High-air-tightness low-haze environment-friendly cover plate glass, and preparation method and application thereof

Abstract

The present application relates to special glass material, especially to a kind of high air-tightness low haze environment-friendly cover plate glass and its preparation method and application.It is composed of the following components:SiO2 53.0~62.0 parts, Al2O3 9.0~15.0 parts, CaO 0.1~2.0 parts, MgO 4.0~8.0 parts, K2O 3.0~7.0 parts, Na2O 9.0~15.0 parts, Li2O 0~2.0 parts, ZrO2 0.5~2.0 parts, B2O3 2.0~6.0 parts, Bi2O3 0~3.0 parts, Ag2O 0~2.0 parts, In2O3 0~3.0 parts, CeO2 0.1~1.0 parts.The cover plate glass provided by the present application not only has good performance in air-tightness, transmittance, haze, strength, chemical stability and environmental protection, but also can reduce the generation of black light absorption layer, and has good processing performance.

Description

Technical Field

[0001] This invention relates to special glass materials, and more particularly to a high-airtightness, low-haze, environmentally friendly cover glass, its preparation method, and its application. Background Technology

[0002] Cover glass (also known as a viewing window protective screen) is mainly used for the front screen and back cover. Behind the cover glass are the OLED panel and many sensitive electronic components. OLEDs and electronic components require a dry working environment; prolonged exposure to humid or oxidizing environments can easily cause oxidation and corrosion, significantly shortening the lifespan of the touch module. As a protective barrier for the display and touch module, the cover glass comes into direct contact with the human body, and sweat is particularly corrosive to the display and touch module and electronic components. The airtightness of the glass is a crucial standard for preventing moisture and oxygen from entering the glass; therefore, the airtightness and corrosion resistance of the cover glass directly affect the lifespan of mobile phones and other digital products.

[0003] On the other hand, cover glass requires high strength and scratch resistance, often necessitating the introduction of large amounts of high-viscosity oxides into the glass. During production, to reduce the difficulty of glass clarification, relatively fusible nitrates are often used as raw materials, along with clarifying agents such as As₂O₃ and Sb₂O₃ to accelerate the removal of air bubbles. However, clarifying agents like As₂O₃ and Sb₂O₃ generate heavy metals such as arsenic and antimony during glass melting, posing serious health risks. Furthermore, nitrates also form nitrogen oxides (NO₃) during glass melting. X This causes pollution to the environment. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a high-airtightness, low-haze, environmentally friendly cover glass, its preparation method, and its application. The cover glass provided by the present invention has excellent performance, not only in terms of airtightness, transmittance, haze, strength, and environmental friendliness, but also in the ability to produce a black anti-impurity layer under a reducing atmosphere, as well as good chemical stability and processing performance, thus having broad application prospects.

[0005] To achieve the above objectives, the present invention provides a high-airtightness, low-haze, environmentally friendly cover glass material that contains SiO2, Al2O3, CaO, MgO, K2O, Na2O, Li2O, ZrO2, B2O3, Bi2O3, Ag2O, In2O3, and CeO2. Furthermore, by controlling its composition and content, it achieves excellent comprehensive performance, including haze, strength, water vapor transmittance, optical transmittance, and environmental friendliness. The specific technical solution is as follows.

[0006] Firstly, a high-airtightness, low-haze, environmentally friendly cover glass, by weight, is composed of the following components: 53.0–62.0 parts SiO2, 9.0–15.0 parts Al2O3, 0.1–2.0 parts CaO, 4.0–8.0 parts MgO, 3.0–7.0 parts K2O, 9.0–15.0 parts Na2O, 0–2.0 parts Li2O, 0.5–2.0 parts ZrO2, 2.0–6.0 parts B2O3, 0–3.0 parts Bi2O3, 0–2.0 parts Ag2O, 0–3.0 parts In2O3, and 0.1–1.0 parts CeO2; wherein at most one of Bi2O3, Ag2O, and In2O3 has a weight of 0.

[0007] In this invention, the sum of the weight parts of the components is 100 parts.

[0008] In the aforementioned cover glass system, this invention reduces the viscosity of the molten glass and simplifies glass forming by controlling the contents of CaO, K₂O, Na₂O, Bi₂O₃, and B₂O₃. Controlling the contents of SiO₂, Al₂O₃, Na₂O, K₂O, Bi₂O₃, and Ag₂O reduces the glass's crystallization tendency and improves its transmittance after forming. Controlling the contents of SiO₂, Al₂O₃, CaO, MgO, and Ag₂O improves the glass's chemical stability and airtightness, enhances its resistance to corrosion in complex environments, and extends its service life. Controlling the contents of Al₂O₃, Ag₂O, MgO, ZrO₂, and Ag₂O increases the glass's strength and enhances its scratch and drop resistance. Furthermore, the presence of Na₂O and K₂O endows the glass with chemical strengthening capabilities. Meanwhile, by controlling the content and ratio of reducing substances Bi2O3, Ag2O, In2O3, and alkali metal compounds K2O and Na2O, the water vapor transmittance, bending strength, and optical properties can be further adjusted.

