High-hardness electronic glass, its manufacturing method, and applications.

Abstract

The present invention belongs to the technical field of electronic glass, and discloses a high-hardness electronic glass and its manufacturing method and application. Calculated by mass percentage, the raw materials of the high-hardness electronic glass according to the present invention include the following components: 58.3 to 62.93% of SiO2, 23.02 to 25.94% of Al2O3, 1.95 to 5.02% of B2O3, 2.07 to 4.21% of Li2O, 0 to 2.88% of Na2O, 0 to 2.29% of K2O, 0 to 3.30% of TiO2, 0 to 3.99% of ZrO2, and 0 to 4.17% of P2O5, and the total mass percentage of all components is 100%.

Description

[Technical Field]

[0001] This application belongs to the field of electronic glass technology, and more specifically relates to high-hardness electronic glass, its manufacturing method, and applications. [Background technology]

[0002] The front touchscreens of mobile electronic devices such as cell phones and PDAs typically include a protective cover glass, and the back cover material uses glass, plastic, metal, and glass ceramics. With the spread of 5G, it has become clear that metal materials absorb 5G high-frequency signals, and the back covers of 5G cell phones are gradually being replaced with glass, and glass is now applied as protection to both the front and back covers of mobile electronic devices. Because they are frequently touched and used, the cover glass used needs to have excellent impact resistance and scratch resistance. However, current chemically strengthened high aluminosilicate cover glass can get scratched or micro-damaged on the surface when it comes into contact with hard objects such as keys during use. Such damage shortens the lifespan of the device and increases repair costs. Therefore, people are constantly striving to develop microcrystalline glass and its products that have drop resistance, pressure resistance, scratch resistance, and high transmittance. [Overview of the project] [Problems that the invention aims to solve]

[0003] However, glass is a brittle material and contains many Griffith cracks. While the surface compressive stress layer formed after chemical strengthening has some effect in containing cracks, once the crack expands beyond the depth of the compressive stress layer, it loses its ability to prevent crack propagation. Therefore, the existence of crystallized glass, which has both a crystalline phase and a glass phase, has attracted attention. The presence of the crystalline phase prevents crack propagation and improves the scratch resistance and crack resistance of the glass. However, since the presence of the crystalline phase also affects the transparency of the glass, developing electronic glass that combines high transmittance and high hardness to meet the performance requirements of front and back protective materials for mobile electronic display devices has become an urgent task. [Means for solving the problem]

[0004] To overcome the shortcomings of the conventional technology described above, the present invention aims to provide high-hardness electronic glass, a method for manufacturing the same, and its applications. In this invention, a high-transmittance matrix glass is first manufactured, and then a second phase that prevents crack propagation is formed by subsequent processing, thereby achieving high-transmittance and high-hardness electronic glass with enhanced hardness, which can be applied as a protective layer for mobile electronic devices.

[0005] To achieve the above objective, the present invention employs the following technical means. The present invention discloses a high-hardness electronic glass characterized in that, when calculated by mass percentage, the raw materials for the high-hardness electronic glass contain 58.3-62.93% SiO2, 23.02-25.94% Al2O3, 1.95-5.02% B2O3, 2.07-4.21% Li2O, 0-2.88% Na2O, 0-2.29% K2O, 0-3.30% TiO2, 0-3.99% ZrO2, and 0-4.17% P2O5, and the sum of the mass percentages of all components is 100%.

[0006] The Vickers hardness value of the aforementioned high-hardness electronic glass is 580-680 kgf / mm². 2 That is the case.

[0007] The present invention discloses a method for manufacturing high-hardness electronic glass, including the following steps S1 to S3: Step S1 of mixing the raw materials of the high-hardness electronic glass described in claim 1, then melting, casting and forming, and performing annealing treatment to obtain a formed glass block; Step S2 of slicing the formed glass block, polishing and buffing to obtain a substrate glass sheet; Step S3 of subjecting the substrate glass sheet to heat treatment to obtain high-hardness electronic glass including a crystal phase part and a glass phase part.

[0008] In step S1: In the melting process, the temperature is raised to the first set temperature at the first heating rate, the first set temperature is maintained for the first set time, then the temperature is raised to the second set temperature at the second heating rate, the second set temperature is maintained for the second set time, then the temperature is raised to the third set temperature at the third heating rate, and the third heating rate is maintained for the third set time; the first heating rate is 10 to 15 °C / min, the first set temperature is 1000 to 1100 °C, the first set time is 30 to 45 minutes, the second heating rate is 5 to 7 °C / min, the second set temperature is 1350 to 1400 °C, the second set time is 1 to 2 hours, the third heating rate is 5 to 8 °C / min, the third set temperature is 1,645 to 1,650 °C, and the third set time is 4 to 5 hours.

