A high-borosilicate optical lens glass and its preparation process

Abstract

The present invention discloses a high borosilicate optical lens glass and its preparation process, which relates to the technical field of glass surface treatment. The preparation process of a high borosilicate optical lens glass is as follows: Mix and melt the raw materials, form them, and perform heat treatment to obtain high borosilicate glass; Etch, apply sol coating to form an antireflection layer, and obtain optical lens glass. The present invention prepares an antireflection layer on the surface of high borosilicate glass through etching and sol coating. The sol coating first uses hydrosilane to load fluorinated POSS on the glass surface to form a POSS modification layer, and then uses polyvinylpyrrolidone and a polymer of fluorinated POSS as templates to prepare hollow silica sol. After coating and curing, a composite structure is formed, which greatly reduces the refractive index of the glass surface, can reduce the reflection of light, improve the light transmittance and clarity of the glass, and make the visual experience more comfortable and natural.

Description

Technical Field

[0001] The present invention relates to the technical field of glass surface treatment, and specifically to a high borosilicate optical lens glass and a preparation process thereof. Background Art

[0002] Optical materials are generally divided into optical glass, optical crystals and special optical materials. Among them, optical glass is a non-crystalline (glass state) optical medium material that can transmit light, and is commonly used in the production of optical elements such as prisms, lenses, mirrors, window plates, and filters in optical instruments or optical systems. High borosilicate glass is a borosilicate glass with a silicon dioxide (SiO2) content > 78 wt%, and a boron trioxide (B2O3) content > 10 wt%. It has high strength, high hardness, low expansion coefficient, and excellent thermal stability and chemical stability. However, the glass surface has a certain reflectivity, which will cause light loss, which is not conducive to its application. The prior art achieves the anti-reflection effect through the interference cancellation of thin films. According to the existing formula calculation, when the refractive index of the glass substrate is 1.5, the ideal single-layer anti-reflection film should be around 1.23. And a dense single-layer substance cannot have such a low refractive index. Therefore, we propose a high borosilicate optical lens glass and a preparation process thereof. Summary of the Invention

[0003] The purpose of the present invention is to provide a high borosilicate optical lens glass and a preparation process thereof, so as to solve the problems proposed in the above background art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: A preparation process of a high borosilicate optical lens glass, including the following processes:

[0005] Mix and melt the raw materials, form, and perform heat treatment to obtain high borosilicate glass;

[0006] Etch, coat with sol to form an anti-reflection layer to obtain optical lens glass.

[0007] Further, the raw materials include the following mass components: 78 - 85 parts of silicon dioxide, 10 - 15 parts of boron trioxide, 5 - 10 parts of borax, 3 - 6 parts of sodium oxide, 2 - 10 parts of sodium silicate, 2.0 - 4.5 parts of aluminum hydroxide, 1 - 3 parts of zirconium phosphate, 0.1 - 0.5 parts of lithium oxide, 0.065 - 0.075 parts of cerium dioxide.

[0008] In the above technical solution, silicon dioxide and boron oxide serve as the framework of the glass and are the main preparation components. Borax (Na2B4O7·10H2O) decomposes when heated in the melting process to form boron oxide (B2O3), sodium oxide (Na2O), and water. Boric acid decomposes when heated to produce boron oxide (B2O3) and water. Sodium silicate (Na2SiO3) decomposes when heated to produce silicon dioxide (SiO2) and sodium oxide. Aluminum hydroxide decomposes when heated to form aluminum oxide (Al2O3) and water. Boron oxide, sodium oxide, and silicon dioxide are the basic components to form borosilicate glass, endowing it with a low expansion coefficient, high thermal stability, and chemical stability. Sodium oxide acts as a flux, providing free oxygen to transform the structure of boron oxide from layered to framework, making it easier to form a homogeneous melt with silicon dioxide, promoting the melting of the glass components, adjusting the refractive index of the glass, and enhancing its strength and chemical stability. Boron oxide can lower the melting point and viscosity of the glass, promote the flow and shaping of the molten glass, improve the physical and chemical properties of the glass, and enhance its transparency, heat resistance, and corrosion resistance. The generated water is transformed into water vapor and released in the high-temperature melting process, which can carry the bubbles in the molten glass out and produce a clarification effect; in synergy with cerium dioxide (CeO2) in the raw materials, it plays a phased clarification role. The decomposition temperature of cerium dioxide is higher. It decomposes at high temperature to form cerium sesquioxide (Ce2O3) and releases oxygen, accelerating clarification and achieving homogenization of the molten glass; at the same time, the ionic compound cerium sesquioxide has the effects of high field strength, high coordination, and high accumulation, making the structure of the fabricated glass tend to be densified, thus contributing to improving its mechanical properties and thermal stability. Aluminum oxide can improve the chemical stability, thermal stability, strength, and hardness of the glass while also enhancing its refractive index and improving the optical properties of the glass. Lithium oxide (LiO2) can play a fluxing role, reduce the thermal expansion coefficient of the glass, and improve its chemical stability and thermal stability. The ionic radius of lithium is the smallest, and it is easy to enter the glass network structure to form ion exchange. Due to its relatively high electronegativity, it attracts surrounding molecules, making the glass denser and improving the gloss and strength and hardness of the glass. Zirconium phosphate has the commonalities of layered compounds, with a relatively high specific surface area and surface charge, having ion exchange characteristics and adsorption capacity. It can carry out ion exchange with lithium oxide, enhancing the connection between glass components and improving the thermal stability, chemical stability, and strength of the glass.