[0009] In the glass system of this invention, the integrated effect of SiO2, CaO, Al2O3, B2O3, and MgO jointly enhances the thermal and chemical stability of the glass. The synergistic effect of CaO, Al2O3, B2O3, and MgO regulates the coefficient of thermal expansion and enhances chemical stability. The addition of MgO further improves the glass's resistance to corrosion in complex environments and extends its service life. The introduction of Al2O3, MgO, B2O3, Ag2O, and Bi2O3 improves optical quality and enhances the optical transmittance of the glass material. The combined effect of Na2O, Bi2O3, B2O3, and CeO2 reduces the difficulty of glass refining and decreases defects such as bubbles during the glass melting process.

[0010] In summary, the high airtightness, low haze, and environmentally friendly cover glass provided by this invention contains SiO2, Al2O3, CaO, MgO, K2O, Na2O, Li2O, ZrO2, B2O3, Bi2O3, Ag2O, In2O3, and CeO2. By precisely controlling the content of SiO2, Al2O3, CaO, MgO, K2O, Na2O, Li2O, ZrO2, B2O3, Bi2O3, Ag2O, In2O3, and CeO2, it exhibits excellent comprehensive performance in terms of haze, strength, water vapor transmittance, optical transmittance, environmental friendliness, and reduction blackening layer thickness.

[0011] Experiments have shown that the cover glass provided by this invention has a water vapor transmission rate of ≤8×10⁻⁶. -9 g / m 2 It possesses excellent comprehensive properties, including haze ≤0.39%, bending strength ≥129MPa, and maximum optical transmittance of 2mm glass samples within the wavelength range of 400~1000nm not less than 90.0%.

[0012] Secondly, a method for preparing the above-mentioned high airtightness, low haze, and environmentally friendly cover glass involves mixing the raw materials evenly according to the proportions of each component, and then sequentially melting, stirring, clarifying, and molding the mixture to obtain the final product.

[0013] Thirdly, the application of the aforementioned high airtightness, low haze, and environmentally friendly cover glass in the preparation of screen substrates.

[0014] Fourthly, the application of the aforementioned high airtightness, low haze, and environmentally friendly glass cover in the manufacture of digital product cover plates.

[0015] The beneficial effects of this invention are as follows:

[0016] 1. The high airtightness, low haze, and environmentally friendly cover glass provided by this invention, by adjusting the composition and content of each component, possesses the following excellent properties: water vapor transmission rate ≤ 8 × 10⁻⁶. -9 g / m 2 •d, haze ≤0.39%, bending strength ≥129MPa, maximum optical transmittance of 2mm glass sample in the wavelength range of 400~1000nm ≥90.0%; at the same time, the cover glass is harmless to the human body and the environment during the melting process.

[0017] 2. The high airtightness, low haze, and environmentally friendly cover glass provided by this invention also has the following properties: acid resistance and moisture resistance are level 1, and mechanical and processing properties are good. Therefore, it can be used as the main material for cover plates of various digital products. Attached Figure Description

[0018] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0019] Figure 1 This is a comparison curve of the transmittance of 2mm thick glass products of Comparative Example 1 and Example 1 in the wavelength range of 400-1000nm.

[0020] Figure 2 The graphs show a comparison of the bending strength (a), haze (b), and water vapor transmittance (c) of the glass materials in Examples 1-9 and Comparative Examples 1-5. Detailed Implementation

[0021] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0022] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0023] Given that the airtightness and corrosion resistance of existing substrate glass cannot meet the increasing lifespan of digital products, this invention proposes a high-airtightness, low-haze, environmentally friendly cover glass, its preparation method, and its application.

[0024] A typical embodiment of the present invention provides a high-airtightness, low-haze, environmentally friendly cover glass, which, by weight, is composed of the following components: SiO2 53.0–62.0 parts, Al2O3 9.0–15.0 parts, CaO 0.1–2.0 parts, MgO 4.0–8.0 parts, K2O 3.0–7.0 parts, Na2O 9.0–15.0 parts, Li2O 0–2.0 parts, ZrO2 0.5–2.0 parts, B2O3 2.0–6.0 parts, Bi2O3 0–3.0 parts, Ag2O 0–2.0 parts, In2O3 0–3.0 parts, CeO2 0.1–1.0 parts; wherein, at most one of Bi2O3, Ag2O, and In2O3 has a weight of 0.