[0009] In step S1, the temperature of the annealing treatment is 600 to 650 °C.

[0010] In step S2, the Vickers hardness value of the substrate glass sheet is 550 to 610 kgf / mm 2 is.

[0011] In step S2, the average transmittance of the substrate glass sheet within the visible light range exceeds 85%.

[0012] In step S3, the crystal phase part is any one or more of lithium silicate, lithium titanate, lithium aluminosilicate, and mullite.

[0013] A method for producing high-hardness electronic glass according to claim 3, wherein in step S3, the heat treatment includes a nucleation treatment and a crystallization treatment performed sequentially, the temperature of the nucleation treatment being 750 to 780°C and the duration of the nucleation treatment being 0.5 to 1 hour, and the temperature of the crystallization treatment being 850 to 880°C and the duration of the crystallization treatment being 0.5 to 1 hour.

[0014] An application of high-hardness electronic glass, characterized in that the aforementioned high-hardness electronic glass is used as a protective layer in mobile electronic devices. [Effects of the Invention]

[0015] The high-hardness electronic glass of the present invention has the following beneficial effects.

[0016] In the high-hardness electronic glass according to the present invention, SiO2 is a network-forming element within the glass, forming an irregular continuous network in the structure of silicon-oxygen tetrahedra [SiO4], and constituting the glass skeleton. SiO2 plays a role in reducing the thermal expansion coefficient of the glass and minimizing the difference in thermal expansion coefficients with the second phase. Al2O3 is an intermediate oxide; when there is a deficiency of oxygen atoms in the glass, aluminum is placed in the gaps of the network as aluminum-oxygen octahedra [AlO6]. When there are excess oxygen atoms in the glass, aluminum enters the glass structure as aluminum-oxygen tetrahedra [AlO4], playing a role in network reinforcement, increasing the stability of the glass, reducing the thermal expansion coefficient, and improving hardness. B2O3 in the glass acts as a co-solvent because it reduces the viscosity of the glass at high temperatures. Li2O is an alkali metal oxide and is also an important element in forming the second phase of the matrix glass. It lowers the melting temperature of the glass, improves moldability, and functions as a co-solvent without affecting the stability of the glass, allowing for easy control of the generation and size of the second phase. Na2O and K2O are also alkali metal oxides and function as good cosolvents for glass, lowering the melting temperature of the glass and improving its moldability. P2O5 exhibits two functions in glass: network reinforcement and phase separation. As a network reinforcement function, P2O5 forms phosphate tetrahedra [PO4] in the glass and combines with aluminum-oxygen tetrahedra [AlO4] to be incorporated into the silicon-oxygen network, thereby reinforcing the network and suppressing phase separation of the glass. On the other hand, as a phase separation function, P2O5 5+ The strong field of Zr breaks down the silicon-oxygen tetrahedron, and during the heat treatment process, it separates from the silicate network, promoting phase separation and leading to crystallization. ZrO2 is a good crystal nucleating agent for glass, and Zr 4+ Because the field strength is high, O 2ー Zr 4+ They gather according to their coordination number, and the Si-O bond is formed by removing free oxygen from within the structure. 4+ It forms a Si-O-Zr-O-Si structure that is biased toward Ti, and phase separation and crystallization are promoted by heat treatment under appropriate conditions. TiO2 is also a good crystal nucleating agent for glass, and it dissolves easily in the glass molten at high temperatures, Ti 4+participates in the silicon-oxygen network with a four-coordination, resulting in good compatibility with the glass skeleton. However, during cooling or reheating, Ti 4+ aggregates to form titanium-containing droplets, promoting phase separation. The electronic glass composed of the above components has both high transmittance and hardness.

[0017] The present invention provides a method for manufacturing a high-hardness electronic glass. The method uses a matrix glass having a high transmittance, polishes and polishes the surface to make it smooth and transparent, and then performs a heat treatment to generate a second phase (crystalline phase) different from the glass phase, thereby preventing further crack expansion and improving the hardness of the glass. By this method, a high-hardness electronic glass suitable for a protective layer of a mobile electronic device can be obtained.