[0009] Further, the mixed melting process is as follows: Heat the raw materials to melt at a temperature of 1400 - 1550 °C and keep warm for 30 - 60 min; raise the temperature to 1600 - 1700 °C, introduce oxygen, and melt for 1 - 3 h;

[0010] The oxygen flow rate is 0.5 - 3.0 L / min, and the introduction duration is 10 - 60 min.

[0011] In the above technical solution, the raw materials are melted at a relatively low temperature, enabling the raw materials to react and effectively avoiding the volatilization of the raw materials. Then, the temperature is increased to reduce the viscosity of the glass melt, and the oxygen introduced can form uniform bubbles, which helps to homogenize the composition, structure, and quality of the prepared high-borosilicate glass.

[0012] Furthermore, the forming process adopts a leakage forming technique, with higher raw material utilization rate and better optical quality of the prepared high-borosilicate glass.

[0013] Furthermore, the heat treatment process is as follows: keep the temperature at 540 - 650 °C for 1 - 3 h; cool naturally to room temperature.

[0014] In the above technical solution, the obtained high-borosilicate glass is annealed to eliminate the residual stress in the glass, promote the homogenization of its optical and structural properties, and improve the stability of the glass.

[0015] Furthermore, the etching process is as follows:

[0016] Place the high-borosilicate glass in the etching solution, carry out a hydrothermal reaction at 158 - 162 °C for 450 - 500 min; take it out after the reaction, wash, and dry to form an etched layer.

[0017] Furthermore, in step S1, the etching solution includes the following mass components: 3.0 - 22.5 g / L disodium ethylenediaminetetraacetate, 5.5 - 35 g / L tetrasodium ethylenediaminetetraacetate;

[0018] The mass ratio of disodium ethylenediaminetetraacetate to tetrasodium ethylenediaminetetraacetate is (30 - 45):(55 - 70).

[0019] In the above technical solution, the obtained high-borosilicate glass is surface-etched using disodium ethylenediaminetetraacetate and tetrasodium ethylenediaminetetraacetate. The above two components show acidity and alkalinity in water respectively. By controlling the dosages of disodium ethylenediaminetetraacetate and tetrasodium ethylenediaminetetraacetate, the pH value of the etching solution can be regulated, and it has a strong complexing ability, stabilizing the etching process. Under hydrothermal conditions, the components of the etching solution carry out ion exchange with the high-borosilicate glass, forming pores on the glass surface, increasing the porosity of the glass surface, reducing the refractive index of the prepared etched layer, and reducing the surface reflectivity of the glass through destructive interference to improve its transmittance.

[0020] Furthermore, the sol coating process is as follows:

[0021] Modify the etched high-borosilicate glass using hydrosilane; use trifluoroethyltriethoxysilane and vinylsiloxane as raw materials to prepare fluorine-containing POSS; add dichloromethane and a photoinitiator to prepare a fluorine-containing POSS / dichloromethane dispersion; add the high-borosilicate glass obtained in the previous step and irradiate with ultraviolet light to form a POSS modification layer;

[0022] Take fluorinated POSS and polyvinylpyrrolidone, mix them in a solvent, add an initiator, and heat for reaction; then add tetraethyl orthosilicate, ammonia water, and absolute ethanol, react to obtain a sol; impregnate and lift the high borosilicate glass obtained in the previous step, and calcine to form a hollow silica layer to obtain an antireflection layer.

[0023] Furthermore, the sol coating process is as follows:

[0024] (1) Place the etched high borosilicate glass in a hydrogen silane / ethanol solution and ultrasonicate for 20 - 30 min; take it out and hydrolyze it at a temperature of 23 - 27 °C and a humidity of 40% - 50% for 18 - 24 h to form a hydrogen silane modification layer;

[0025] (2) Mix trifluoroethyltriethoxysilane, vinyl siloxane, ethanol, hydrochloric acid, and deionized water, heat to 70 - 80 °C, stir and reflux for 5 - 12 h; cool to room temperature and continue to react for 15 - 24 h; recrystallize with a mixed solution of tetrahydrofuran and methanol, filter, wash, and dry to obtain fluorinated POSS; add dichloromethane and a photoinitiator to prepare a fluorinated POSS / dichloromethane dispersion;

