1 part of glyceryl stearate (STP) release agent, and 3 parts of UV329 (UV absorber).

[0071] The preparation method of the lens substrate in this comparative example is the same as that in Example 1, except that the composition of the lens substrate is different from that in Example 1.

[0072] Comparative Example 2 This comparative example provides a resin lens and its preparation method.

[0073] In this comparative example, the resin lens includes a lens substrate and an anti-abrasion coating, and the composition and preparation method of the lens substrate are the same as in Example 1.

[0074] The difference lies in the fact that the anti-wear film in this comparative example, by weight, includes the following components: 20 parts of sulfobetaine methacrylate, 10 parts of vinyltriethoxysilane, and 0.3 parts of azobisisobutyronitrile.

[0075] In this comparative example, the preparation method of the resin lens is the same as that of Example 1, the only difference being that the composition of the anti-wear film layer is different from that of Example 1.

[0076] Comparative Example 3 This comparative example provides a resin lens and its preparation method.

[0077] In this comparative example, the resin lens includes a lens substrate and an anti-abrasion coating, and the composition and preparation method of the lens substrate are the same as in Example 1.

[0078] The difference lies in the fact that the anti-wear film in this comparative example, by weight, includes the following components: 20 parts of sulfobetaine methacrylate, 3 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.3 parts of azobisisobutyronitrile.

[0079] Comparative Example 4 This comparative example provides a resin lens and its preparation method.

[0080] In this comparative example, the resin lens includes a lens substrate, and the composition and preparation method of the lens substrate are the same as in Example 1.

[0081] Hardness and scratch resistance were determined using a steel wool test, the specific method of which is as follows:

[0082] Five layers of 000# steel wool were folded, with dimensions of 40mm × 40mm, a single layer thickness of 5mm, and a mass of 8g. The initial haze values ​​of the resin lenses obtained in Examples 1-3 and Comparative Examples 1-4 were measured. Then, the lenses of the seven samples were rubbed repeatedly with steel wool at a friction pressure of 7.35N 1000 times. The haze values ​​of the seven samples were measured four times for each sample, and the arithmetic mean was taken. The difference between the haze value of the lens after rubbing and the haze value of the lens before rubbing was calculated as the friction haze value of the lens. The experimental results are shown in Table 1.

[0083] Table 1. Results of frictional haze values ​​for resin lenses in Examples 1-3 and Comparative Examples 1-4

[0084]

[0085] The surface hardness of the resin lenses obtained in Examples 1-3 and Comparative Examples 1-4 was determined using a microhardness tester. The measuring load of the microhardness tester was 5g (0.049N), and the measurement results are shown in Table 2.

[0086] Table 2. Microhardness results of resin lenses in Examples 1-3 and Comparative Examples 1-4

[0087]

[0088] As can be seen from Tables 1 and 2, the friction haze values ​​of the resin lenses in Examples 1-3 of the present invention are all lower than those in the comparative examples. By comparing the results of Examples 1-3 with those of Comparative Examples 1 and 4, it is shown that adding modified nano-zirconia to the lens matrix of the present invention can improve the hardness and scratch resistance of the lens matrix. By comparing the results of Examples 1-3 with those of Comparative Examples 2 and 3, it is shown that adding vinyltriethoxysilane to the anti-wear film layer of the present invention can greatly improve the hardness and scratch resistance of the resin lens. Adding 2-hydroxy-4-acryloyloxybenzophenone to the anti-wear film layer can also improve the hardness and scratch resistance of the resin lens to a small extent. This is because the reduction in bonding strength also affects the hardness and scratch resistance.

[0089] According to the national standard GB / T 33049-2016, the bonding strength between the anti-abrasion film and the lens substrate in the resin lenses obtained in Examples 1-3 and Comparative Examples 2-3 was determined, and the proportion of the coating surface area that was peeled off was recorded. The experimental results are shown in Table 3.

[0090] Table 3. Bond strength between the anti-abrasion film and the lens substrate in Examples 1-3 and Comparative Examples 2-3

[0091]

[0092] As can be seen from Table 3, compared with the data of Comparative Example 2, the addition of 2-hydroxy-4-acryloyloxybenzophenone to the anti-wear film layer of this application shows that during the UV curing and high-temperature curing process, the hydroxyl groups and the epoxy groups on the bisphenol A epoxy acrylate of the lens substrate form a β-hydroxy ether structure, which improves the bonding strength between the anti-wear film layer and the lens substrate.

[0093] The resin lens samples obtained in Examples 1-3 and Comparative Examples 1-4 were transferred from room temperature to 3 cm above an 80°C water bath and held for 10 s, and the transparency of the samples was measured. Then, the resin lens samples in Examples 1-3 and Comparative Examples 1-4 were transferred from room temperature to 3 cm above an 80°C water bath and held for 300 s, and the transparency of the samples was measured. The results are shown in Table 4.

[0094] Table 4. Transparency results of Examples 1-3 and Comparative Examples 1-4

[0095]

[0096] As shown in Table 4, comparing the data of Examples 1-3 with Comparative Examples 1 and 4, it can be seen that the anti-abrasion film layer in this invention can greatly improve the anti-fogging effect of the lens substrate. The transparency of Comparative Examples 1-3 and Comparative Examples 2 and 3 is relatively high at 10s, indicating that the addition of sulfobetaine methacrylate to the anti-abrasion film layer in this invention can effectively improve the short-term anti-fogging performance of the anti-abrasion film layer. However, the anti-fogging performance of the resin lens in Comparative Example 3 drops significantly at 300s, indicating that the vinyltriethoxysilane in this invention can not only improve the hardness and scratch resistance of the anti-abrasion film layer, but also inhibit the swelling of the coating caused by excessive moisture absorption of sulfobetaine methacrylate, thus solving the problem of poor anti-fogging effect caused by moisture absorption and swelling of strongly hydrophilic substances.