[0025] In this invention, SiO2 is a glass-forming oxide. As a major component of glass, it provides the basic structural framework, endowing the glass with good chemical stability and mechanical strength. A suitable SiO2 content can reduce the coefficient of thermal expansion of the glass and improve its thermal stability, chemical stability, softening temperature, heat resistance, hardness, and mechanical strength. Excessive SiO2 content may lead to an increased melting point and processing difficulties; insufficient SiO2 content may weaken chemical stability and mechanical strength. The preferred SiO2 content is 53.0–60.0 parts, 53.0–58.0 parts, 55.0–58.0 parts, 56.0–58.0 parts, or 56.5–57.5 parts.

[0026] Al₂O₃ is an essential component for improving the chemical stability of glass, reducing its tendency to crystallize, and also increasing its hardness, mechanical strength, and tensile modulus. In the glass network structure, alumina is an intermediate oxide, situated between the network generator and the network exogenous body. The preferred proportions of Al₂O₃ are 9.0–9.5 parts, 11.0–15.0 parts, 11.0–14.0 parts, 12.0–14.0 parts, and 12.5–13.5 parts.

[0027] In this invention, the introduction of CaO can increase the chemical stability and mechanical strength of the glass. However, excessive CaO can easily cause crystallization and reduce the thermal stability of the glass. Simultaneously, CaO can reduce the viscosity of the glass at high temperatures, which is beneficial for clarification. The introduction of MgO can improve the thermal stability of the glass and reduce its coefficient of thermal expansion. However, excessive MgO can increase the viscosity of the glass, making glass forming difficult. MgO and CaO work together to enhance the mechanical strength and chemical durability of the glass in this invention. The addition of MgO is particularly helpful in reducing the increase in the coefficient of thermal expansion caused by CaO. The preferred CaO content is 0.4–2.0 parts, 0.7–2.0 parts, 0.7–1.3 parts, 1.7–2.0 parts, etc. The preferred MgO content is 4.9–8.0 parts, 5.0–8.0 parts, 5.0–7.0 parts, 5.5–6.5 parts, etc.

[0028] In this invention, K₂O and Na₂O are network oxides of the glass. Alkali metal ions readily move and diffuse within the glass, reducing the viscosity during high-temperature melting and facilitating melting. They are excellent fluxes, but their introduction should not be excessive, as this increases the coefficient of thermal expansion and reduces the glass's chemical stability, thermal stability, and mechanical strength. Furthermore, K₂O can enhance glass gloss, reduce surface haze, and improve transmittance after forming. Preferably, the K₂O content is 3.5–6.5 parts, 3.5–6.0 parts, 4.0–6.0 parts, or 4.5–5.5 parts. Preferably, the Na₂O content is 9.2–15.0 parts, 9.0–14.0 parts, 9.0–14.0 parts, 10.0–12.0 parts, or 11.0–12.0 parts.

[0029] In this invention, Li₂O can combine with oxygen atoms in the glass network to form Li-O bonds, which helps to enhance the network structure of the glass and improve its physical properties. Furthermore, the introduction of Li₂O in this invention can reduce the tendency for crystal formation during the cooling and solidification process, helping to maintain the amorphous state of the glass, improving its optical transparency, making it easier to achieve transparency, increasing optical transmittance, and reducing haze. However, it is important to note that the amount of Li₂O used needs to be precisely controlled. Excessive Li₂O will reduce the chemical stability of the glass and may cause it to be more prone to crystallization and phase separation. The preferred amounts of Li₂O are 0.1–2.0 parts, 0–1.0 parts, 0–0.9 parts, 0.1–0.9 parts, and 0.3–0.7 parts.

[0030] In this invention, ZrO2 is a glass intermediate oxide that improves chemical stability, prevents the exposure of alkali metal and alkaline earth metal ions, and is also an important component for improving tensile elastic modulus, greatly contributing to the increase in hardness after chemical strengthening of glass. The preferred amounts of ZrO2 are 0.5–1.3 parts, 1.3–2.0 parts, and 0.7–1.3 parts, etc.

[0031] In this invention, B2O3 is also a glass-forming oxide. It uses boron-oxygen trigonals [BO3] and boron-oxygen tetrahedra [BO4] as structural units, forming a structural network with silicon tetrahedra in borosilicate glass. B2O3 reduces the viscosity of glass at high temperatures and increases it at low temperatures, thus glasses with higher B2O3 content have a wider forming temperature range. B2O3 also acts as a flux, accelerating the dissolution and clarification of the glass. However, when the amount of B2O3 added is too high, the increased boron-oxygen trigonals lead to an increase in the glass's coefficient of thermal expansion, resulting in boron anomalies and reducing the glass's chemical stability. The preferred amounts of B2O3 are 2.0–5.5 parts, 2.0–5.0 parts, 2.0–4.5 parts, 2.0–4.0 parts, 2.0–3.5 parts, 2.5–3.5 parts, and 2.8–3.2 parts.