[0026] Place the high borosilicate glass obtained in the previous step in the fluorinated POSS / dichloromethane dispersion, irradiate with ultraviolet light for 10 - 50 min; then place it at a temperature of 150 - 160 °C and cure for 100 - 150 min; wash and dry to form a POSS modification layer;

[0027] (3) Mix deionized water, fluorinated POSS, and polyvinylpyrrolidone, heat to 28 - 82 °C, add an initiator, and react for 1 - 15 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate and stir at a temperature of 68 - 72 °C for 10 - 12 h to obtain a sol;

[0028] Place the high borosilicate glass obtained in the previous step in the sol, impregnate for 6 - 10 min, then lift it out, with a lifting speed of 70 - 80 cm / min; place it at room temperature for 10 - 15 min to volatilize the alcohol; place it at a temperature of 60 - 70 °C and dry for 8 - 12 h, and calcine at a temperature of 400 - 500 °C for 2 - 3 h to form a hollow silica layer to obtain an antireflection layer.

[0029] Furthermore, in step (1), the concentration of the hydrogen silane / ethanol solution is 3 - 5 v%; the hydrogen silane is one of triethoxysilane and trimethoxysilane.

[0030] Furthermore, in step (2), the mass ratio of trifluoroethyltriethoxysilane, vinyl siloxane, ethanol, deionized water, and hydrochloric acid is (67 - 80):(14 - 58):100:(12 - 16):(7.5×10-4 ~8.3×10 -4 );

[0031] Hydrochloric acid is added in the form of 0.12 M dilute hydrochloric acid.

[0032] Furthermore, in step (2), the concentration of the fluorinated POSS / dichloromethane dispersion is 5-15 wt%.

[0033] The photoinitiator is Irgacure 2959, and the dosage is 5% of the mass of the fluorinated POSS.

[0034] Furthermore, in step (2), the vinyl siloxane is one of methyl vinyl dimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, γ-(methacryloyloxy)propyl trimethoxysilane, γ-(methacryloyloxy)propyl triethoxysilane, γ-(methacryloyloxy)propyl methyl dimethoxysilane.

[0035] Furthermore, in step (3), the sol is prepared from the following components: in terms of parts by mass, 2.5-3.0 parts of fluorinated POSS, 0.3-0.4 part of polyvinylpyrrolidone, 0.1-0.2 part of initiator, 6-8 parts of ammonia water, 5-6 parts of tetraethyl orthosilicate, 100-120 parts of absolute ethanol, and 45-50 parts of deionized water.

[0036] The initiator is one of aluminum chloride and ammonium persulfate.

[0037] In the above technical solution, the fluorinated siloxane and the vinyl siloxane are mixed, and under the catalysis of an acid, POSS (cage-shaped polyhedral oligomeric silsesquioxane) is formed. Its structure contains fluorine groups and vinyl groups, which can effectively reduce the refractive index of the prepared POSS and endow it with reactivity. The surface pores of the etched borosilicate glass are modified with hydrosilane. Under the action of the initiator and irradiation, through the addition of silicon-hydrogen bonds and vinyl groups, the loading of POSS on the glass surface is realized, and the pores are further modified and filled to form a POSS modification layer, making it have low reflection characteristics and realizing a further reduction in reflectivity; at the same time, the POSS modification layer has good mechanical strength, hardness, and hydrophobicity, which helps to maintain the morphology of the etched layer for a long time and improve the surface performance of the prepared glass.

[0038] Mix the fluorinated POSS with polyvinylpyrrolidone. The fluorinated POSS is adsorbed to polyvinylpyrrolidone through electrostatic interaction, and under the action of an initiator, polymerization occurs to form a porous polymer. As a template, tetraethyl orthosilicate penetrates and hydrolyzes under the action of ammonia water, and polymerizes on the surface of the template to form hollow silica doped with the fluorinated POSS porous polymer and its sol, which has a lower refractive index. After coating it on the surface of the POSS-modified borosilicate glass (POSS modification layer) and curing, a hollow silica layer is formed, and thus the preparation of the antireflection layer on the glass surface is completed. Through the multi-layer structure composite of the etching layer, POSS modification layer and hollow silica layer, the refractive index of the film layer on the surface of the borosilicate is greatly reduced. The prepared glass has effective antireflection ability, can reduce the reflection of light, improve the light transmittance and clarity of the glass, and make the visual experience more comfortable and natural. At the same time, the doping of the fluorinated POSS porous polymer makes the prepared antireflection layer have higher strength, hardness and hydrophobicity, realizing wear resistance and easy cleaning.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] A preparation process of a borosilicate optical lens glass described in the present invention prepares an antireflection layer by etching and sol coating on the surface of the borosilicate glass. The sol coating first uses hydrosilane to load the fluorinated POSS on the glass surface to form a POSS modification layer, and then uses the polymer of polyvinylpyrrolidone and fluorinated POSS as a template to prepare hollow silica sol. After coating and curing, a composite structure is formed, which greatly reduces the refractive index of the glass surface, can reduce the reflection of light, improve the light transmittance and clarity of the glass, and make the visual experience more comfortable and natural. Specific embodiments