Embodiments for Carrying Out the Invention

[0018] In order for those skilled in the art to understand the features and effects of the present invention, general explanations and definitions will be given below for the terms mentioned in the specification and claims. Unless otherwise specified, all technical terms and scientific terms used in this specification shall have the ordinary meanings understood by those skilled in the art related to the present invention. In case of any conflict in interpretation, the definitions in this specification shall prevail.

[0019] The theories or mechanisms described and disclosed in this specification, regardless of their correctness, do not limit the scope of the present invention in any form. That is, the content of the present invention can be implemented without being limited to specific theories or mechanisms.

[0020] In this specification, properties such as numerical values, quantities, contents, concentrations, etc. defined in the form of numerical ranges or percentage ranges are for the sake of brevity and convenience. Therefore, the description of these numerical ranges or percentage ranges is considered to include all possible sub-ranges and individual numerical values (including integers and fractions) within the range, and is specifically disclosed.

[0021] In this specification, unless otherwise specified, the terms “include,” “contain,” “have,” or similar terms include the meanings of “consist of…” and “consist primarily of….” For example, “A contains a” includes both the meanings of “A contains a and other things” and “A contains a only.”

[0022] For the sake of brevity, this specification does not describe all possible combinations of each technical feature in each embodiment or example. Therefore, as long as these combinations are inconsistent, each technical feature in each embodiment or example can be combined in any way, and all possible combinations are considered to fall within the scope described herein.

[0023] This invention provides high-hardness electronic glass, a method for manufacturing the same, and its applications.

[0024] The present invention will be described in more detail below based on specific examples. These examples are for illustrative purposes only and should not be used to limit the scope of the invention. Furthermore, those skilled in the art may make various changes and modifications to the invention after reading its contents, and these equivalent forms are also included within the scope of the claims attached to this application.

[0025] In the following embodiments, common equipment and devices in the art may be used. Experimental methods in the following embodiments that do not specify concrete conditions shall be carried out under normal conditions or conditions recommended by the manufacturer. Unless otherwise specified, the various raw materials used in the following embodiments are common commercially available products, and their specifications are those of standards commonly used by those skilled in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" indicates mass percentage, "mass parts" indicates parts by mass, and "ratio" indicates mass ratio.

[0026] In this invention, SiO2 is a network-forming element in the glass, forming an irregular continuous network with a silicon-oxygen tetrahedron [SiO4] structure, and constituting the glass skeleton. SiO2 can reduce the thermal expansion coefficient of the glass and decrease the difference in thermal expansion coefficient with respect to the second phase. However, if the SiO2 content is excessively high, the high-temperature viscosity of the glass increases, making it easier to form a silicon-rich phase and inducing the generation of the second phase. Therefore, by controlling the SiO2 content within the range of 58.3% to 62.93%, the glass can be given a low thermal expansion coefficient.

[0027] Al2O3 is an intermediate oxide. When there is a deficiency of oxygen atoms in the glass, the coordination state of aluminum becomes an alumino-oxygen octahedron [AlO6], and it occupies the gaps in the network. On the other hand, when there are excess oxygen atoms in the glass, the coordination state of aluminum becomes an alumino-oxygen tetrahedron [AlO4], and it enters the glass structure, playing a role in network reinforcement, improving the stability of the glass, lowering the coefficient of thermal expansion, and increasing hardness. However, if the Al2O3 content is excessively high, the viscosity of the matrix glass tends to increase, and the moldability decreases. Therefore, by controlling the Al2O3 content within the range of 23.02% to 25.94%, it is possible to achieve a low coefficient of thermal expansion and high surface hardness while ensuring the stability of the glass structure.

[0028] B2O3 primarily reduces the viscosity of glass at high temperatures and acts as a flux during melting. However, if the content is too high, the coefficient of thermal expansion increases, reducing the surface hardness of the matrix glass. Therefore, by controlling the B2O3 content within the range of 1.95% to 5.02%, it is possible to achieve a flux effect without affecting the thermal stability and surface hardness of the glass.

[0029] Li2O is an alkali metal oxide and an important component in the formation of the second phase of the matrix glass, lowering the melting temperature of the glass and improving its moldability. However, if the Li2O content exceeds 5%, the stability of the glass decreases, making it difficult to control the precipitation of the second phase and prone to devitrification. Therefore, by controlling the Li2O content within the range of 2.07% to 4.21%, the appearance (formation) and size of the second phase can be easily controlled without compromising the stability of the glass while maintaining the flux effect.