[0032] In this invention, the synergistic effect of two or all three of Bi₂O₃, Ag₂O, and In₂O₃ can enhance the light absorption rate of the glass after reduction blackening. The addition of Bi₂O₃ can improve the refractive index and dispersion. Bi₂O₃ also helps improve the thermal stability of the glass and enhances its light absorption capacity. Furthermore, since Bi (usually introduced as Bi₂O₃ or Bi(NO₃)₃) can be reduced to black in a high-temperature hydrogen atmosphere, this property can be used to optimize stray light absorption. However, the introduction of Bi₂O₃ needs to be precisely controlled. Excessive addition of Bi₂O₃ may lead to a significant decrease in the chemical stability of the glass, especially when reacting with reducing gases. In addition, high concentrations of Bi₂O₃ may cause severe corrosion to the melting vessel during glass melting, limiting its application in glass production. Furthermore, excessive Bi₂O₃ may also promote glass crystallization, affecting its transparency and optical uniformity. Conversely, insufficient Bi₂O₃ content makes it difficult to improve optical performance. The introduction of Ag₂O can improve the optical properties of glass. Ag₂O has good absorption and reflection properties, thus effectively blocking the penetration of ultraviolet and visible light, improving the light transmittance and shading performance of the glass. Secondly, it can improve the chemical stability and mechanical strength of glass. Ag₂O can form composite glass structures and crystal hardening layers with other glass additives, improving the corrosion resistance, hardness, and toughness of the glass material, thereby enhancing its mechanical strength and impact resistance. In₂O₃ can improve the thermal conductivity and mechanical properties of glass materials. When the indium content is low, it can effectively improve the thermal stability and heat resistance of the glass; while when the indium content increases, the density and refractive index of the glass also increase. However, excessive In₂O₃ content can also easily lead to severe discoloration of the glass. The preferred amounts of Bi₂O₃ are 0.1–3.0 parts, 0.1–2.5 parts, 0.1–2.0 parts, 0.1–1.5 parts, 0.1–1.0 parts, 0.1–0.9 parts, and 0.3–0.7 parts. The preferred amounts of Ag2O are 0.1–2.0 parts, 0.1–1.5 parts, 0.1–1.0 parts, 0.1–0.9 parts, and 0.3–0.7 parts. The preferred amounts of In2O3 are 0.1–3.0 parts, 0.1–2.5 parts, 0.1–2.0 parts, 0.1–1.5 parts, 0.1–1.0 parts, 0.1–0.9 parts, and 0.3–0.7 parts.

[0033] Cerium oxide is an environmentally friendly clarifying agent. Its clarifying mechanism is that cerium oxide is an oxide with a variable valence state, and it decomposes to release oxygen at high temperatures. For every 1°C increase in temperature, more oxygen can be separated from its chemical bonds, resulting in a better clarifying effect. The solubility of oxygen decreases with increasing temperature, thus producing a clarifying effect. No toxic gases are generated during the clarification process. The preferred concentrations of CeO2 are 0.1–0.8 parts, 0.1–0.7 parts, 0.1–0.6 parts, 0.1–0.5 parts, 0.1–0.4 parts, 0.1–0.3 parts, 0.3–0.8 parts, 0.4–0.8 parts, 0.4–0.7 parts, and 0.5–0.7 parts.

[0034] In some embodiments, the weight percentage of Na₂O is greater than nine-sevenths of the weight percentage of K₂O. Studies have shown that the glass properties are better under these compositional conditions.

[0035] In some embodiments, the weight fraction of B2O3 is less than two-thirds the weight fraction of Al2O3. Studies have shown that the glass properties are better under these compositional conditions.

[0036] In some embodiments, the sum of the weight parts of Bi2O3, Ag2O, and In2O3 is greater than 1 part, preferably 1.1 to 5 parts, more preferably 1.1 to 4 parts, and even more preferably 1.1 to 2 parts. Studies have shown that the glass properties are better under these composition conditions.

[0037] In some embodiments, the water vapor transmission rate is ≤8×10⁻⁶. -9 g / m 2 ·d, preferably (2~8)×10 -9 g / m 2 ·d, preferably (2~6)×10 -9 g / m 2 ·d, preferably (2~5)×10 -9 g / m 2 ·d, preferably (2~3)×10 -9 g / m 2 ·d.