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0042] In the following specific embodiments,

[0043] In Examples 1-3, the raw materials include the following mass components: 80 parts of silica, 12 parts of boron oxide, 7 parts of borax, 4 parts of sodium oxide, 8 parts of sodium silicate, 3.5 parts of aluminum hydroxide, 1 part of zirconium phosphate, 0.2 part of lithium oxide, and 0.07 part of cerium dioxide;

[0044] The photoinitiator is Irgacure 2959, and the dosage is 5% of the mass of the fluorinated POSS;

[0045] The initiator is ammonium persulfate.

[0046] Example 1: A preparation process of high-borosilicate optical lens glass, including the following processes:

[0047] 1. Heat the raw materials to melt at a temperature of 1400 °C and keep warm for 60 min; raise the temperature to 1600 °C, introduce oxygen, and melt for 3 h; the oxygen flow rate is 0.5 L / min, and the introduction duration is 60 min; leak and form, and keep warm at a temperature of 540 °C for 3 h; naturally cool to room temperature to obtain high-borosilicate glass;

[0048] 2. Place the high-borosilicate glass in the etching solution and carry out hydrothermal reaction at a temperature of 158 °C for 450 min; take it out after the reaction, wash and dry it to form an etching layer; the etching solution includes the following mass components: 3.0 g / L disodium ethylenediaminetetraacetate, 7.0 g / L tetrasodium ethylenediaminetetraacetate;

[0049] 3.1 Place the etched high-borosilicate glass in a 3 v% triethoxysilane / ethanol solution and ultrasonicate for 20 min; take it out and hydrolyze at a temperature of 23 °C and a humidity of 40% for 18 h to form a hydrosilane modification layer;

[0050] 3.2 Mix trifluoroethyltriethoxysilane, methylvinyldimethoxysilane, ethanol, hydrochloric acid (0.12 M dilute hydrochloric acid) and deionized water, raise the temperature to 70 °C, stir and reflux for 5 h; cool to room temperature and continue to react for 15 h; recrystallize with a mixed solution of tetrahydrofuran and methanol, filter, wash and dry to obtain fluorine-containing POSS; add dichloromethane and a photoinitiator to prepare a 5 wt% fluorine-containing POSS / dichloromethane dispersion; the mass ratio of trifluoroethyltriethoxysilane, vinylsiloxane, ethanol, deionized water, hydrochloric acid is 67:14.3:100:12:7.5×10 -4 ;

[0051] Place the high-borosilicate glass obtained in the previous step in the fluorine-containing POSS / dichloromethane dispersion and irradiate with ultraviolet light for 10 min; then take it out and cure at a temperature of 150 °C for 100 min; wash and dry to form a POSS modification layer;

[0052] 3.3 Mix deionized water, fluorine-containing POSS and polyvinylpyrrolidone, heat to 78 °C, add an initiator and react for 9 h; add ammonia water and anhydrous ethanol, and slowly add tetraethyl orthosilicate at a temperature of 68 °C and finish adding it within 30 min, and stir for 10 h to obtain a sol; the sol is prepared from the following components: by mass, 2.5 parts of fluorine-containing POSS, 0.3 part of polyvinylpyrrolidone, 0.1 part of initiator, 6 parts of ammonia water, 5 parts of tetraethyl orthosilicate, 100 parts of anhydrous ethanol and 45 parts of deionized water;

[0053] The high-borosilicate glass obtained in the previous step was immersed in the sol for 6 min and then taken out by pulling at a pulling speed of 70 cm / min; it was placed at room temperature for 10 min to volatilize the alcohol; it was dried at 60 °C for 8 h and calcined at 400 °C for 3 h to form a hollow silica layer, obtaining an antireflection layer and getting the optical lens glass.

[0054] Example 2: A preparation process of high-borosilicate optical lens glass, including the following processes:

[0055] 1. The raw materials were heated to melt at 1475 °C and kept warm for 45 min; the temperature was raised to 1650 °C, oxygen was introduced, and melting was carried out for 2 h; the oxygen flow rate was 1.8 L / min and the introduction duration was 30 min; leakage molding was carried out, and it was kept warm at 600 °C for 2 h; it was naturally cooled to room temperature to obtain high-borosilicate glass;

[0056] 2. The high-borosilicate glass was placed in the etching solution, and hydrothermal reaction was carried out at 160 °C for 475 min; after the reaction, it was taken out, washed, and dried to form an etching layer; the etching solution included the following mass components: 13 g / L disodium ethylenediaminetetraacetate, 20 g / L tetrasodium ethylenediaminetetraacetate;