[0097] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A high-hardness resin lens, characterized in that, Including the lens substrate and the anti-abrasion coating; The lens matrix comprises the following components by weight: 50-60 parts of bisphenol A epoxy acrylate, 3-5 parts of modified nano-zirconia, 30-35 parts of tripropylene glycol diacrylate, 0.5-1 part of azobisisobutyronitrile initiator, 1-1.5 parts of release agent, and 3-3.5 parts of ultraviolet absorber. By weight, the anti-wear film layer comprises the following components: 20-30 parts of sulfobetaine methacrylate, 10-15 parts of vinyltriethoxysilane, 3-8 parts of 2-hydroxy-4-acryloyloxybenzophenone, and 0.3-0.5 parts of azobisisobutyronitrile; The modified nano-zirconia is prepared as follows: dried nano-zirconia is weighed and added to toluene, ultrasonically dispersed at 25°C for 40 min, then 10% by mass of γ-methacryloxypropyltrimethoxysilane aqueous solution is added, ultrasonically dispersed for 10 min, and then reacted at 80~85°C for 25~30 min. After the reaction is completed, the mixture is cooled, centrifuged at 16000 rpm for 20 min, ultrasonically dispersed for 10 min, the solid material is filtered, washed, and dried to obtain modified nano-zirconia. The preparation method of the high-hardness resin lens is as follows: sulfobetaine methacrylate, vinyltriethoxysilane, and 2-hydroxy-4-acryloyloxybenzophenone are mixed, dissolved in anhydrous ethanol, and then the initiator azobisisobutyronitrile is added. The mixture is then deoxygenated with argon for 30 minutes and reacted at 70-80℃ for 10-12 hours. After the reaction is complete, the mixture is centrifuged at 3000rpm for 15 minutes. The supernatant is removed, and the precipitate is redispersed in anhydrous ethanol. This process is repeated three times. Finally, the precipitate is dried and dissolved in trifluoroethanol to obtain a solution. The lens substrate is placed in the solution and allowed to stand for 5 minutes. It is then cured with 365nm, 100W UV light for 30 minutes. After UV curing, the lens is cured at 115℃-120℃ to obtain the resin lens.

2. The high-hardness resin lens according to claim 1, characterized in that, The ultraviolet absorber is UV329 or UV326, and the release agent is glyceryl stearate or polyethylene wax.

3. A method for preparing a high-hardness resin lens according to claim 1, characterized in that, Includes the following steps: S1. Preparation of the lens substrate; Bisphenol A epoxy acrylate, modified nano-zirconia, tripropylene glycol diacrylate, mold release agent and ultraviolet absorber are mixed, and then the initiator azobisisobutyronitrile is added. The mixture is vacuumed at 30°C for 30-40 minutes, and the mixture is continuously shaken and mixed evenly to obtain a viscous prepolymer. The viscous prepolymer is then poured into a glass mold, cured once, and then the mold is opened, the edges are trimmed, and the mold is cleaned. A second curing is then performed to obtain the lens substrate. S2. Sulfobetaine methacrylate, vinyltriethoxysilane and 2-hydroxy-4-acryloyloxybenzophenone were mixed and dissolved in anhydrous ethanol. Then, azobisisobutyronitrile (AIBN) was added and the mixture was deoxygenated with argon for 30 min. The mixture was reacted at 70-80 °C for 10-12 h. After the reaction was completed, the mixture was centrifuged at 3000 rpm for 15 min. After removing the supernatant, the precipitate was redispersed in anhydrous ethanol. The centrifugation was repeated 3 times. Finally, the precipitate was dried and dissolved in trifluoroethanol to obtain a solution. S3. Place the lens substrate in the solution, let it stand for 5 minutes, then remove it and cure it with 365nm, 100w UV light for 30 minutes. After UV curing, place it at 115℃~120℃ for curing to obtain the resin lens.

4. The method for preparing a high-hardness resin lens according to claim 3, characterized in that, In step S1, the first curing process specifically involves: an initial temperature of 25~35℃, a temperature increase to 40~45℃ in 0.5h, a temperature increase to 45~50℃ in 2.5h, a temperature increase to 52~54℃ in 9h, a temperature increase to 65~70℃ in 3h, and a temperature increase to 75~80℃ in 2h; the second curing process specifically involves: a temperature increase to 120~125℃, followed by curing for 2~2.5h.

5. The method for preparing a high-hardness resin lens according to claim 3, characterized in that, In step S1, the modified nano-zirconia is prepared as follows: dried nano-zirconia is weighed and added to toluene, ultrasonically dispersed at 25°C for 40 min, then 10% by mass of γ-methacryloxypropyltrimethoxysilane aqueous solution is added, ultrasonically dispersed for 10 min, and then reacted at 80~85°C for 25~30 min. After the reaction is completed, it is cooled, then centrifuged at 16000 rpm for 20 min, ultrasonically dispersed for 10 min, the solid material is filtered, washed, and dried to obtain modified nano-zirconia.

6. The method for preparing a high-hardness resin lens according to claim 5, characterized in that, For every 2g of dried nano-zirconia added, the amount of γ-methacryloxypropyltrimethoxysilane aqueous solution used is 10mL.

7. The method for preparing a high-hardness resin lens according to claim 3, characterized in that, In step S2, the concentration of the precipitate in the solution is 2 g / mL.

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