[0038] In some embodiments, the haze is ≤0.39%, preferably 0.18–0.39%, preferably 0.18–0.32%, preferably 0.18–0.26%, preferably 0.18–0.24%, preferably 0.18–0.20%, and preferably 0.18–0.19%.

[0039] In some embodiments, the bending strength is ≥129 MPa, preferably 129–141 MPa, preferably 132–141 MPa, and more preferably 139–141 MPa.

[0040] In some embodiments, the maximum optical transmittance of the 2mm glass sample in the wavelength range of 400–1000nm is ≥90.0%, preferably 90.0–91.8%, and more preferably 91.0–91.8%.

[0041] Another embodiment of the present invention provides a method for preparing the above-mentioned high airtightness, low haze, and environmentally friendly cover glass, wherein the raw materials are mixed evenly according to the proportion of each component, and then the mixture is melted, stirred, clarified, and shaped in sequence to obtain the final product.

[0042] In some embodiments, the melting temperature is 1500–1580°C. Specifically, the melting time is 8–30 hours. Under these melting time conditions, it is beneficial for the glass melt to become clear.

[0043] When the uniformity of the feed solution is low, it is prone to stratification or clumping, making glass melting and homogenization difficult, and in severe cases, even causing streaks or stone defects. In some embodiments, the stirring speed is 10-20 r / min, and the stirring time is 3-12 h. These stirring conditions are beneficial to the uniformity of the feed solution.

[0044] In some embodiments, the forming temperature is 1350–1400°C, and the forming time is 5–25 minutes. Under these forming conditions, the glass forming speed can be increased, while secondary bubbles and impurities can be avoided.

[0045] A third embodiment of the present invention provides an application of the above-mentioned high airtightness, low haze, and environmentally friendly cover glass in the preparation of screen substrates.

[0046] A fourth embodiment of the present invention provides an application of the above-mentioned high airtightness, low haze, and environmentally friendly cover glass in the manufacture of cover plates for digital products.

[0047] In some embodiments, the cover glass includes a light-absorbing region, wherein the maximum optical transmittance of the light-absorbing region is ≤2.9%, preferably 1.3 to 2.9%, and more preferably 1.3 to 2.0%.

[0048] In one or more embodiments, the light-absorbing region is obtained by further blackening the high-airtightness, low-haze, environmentally friendly cover glass. Specifically, the blackening process is carried out in a reducing atmosphere for 4000–16000 min, with a pressure of 0.01–0.5 MPa and a temperature of 450–620 °C. For example, under reducing atmosphere conditions, the pressure is 0.01 MPa, the blackening temperature is 600 °C, and the blackening time is 10000 min. More specifically, the reducing atmosphere is a hydrogen atmosphere, and there are multiple cycles of gas filling and venting during the entire reduction process, with each cycle lasting 160–300 min.

[0049] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments and comparative examples.

[0050] The performance parameters in the following embodiments were obtained by measuring them using the following method:

[0051] The coefficient of thermal expansion α of the glass samples was measured using a DIL 402 thermal expansion meter manufactured by Netzsch AG, Germany. Sample preparation involved grinding the glass sample into a cylindrical strip with dimensions Φ6×50mm, ensuring both ends were parallel. The heating rate was set to 5℃ / min, and the data acquisition period was 20ms. Reference was made to GB / T7962.16-2010.

[0052] The softening point temperature of glass samples was tested using an Orton Model PPV-1000 / 1200 plate viscometer. Sample preparation: The glass sample was ground into a cylindrical strip of Φ6×6mm, with both ends parallel. The sample was placed between top and bottom discs made of a heat-resistant metal alloy, 44mm in diameter and 6mm thick. The top metal disc was attached to the bottom of the probe bar. Two very thin platinum films (40mm in diameter and 0.001 inch thick) were placed between the sample and the top and bottom discs for easy sampling and sample placement. Refer to ASTM C-1351M.

[0053] Transmittance was tested using a UV-Vis-IR spectrophotometer.

[0054] After polished glass samples were eroded by test media with acidities of pH 2.9, pH 4.6, and pH 6.0, the time it took for the glass surface to exhibit violet-blue interference colors, surface discoloration, or peeling under incandescent light was observed. The acid resistance stability of colorless optical glass was classified in descending order based on the duration of this time. (Refer to GB / T 7962.14-2010)

[0055] Polished glass samples were kept at a constant temperature and humidity of 50℃ and 85% for 20 hours. The moisture resistance stability of the colorless optical glass was classified in descending order by comparing its turbidity values ​​with those of standard samples H(BaK7) and H(ZK9). (Refer to GB / T7962.15-2010)

[0056] The haze of glass samples was tested using a Qunlong CS series haze meter. Sample preparation involved grinding and polishing the glass samples into circular glass slides measuring Φ32×20mm. The spectral response was determined using the CIE spectral function Y / V(λ), with a wavelength range of 400-700nm, wavelength intervals of 10nm, and a resolution of 0.01 units. Reference was made to GB / T24010.