[0057] 3.1 The etched high-borosilicate glass was placed in a 4 v% trimethoxysilane / ethanol solution and sonicated for 25 min; it was taken out and hydrolyzed at 25 °C and 45% humidity for 21 h to form a hydrosilane modification layer;

[0058] 3.2 Trifluoroethyltriethoxysilane, vinyltriethoxysilane, ethanol, hydrochloric acid (0.12 M dilute hydrochloric acid), and deionized water were mixed, the temperature was raised to 75 °C, and stirring and reflux reaction were carried out for 8 h; it was cooled to room temperature and reacted for another 20 h; recrystallization was carried out using a mixed solution of tetrahydrofuran and methanol, filtered, washed, and dried to obtain fluorine-containing POSS; dichloromethane and a photoinitiator were added to prepare a 10 wt% fluorine-containing POSS / dichloromethane dispersion; the mass ratio of trifluoroethyltriethoxysilane, alkenyl siloxane, ethanol, deionized water, and hydrochloric acid was 72:28.7:100:14:8.0×10 -4 ;

[0059] The high-borosilicate glass obtained in the previous step was placed in the fluorine-containing POSS / dichloromethane dispersion and irradiated with ultraviolet light for 30 min; then it was taken out and cured at 155 °C for 120 min; washed and dried to form a POSS modification layer;

[0060] 3.3 Mix deionized water, fluorinated POSS, and polyvinylpyrrolidone, heat to 80 °C, add an initiator, and react for 12 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate while stirring at 70 °C for 11 h to obtain a sol; the sol is prepared from the following components: by mass, 2.8 parts of fluorinated POSS, 0.35 part of polyvinylpyrrolidone, 0.15 part of initiator, 7 parts of ammonia water, 5.5 parts of tetraethyl orthosilicate, 110 parts of absolute ethanol, and 48 parts of deionized water;

[0061] Immerse the high borosilicate glass obtained in the previous step in the sol for 8 min, then lift it out, with a lifting speed of 75 cm / min; place it at room temperature for 12 min to volatilize the alcohol; dry it at 65 °C for 10 h and calcine it at 450 °C for 2.5 h to form a hollow silica layer, thus obtaining an antireflection layer and an optical lens glass.

[0062] Example 3: A preparation process of high borosilicate optical lens glass, including the following processes:

[0063] 1. Heat the raw materials to 1550 °C for melting and keep warm for 30 min; raise the temperature to 1700 °C, introduce oxygen, and melt for 1 h; the oxygen flow rate is 3.0 L / min and the introduction duration is 10 min; leak and form, keep warm at 650 °C for 1 h; naturally cool to room temperature to obtain high borosilicate glass;

[0064] 2. Immerse the high borosilicate glass in the etching solution and carry out hydrothermal reaction at 162 °C for 500 min; take it out after the reaction, wash and dry it to form an etching layer; the etching solution includes the following mass components: 22.5 g / L of disodium ethylenediaminetetraacetate and 35 g / L of tetrasodium ethylenediaminetetraacetate;

[0065] 3.1 Immerse the etched high borosilicate glass in a 5 v% triethoxysilane / ethanol solution and ultrasonicate for 30 min; take it out and hydrolyze it at 27 °C and 50% humidity for 24 h to form a hydrosilane modification layer;

[0066] 3.2 Mix trifluoroethyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, ethanol, hydrochloric acid (0.12 M dilute hydrochloric acid), and deionized water, heat to 80 °C, stir and reflux for 12 h; cool to room temperature and continue to react for 24 h; recrystallize with a mixed solution of tetrahydrofuran and methanol, filter, wash, and dry to obtain fluorinated POSS; add dichloromethane and a photoinitiator to prepare a 15 wt% fluorinated POSS / dichloromethane dispersion; the mass ratio of trifluoroethyltriethoxysilane, alkenylsiloxane, ethanol, deionized water, and hydrochloric acid is 80:58:100:16:8.3×10 -4 ;

[0067] Place the high borosilicate glass obtained in the previous step in a fluorinated POSS / dichloromethane dispersion and irradiate it with ultraviolet light for 50 min; then take it out, place it at 160 °C, and cure for 150 min; wash and dry to form a POSS modification layer;

[0068] 3.3 Mix deionized water, fluorinated POSS, and polyvinylpyrrolidone, heat to 82 °C, add an initiator, and react for 15 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate with stirring at 72 °C for 12 h to obtain a sol; the sol is prepared from the following components: by mass, 3.0 parts of fluorinated POSS, 0.4 part of polyvinylpyrrolidone, 0.2 part of initiator, 8 parts of ammonia water, 6 parts of tetraethyl orthosilicate, 120 parts of absolute ethanol, and 50 parts of deionized water;

[0069] Place the high borosilicate glass obtained in the previous step in the sol, impregnate it for 10 min, then lift it out at a lifting speed of 80 cm / min; leave it at room temperature for 15 min to volatilize the alcohol; dry it at 70 °C for 12 h and calcine it at 500 °C for 2 h to form a hollow silica layer, obtain an antireflection layer, and obtain optical lens glass.

[0070] Comparative Example 1: A preparation process of high borosilicate optical lens glass includes the following processes:

[0071] Processes 1 - 2 are the same as those in Example 1 to obtain high borosilicate glass and its surface etching layer in sequence;

[0072] Steps 3.1 and 3.2 are the same as those in Example 1 to form a POSS modification layer;

[0073] 3.3 Mix deionized water, styrene, and polyvinylpyrrolidone, heat to 78 °C, add an initiator, and react for 9 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate at 68 °C and finish adding it within 30 min, then stir for 10 h to obtain a sol; the sol is prepared from the following components: by mass, 2.5 parts of styrene, 0.3 part of polyvinylpyrrolidone, 0.1 part of initiator, 6 parts of ammonia water, 5 parts of tetraethyl orthosilicate, 100 parts of absolute ethanol, and 45 parts of deionized water;

[0074] Place the high borosilicate glass obtained in the previous step in the sol, impregnate it for 6 min, then lift it out at a lifting speed of 70 cm / min; leave it at room temperature for 10 min to volatilize the alcohol; dry it at 60 °C for 8 h and calcine it at 400 °C for 3 h to form a hollow silica layer, obtain an antireflection layer, and obtain optical lens glass;

[0075] Steps 3.1 and 3.3 are the same as those in Example 1 to form an antireflection layer and obtain optical lens glass.

[0076] Comparative Example 2: A preparation process of high borosilicate optical lens glass, including the following processes:

[0077] Process 1-2 is the same as that in Example 1, and high borosilicate glass and its surface etching layer are obtained in sequence;

[0078] 3.2 Mix methylvinyl dimethoxysilane, ethanol, hydrochloric acid (0.12M dilute hydrochloric acid) and deionized water, heat up to 70 °C, stir and reflux for 5 h; cool to room temperature and continue to react for 15 h; recrystallize with a mixed solution of tetrahydrofuran and methanol, filter, wash, and dry to obtain fluorinated POSS; add dichloromethane and photoinitiator to prepare a 5wt% fluorinated POSS / dichloromethane dispersion; the mass ratio of alkenyl siloxane, ethanol, deionized water, and hydrochloric acid is 58:100:12:7.5×10 -4 ;

[0079] Place the high borosilicate glass obtained in the previous step into the fluorinated POSS / dichloromethane dispersion, and irradiate with ultraviolet light for 10 min; then take it out, place it at 150 °C for 100 min for curing; wash and dry to form a POSS modification layer;

[0080] Steps 3.1 and 3.3 are the same as those in Comparative Example 1 to form an antireflection layer, and optical lens glass is obtained.

[0081] Comparative Example 3: A preparation process of high borosilicate optical lens glass, including the following processes:

[0082] Process 1-2 is the same as that in Example 1, and high borosilicate glass and its surface etching layer are obtained in sequence;

[0083] 3. Mix deionized water, styrene and polyvinylpyrrolidone, heat to 78 °C, add initiator and react for 9 h; add ammonia water and absolute ethanol, slowly add tetraethyl orthosilicate at 68 °C within 30 min, stir for 10 h to obtain a sol; the sol is prepared from the following components: by mass, 2.5 parts of styrene, 0.3 parts of polyvinylpyrrolidone, 0.1 part of initiator, 6 parts of ammonia water, 5 parts of tetraethyl orthosilicate, 100 parts of absolute ethanol and 45 parts of deionized water;

[0084] Place the high borosilicate glass obtained in the previous step into the sol, impregnate for 6 min, then lift it out at a lifting speed of 70 cm / min; place it at room temperature for 10 min to volatilize the alcohol; dry at 60 °C for 8 h and calcine at 400 °C for 3 h to form a hollow silica layer, prepare an antireflection layer, and obtain optical lens glass.

[0085] Comparative Example 4: A preparation process of high borosilicate optical lens glass, including the following processes:

[0086] The process 1 is the same as that in Example 1 to obtain high borosilicate glass;

[0087] 2. Mix deionized water, styrene and polyvinylpyrrolidone, heat to 78 °C, add an initiator, and react for 9 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate at 68 °C, and finish adding within 30 min, and stir for 10 h to obtain a sol; the sol is prepared from the following components: by mass, 2.5 parts of styrene, 0.3 part of polyvinylpyrrolidone, 0.1 part of initiator, 6 parts of ammonia water, 5 parts of tetraethyl orthosilicate, 100 parts of absolute ethanol and 45 parts of deionized water;

[0088] Immerse the high borosilicate glass obtained in the previous step in the sol for 6 min, then lift it out, and the lifting speed is 70 cm / min; place it at room temperature for 10 min to volatilize the alcohol; dry it at 60 °C for 8 h and calcine it at 400 °C for 3 h to form a hollow silica layer, and obtain an antireflection layer to obtain optical lens glass.