[0057] The bending strength of glass samples is tested using the three-point bending method. The glass sample is machined to the required dimensions for the test, then placed between two support points, and a fixed load perpendicular to the center of the sample is applied. Then, by applying different bending moments, the bending stress and strain of the glass are measured under different conditions. The bending strength of the glass is finally determined. Refer to GB / T 37781-2019.

[0058] Example 1

[0059] The components, weight percentages of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figures 1-2 .

[0060] The preparation method of high airtightness, low haze, and environmentally friendly cover glass is as follows: Quartz sand, aluminum hydroxide, calcium carbonate, basic magnesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, zirconium oxide, bismuth oxide, silver phosphate, indium oxide, and cerium oxide are used as raw materials. After thorough mixing, the mixture is melted at 1540℃ for 12 hours, mechanically stirred (15 r / min, 4 hours), assisted with high-temperature clarification, and pressed into shape at 1380℃ (forming time is 5 minutes) to obtain glass blanks. The glass blanks are then placed in an annealing furnace preheated to 580℃ for annealing to eliminate internal stress and meet the requirements of subsequent cold working.

[0061] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 600℃, a reducing gas hydrogen pressure of 0.01MPa, and a blackening time of 10000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0062] Example 2

[0063] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0064] In the preparation method of high airtightness, low haze, and environmentally friendly cover glass, the melting temperature is 1550℃ and the melting time is 16h; mechanical stirring (20r / min, 12h), the forming temperature is 1400℃ and the forming time is 15min, and other preparation steps and parameters are the same as in Example 1.

[0065] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 620℃, a reducing gas hydrogen pressure of 0.2MPa, and a blackening time of 10,000 min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0066] Example 3

[0067] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0068] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1580℃ and the melting time is 30h; mechanical stirring (20r / min, 12h) is used; the forming temperature is 1400℃ and the forming time is 25min; other preparation steps and parameters are the same as in Example 1.

[0069] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 450℃, a reducing gas hydrogen pressure of 0.3MPa, and a blackening time of 4000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0070] Example 4

[0071] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0072] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1560℃ and the melting time is 20h; mechanical stirring (10r / min, 14h) is used; the forming temperature is 1400℃ and the forming time is 25min; other preparation steps and parameters are the same as in Example 1.

[0073] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 500℃, a reducing gas hydrogen pressure of 0.4MPa, and a blackening time of 6000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0074] Example 5

[0075] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0076] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1500℃ and the melting time is 25h; mechanical stirring (20r / min, 14h) is used; the forming temperature is 1380℃ and the forming time is 25min; other preparation steps and parameters are the same as in Example 1.

[0077] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 530℃, a reducing gas hydrogen pressure of 0.5MPa, and a blackening time of 12000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0078] Example 6

[0079] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0080] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1560℃ and the melting time is 30h; mechanical stirring (20r / min, 12h) is used; the forming temperature is 1400℃ and the forming time is 25min; other preparation steps and parameters are the same as in Example 1.

[0081] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 620℃, a reducing gas hydrogen pressure of 0.2MPa, and a blackening time of 16000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0082] Example 7

[0083] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0084] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1550℃ and the melting time is 30h; mechanical stirring (20r / min, 14h) is performed; the forming temperature is 1400℃ and the forming time is 25min; other preparation steps and parameters are the same as in Example 1.

[0085] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 600℃, a reducing gas hydrogen pressure of 0.2MPa, and a blackening time of 13000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0086] Example 8

[0087] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0088] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1550℃ and the melting time is 30h; mechanical stirring (20r / min, 14h) is performed; the forming temperature is 1400℃ and the forming time is 20min; other preparation steps and parameters are the same as in Example 1.

[0089] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 610℃, a reducing gas hydrogen pressure of 0.2MPa, and a blackening time of 8000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0090] Example 9

[0091] The components, weight percentage of each component, and physical properties of the high airtightness, low haze, environmentally friendly cover glass of this embodiment are shown in Tables 1 and 3. Figure 2 .

[0092] In this embodiment, the preparation method of the high airtightness, low haze, and environmentally friendly cover glass is as follows: the melting temperature is 1560℃ and the melting time is 30h; mechanical stirring (20r / min, 14h) is performed; the forming temperature is 1400℃ and the forming time is 20min; other preparation steps and parameters are the same as in Example 1.