[0089] Comparative Example 5: A preparation process of high borosilicate optical lens glass, including the following processes:

[0090] The process 1 is the same as that in Example 1 to obtain high borosilicate glass;

[0091] 2. Place the high borosilicate glass in the etching solution and carry out hydrothermal reaction at 158 °C for 450 min; take it out after the reaction, wash and dry to form an etching layer; the etching solution includes the following mass components: 3.0 g / L of disodium ethylenediaminetetraacetate and 7.0 g / L of tetrasodium ethylenediaminetetraacetate; obtain an antireflection layer to obtain optical lens glass.

[0092] Experiment: Take the optical lens glasses obtained in Examples 1-3 and Comparative Examples 1-5 to prepare specimens, and detect and record the test results of their performance respectively:

[0093] Optical performance test: Use a UV-visible spectrometer to detect the transmittance of the specimen, and the experimental wavelength is 400-800 nm;

[0094] Hardness test: Use a pencil hardness tester, with GB / T 6739 as the reference standard, to detect the surface hardness of the specimen, the experimental load is 750 g, and the experimental angle is 45°, until a scratch exceeding 3 mm appears on the surface of the specimen. The maximum pencil hardness that fails to cause a scratch exceeding 3 mm on the surface of the specimen is used as the characterization data;

[0095] Abrasion resistance test: Use a steel wool abrasion tester to rub the surface of the specimen back and forth 100 times, the experimental load is 500 g, and then detect the transmittance of the specimen again after the experiment, and calculate the change in transmittance of the specimen before and after the experiment;

[0096] Hydrophobic performance test: Using a contact angle measuring instrument, the contact angle of the sample surface was detected, and the static contact angle of the water droplet was used as the characterization data. The experimental water droplet was 4 μL.

[0097] Transmittance (%) Hardness Contact Angle (°) Transmittance Decrease (%) Example 1 98.2 7H 150.4 0.43 Example 2 98.5 9H 153.5 0.30 Example 3 98.0 9H 157.1 0.14 Comparative Example 1 97.3 6H 145.4 0.74 Comparative Example 2 96.2 6H 144.0 0.66 Comparative Example 3 97.8 3H 142.8 1.05 Comparative Example 4 93.4 4H 128.5 0.90 Comparative Example 5 97.2 2H 121.7 1.78

[0098] From the data in the above table, the following conclusions can be clearly obtained:

[0099] The optical lens glass obtained in Examples 1-3 was compared with the optical lens glass obtained in Comparative Examples 1-5. From the test results,

[0100] Compared with the comparative examples, the optical lens glass obtained in Examples 1-3 has higher transmittance, hardness, and contact angle data, and a lower transmittance decrease rate at the same time. This fully demonstrates that the present invention has achieved an improvement in the optical performance, wear resistance, and hydrophobic self-cleaning performance of the fabricated optical lens glass.

[0101] Compared with Example 1, the sol in Comparative Example 1 was prepared from styrene, polyvinylpyrrolidone, tetraethyl orthosilicate, etc., and the fluorine-containing POSS was replaced with styrene. On the basis of Comparative Example 1, the POSS in Comparative Example 2 was vinyl POSS. Compared with Example 1, no POSS modification layer was provided in Comparative Example 3. Compared with Comparative Example 3, the high borosilicate glass in Comparative Example 4 was not etched, and the optical lens glass was composed of high borosilicate glass and a hollow silica layer. The optical lens glass in Comparative Example 5 was obtained by etching high borosilicate glass. For the optical lens glass obtained in Comparative Examples 1-5, its transmittance, hardness, contact angle, and transmittance decrease rate could not maintain an optimal level simultaneously. It can be seen that the setting of the process of the optical lens glass and the components used in the present invention can promote the comprehensive improvement of its optical performance, wear resistance, and hydrophobic self-cleaning performance.

[0102] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

Claims

1. A preparation process of high borosilicate optical lens glass, characterized in that: It includes the following processes: Mix and melt the raw materials, form them, and perform heat treatment to obtain high borosilicate glass; Etch, apply sol coating to form an antireflection layer, and obtain optical lens glass; The sol coating process is as follows: Modify the etched high borosilicate glass with hydrosilane; Use trifluoroethoxysilane and alkenyl siloxane as raw materials to prepare fluorinated POSS; Add dichloromethane and a photoinitiator to prepare a fluorinated POSS / dichloromethane dispersion; Add the high borosilicate glass obtained in the previous step and irradiate with ultraviolet light to form a POSS modification layer; Take fluorinated POSS and polyvinylpyrrolidone, mix them in a solvent, add an initiator, and heat to react; Then add tetraethyl orthosilicate, ammonia water, and absolute ethanol, and react to obtain a sol; Immerse and lift the high borosilicate glass obtained in the previous step in the sol, and calcine to form a hollow silica layer to obtain an antireflection layer; The hydrosilane is one of triethoxysilane and trimethoxysilane.