[0093] After annealing, the glass blank is processed into a certain size and placed in a blackening reduction furnace. The blackening program is set with a blackening temperature of 590℃, a reducing gas hydrogen pressure of 0.2MPa, and a blackening time of 9000min. After the blackening treatment, a stray light absorbing layer is formed on the glass surface.

[0094] Comparative Examples 1-5

[0095] The composition and weight percentage of each component of the glasses in Comparative Examples 1–5, as well as the physical properties of the resulting glasses, are shown in Tables 2 and 4. Figures 1-2 .

[0096] The glass preparation steps, blackening and reduction steps, and parameters in Comparative Examples 1 to 5 were the same as those in Example 1.

[0097] Table 1. Components and content of environmentally friendly cover glass in Examples 1-9 of the present invention

[0098]

[0099]

[0100] Table 2. Components and contents of the glasses in Comparative Examples 1-5 of this invention

[0101]

[0102]

[0103] Table 3 Performance test results of glass samples from Examples 1-9

[0104]

[0105]

[0106] Table 4 shows the performance test results of the glass samples from Comparative Examples 1 to 5.

[0107]

[0108]

[0109] In Tables 3 and 4, the samples with the test item "maximum optical transmittance after reduction / % (350-1000nm)" are glass samples after reduction blackening treatment, while the samples with other test items are glass samples before reduction blackening treatment.

[0110] Examples 1-9, through the reasonable addition of appropriate components and control of the proportions of each component in the raw materials, show improved haze, strength, water vapor transmittance, optical transmittance, and environmental performance of the glass. Table 3 shows that the optical transmittance of the high-airtightness, low-haze, environmentally friendly cover glass prepared in Examples 1-9 of this invention is as follows: Within the wavelength range of 400-1000 nm, the maximum transmittance is 92.8%. Its overall performance is superior to the glass involved in Comparative Examples 1-5, and it also exhibits good acid / moisture resistance stability, maintaining the stability of the internal structure of the glass over a long period.

[0111] As can be seen from the above, the high-airtightness, low-haze, environmentally friendly cover glass provided in Examples 1-9 of the present invention possesses excellent optical transmittance, low haze, high flexural strength, low water vapor transmittance, and good processing performance. This is because Examples 1-9 of the present invention adjusted the proportions of each component raw material and set appropriate stirring speeds and times during the preparation of the high-airtightness, low-haze, environmentally friendly substrate glass. Therefore, the high-airtightness, low-haze, environmentally friendly cover glass of the present invention has high optical transmittance, high flexural strength, and low haze and water vapor transmittance, and has broad application prospects.

[0112] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-airtightness, low-haze, environmentally friendly cover glass, characterized in that, By weight, it is composed of the following components: SiO2 56.0~58.0 parts, Al2O3 11.0~14.0 parts, CaO 0.7~2.0 parts, MgO 4.0~8.0 parts, K2O 3.5~6.5 parts, Na2O 11.0~12.0 parts, Li2O 0.1~2.0 parts, ZrO2 0.5~2.0 parts, B2O3 2.0~6.0 parts, Bi2O3 0.3~0.7 parts, Ag2O 0.1~2.0 parts, In2O3 0.3~0.7 parts, CeO2 0.1~1.0 parts; Water vapor transmission rate ≤8×10 -9 g / m 2 •d; Haze ≤0.39%; Bending strength ≥129 MPa; Maximum optical transmittance of 2 mm glass samples in the wavelength range of 400~1000 nm ≥90.0%; The weight percentage of Na2O is greater than nine-sevenths of the weight percentage of K2O; the weight percentage of B2O3 is less than two-thirds of the weight percentage of Al2O3; and the sum of the weight percentages of Bi2O3, Ag2O, and In2O3 is greater than one part.

2. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The SiO2 content is 56.5~57.5 parts; Alternatively, Al2O3 may be 12.0 to 14.0 parts; Alternatively, the CaO content may be 0.7 to 1.3 parts. Alternatively, MgO may be 4.9–8.0 parts. Alternatively, K2O should be 3.5 to 6.0 parts; Alternatively, ZrO2 may be 0.5 to 1.3 parts; Alternatively, B2O3 may be 2.0 to 5.5 parts; Alternatively, Ag2O may be 0.1 to 1.5 parts; Alternatively, CeO2 can be 0.1 to 0.8 parts.

3. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The content of Al2O3 is 12.5 to 13.5 parts.

4. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The CaO content is 1.7 to 2.0 parts.

5. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The content of MgO is 5.0 to 8.0 parts.

6. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The content of MgO is 5.0 to 7.0 parts.

7. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The content of MgO is 5.5 to 6.5 parts.

8. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The K2O content is 4.0~6.0 parts.

9. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of K2O is 4.5 to 5.5 parts.

10. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of Li2O is 0.1 to 0.9 parts.

11. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of Li2O is 0.3 to 0.7 parts.

12. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The ZrO2 content is 1.3 to 2.0 parts.

13. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The ZrO2 content is 0.7 to 1.3 parts.

14. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of B2O3 is 2.0 to 5.0 parts.

15. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The B2O3 content is 2.0 to 4.5 parts.

16. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of B2O3 is 2.0 to 4.0 parts.

17. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of B2O3 is 2.0 to 3.5 parts.

18. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of B2O3 is 2.5 to 3.5 parts.

19. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The B2O3 content is 2.8 to 3.2 parts.

20. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of Ag2O is 0.1 to 1.0 parts.

21. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of Ag2O is 0.1 to 0.9 parts.

22. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, The amount of Ag2O is 0.3 to 0.7 parts.

23. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.1 to 0.7 parts.

24. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.1 to 0.6 parts.

25. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.1 to 0.5 parts.

26. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.1 to 0.4 parts.

27. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.1 to 0.3 parts.

28. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.3 to 0.8 parts.

29. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.4 to 0.8 parts.

30. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.4 to 0.7 parts.

31. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, CeO2 content is 0.5 to 0.7 parts.

32. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that Bi The sum of the weight parts of 2O3, Ag2O, and In2O3 is 1.1 to 5 parts.

33. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that Bi The sum of the weight parts of 2O3, Ag2O, and In2O3 is 1.1 to 4 parts.

34. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that Bi The sum of the weight parts of 2O3, Ag2O, and In2O3 is 1.1 to 2 parts.

35. The high airtightness, low haze, environmentally friendly cover glass as described in claim 1, characterized in that, Water vapor permeability is (2~8) ×10 -9 g / m 2 ·d; Alternatively, the haze level is 0.18~0.39%; Alternatively, the bending strength is 129~141 MPa; Alternatively, the maximum optical transmittance of a 2 mm glass sample in the wavelength range of 400~1000 nm is 90.0~91.8%.

36. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, Water vapor transmission rate is (2~6) ×10 -9 g / m 2 ·d.

37. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, Water vapor transmission rate is (2~5) ×10 -9 g / m 2 ·d.

38. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The water vapor transmission rate is (2~3) ×10 -9 g / m 2 ·d.

39. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The haze level is 0.18~0.32%.

40. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The haze level is 0.18~0.26%.

41. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The haze level is 0.18~0.24%.

42. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The haze level is 0.18~0.20%.

43. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The haze level is 0.18~0.19%.

44. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The bending strength is 132~141 MPa.

45. The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The bending strength is 139~141 MPa.

46. ​​The high airtightness, low haze, environmentally friendly cover glass as described in claim 35, characterized in that, The maximum optical transmittance of the 2 mm glass sample in the wavelength range of 400~1000 nm is 91.0~91.8%.

47. A method for preparing a high-airtightness, low-haze, environmentally friendly cover glass as described in claim 1, characterized in that, The raw materials are mixed evenly according to the proportions of each component, and then the mixture is melted, stirred, clarified and shaped in sequence to obtain the final product.

48. The method for preparing high airtightness, low haze, environmentally friendly cover glass as described in claim 47, characterized in that, The melting temperature is 1500~1580 ℃; Alternatively, the stirring speed is 10~20 r / min, and the stirring time is 3~12 h; Alternatively, the molding temperature is 1350~1400 ℃, and the molding time is 5~25 min.

49. The method for preparing high airtightness, low haze, environmentally friendly cover glass as described in claim 48, characterized in that, The melting time is 8~30 h.

50. The application of the high airtightness, low haze, environmentally friendly cover glass according to any one of claims 1 to 46 in the preparation of screen substrates.

51. The application of the high airtightness, low haze, environmentally friendly cover glass according to any one of claims 1 to 46 in the manufacture of cover plates for digital products.

52. The application as described in claim 51, characterized in that, The cover glass includes a light-absorbing region, and the maximum optical transmittance of the light-absorbing region is ≤2.9%.

53. The application as described in claim 52, characterized in that, The maximum optical transmittance of the light absorption region is 1.3~2.9%.

54. The application as described in claim 52, characterized in that, The maximum optical transmittance of the light absorption region is 1.3~2.0%.

55. The application as described in claim 52, characterized in that, The light absorption region is obtained by further blackening the high-airtightness, low-haze, environmentally friendly cover glass.

56. The application as described in claim 55, characterized in that, The blackening treatment is carried out in a reducing atmosphere for a time of 4000~16000 min, with a pressure of 0.01~0.5 MPa and a temperature of 450~620 ℃.

Images