2. The preparation process of a high-borosilicate optical lens glass according to claim 1, characterized in that: The raw materials include the following mass components: 78 - 85 parts of silica, 10 - 15 parts of boron oxide, 5 - 10 parts of borax, 3 - 6 parts of sodium oxide, 2 - 10 parts of sodium silicate, 2.0 - 4.5 parts of aluminum hydroxide, 1 - 3 parts of zirconium phosphate, 0.1 - 0.5 parts of lithium oxide, 0.065 - 0.075 parts of cerium dioxide.

3. The preparation process of a high-borosilicate optical lens glass according to claim 1, characterized in that: The mixing and melting process is as follows: Heat the raw materials to melt at a temperature of 1400 - 1550 °C, and keep warm for 30 - 60 min; Raise the temperature to 1600 - 1700 °C, introduce oxygen, and melt for 1 - 3 h; The oxygen flow rate is 0.5 - 3.0 L / min, and the introduction duration is 10 - 60 min.

4. The preparation process of a high-borosilicate optical lens glass according to claim 1, characterized in that: The heat treatment process is as follows: Keep warm at a temperature of 540 - 650 °C for 1 - 3 h; Cool naturally.

5. The preparation process of a high-borosilicate optical lens glass according to claim 1, characterized in that: The etching process is as follows: Place the high borosilicate glass in an etching solution, and perform hydrothermal reaction at a temperature of 158 - 162 °C for 450 - 500 min to form an etching layer; The etching solution includes the following mass components: 3.0 - 22.5 g / L of disodium ethylenediaminetetraacetate, 5.5 - 35 g / L of tetrasodium ethylenediaminetetraacetate; The mass ratio of disodium ethylenediaminetetraacetate to tetrasodium ethylenediaminetetraacetate is (30 - 45):(55 - 70).

6. The preparation process of a high-borosilicate optical lens glass according to claim 1, characterized in that: The sol coating process is as follows: (1) Place the etched high borosilicate glass in a hydrosilane / ethanol solution, and ultrasonicate for 20 - 30 min; Take it out and hydrolyze at a temperature of 23 - 27 °C and a humidity of 40% - 50% for 18 - 24 h to form a hydrosilane modification layer; (2) Mix trifluoroethoxysilane, alkenyl siloxane, ethanol, hydrochloric acid, and deionized water, heat to 70 - 80 °C, stir and reflux for 5 - 12 h; Cool to room temperature and continue to react for 15 - 24 h to obtain fluorinated POSS; Add dichloromethane and a photoinitiator to prepare a fluorinated POSS / dichloromethane dispersion; Place the high borosilicate glass obtained in the previous step in the fluorinated POSS / dichloromethane dispersion, irradiate with ultraviolet light for 10 - 50 min; Then place it at a temperature of 150 - 160 °C and cure for 100 - 150 min to form a POSS modification layer; (3) Mix deionized water, fluorinated POSS, and polyvinylpyrrolidone, heat to 28 - 82 °C, add an initiator, and react for 1 - 15 h; add ammonia water and absolute ethanol, and slowly add tetraethyl orthosilicate while stirring at a temperature of 68 - 72 °C for 10 - 12 h to obtain a sol. Immerse the high borosilicate glass obtained in the previous step in the sol for 6 - 10 min, then lift it out at a lifting speed of 70 - 80 cm / min; leave it at room temperature for 10 - 15 min, dry it at a temperature of 60 - 70 °C for 8 - 12 h, and calcine it at a temperature of 400 - 500 °C for 2 - 3 h to form a hollow silica layer and obtain an antireflection layer.

7. The preparation process of a high-borosilicate optical lens glass according to claim 6, characterized in that: In step (1), the concentration of the hydrosilane / ethanol solution is 3 - 5 v%.

8. The preparation process of a high-borosilicate optical lens glass according to claim 6, characterized in that: In step (2), the mass ratio of monofluorotriethoxysilane, alkenylsiloxane, ethanol, deionized water and hydrochloric acid is (67-80): (14-58): 100: (12-16): (7.5×10 -4 ~8.3×10 -4 ).

9. The preparation process of a high-borosilicate optical lens glass according to claim 6, characterized in that: In step (3), the sol is prepared from the following components: by mass, 2.5 - 3.0 parts of fluorinated POSS, 0.3 - 0.4 parts of polyvinylpyrrolidone, 0.1 - 0.2 parts of initiator, 6 - 8 parts of ammonia water, 5 - 6 parts of tetraethyl orthosilicate, 100 - 120 parts of absolute ethanol, and 45 - 50 parts of deionized water.

10. A high borosilicate optical lens glass prepared by the preparation process according to any one of claims 1 - 9.