[0030] Na2O and K2O are alkali metal oxides and are excellent fluxes that lower the melting temperature of glass and improve its moldability. They are also necessary components for chemical strengthening to increase the surface strength of electron glass. However, if the content is too high, the stability of the glass decreases, so in this invention, the content of Na2O is controlled to be within the range of 0-2.88% and the content of K2O to be within the range of 0-2.29%, and a small amount of alkali metal oxide is included.

[0031] P2O5 has two functions in glass: network reinforcement and phase separation. The network reinforcement function involves P2O5 forming [PO4] phosphorus-oxygen tetrahedra, which combine with [AlO4] alumino-oxygen tetrahedra to enter the silicon-oxygen network, increasing structural stability and suppressing phase separation in the glass. On the other hand, the phase separation function involves the high coordination number of phosphides and strong P2O5. 5+ The field strength destroys the silicon-oxygen tetrahedron structure, O 2ー This occurs by removing components and forming tetrahedra. During heat treatment, it separates from the silicate network, promoting phase separation, and as the temperature rises during the phase separation process, the glass components become concentrated, further promoting crystallization. In this invention, the P2O5 content is controlled within the range of 0-4.17%, and whether network reinforcement or phase separation plays the primary role is closely related to the content of other components in the glass.

[0032] ZrO2 is an excellent crystal nucleating agent for glass, 4+ The electric field strength of the ions is high, and the surrounding O 2ー Zr 4+They are arranged according to their own coordination number, forming what is called an "accumulation." This accumulation removes free oxygen from the structure, then removes more bridging oxygen from the glass skeleton, and the O in the Si-O bond. 2ー Ions are Zr 4+ By biasing towards a specific region and forming a Si-O-Zr-O-Si structure, aggregates are formed, and under appropriate conditions, heat treatment can cause phase separation and crystallization. ZrO2 improves the chemical durability and hardness of the glass, but if the content is too high, melting becomes difficult and controlling the size of the second phase becomes difficult, so the ZrO2 content is controlled within the range of 0 to 3.99%.

[0033] TiO2 is also an excellent crystal nucleating agent for glass, and at high temperatures, TiO2 has high solubility in glass molten material. 4+ It participates in the silicon-oxygen network in a four-coordinate manner and has good compatibility with the silicon-oxygen tetrahedron structure, which is the skeletal structure of glass. However, Ti 4+ Due to the strong electric field, when the glass is cooled or reheated, Ti 4+ These aggregate to form titanium-containing droplets, promoting phase separation. However, if the TiO2 content is too high, Ti 4+ The valence electrons of TiO2 transition between different energy levels, causing selective absorption of visible light and resulting in the glass exhibiting a yellow color; therefore, the TiO2 content is controlled within the range of 0-3.30%.

[0034] By adjusting the component content as described above, the resulting glass has high transparency and surface hardness, and after heat treatment, it can generate a controllable second phase to prevent crack propagation and improve the hardness of the glass.

[0035] The present invention provides a high-hardness electronic glass whose mass percentage composition is as follows: 58.3% to 62.93% SiO2, 23.02% to 25.94% Al2O3, 1.95% to 5.02% B2O3, 2.07% to 4.21% Li2O, 0% to 2.88% Na2O, 0% to 2.29% K2O, 0% to 3.30% TiO2, 0% to 3.99% ZrO2, and 0% to 4.17% P2O5, with the total mass percentage of all components being 100%.

[0036] The present invention further provides a method for manufacturing high-hardness electronic glass. The specific procedure is as follows. Step S1: Mix the raw materials for high-hardness electronic glass and melt them. Specifically, heat is increased to 1000-1100°C at a rate of 10-15°C / min and held for 30-45 minutes. Next, heat is increased to 1350-1400°C at a rate of 5-7°C / min and held for 1-2 hours. After that, heat is increased to 1645-1650°C at a rate of 5-8°C / min and held for 4-5 hours, then cast and shaped, and annealed at 600-650°C to obtain a shaped glass block. Step S2: The molded glass block is sliced, polished, and buffed to obtain a substrate glass sheet. Step S3: The substrate glass sheet is subjected to heat treatment. Specifically, a nucleation treatment is performed at 750-780°C for 0.5-1 hour, followed by a crystallization treatment at 850-880°C for 0.5-1 hour to obtain a high-hardness electronic glass containing a crystalline phase portion and a glass phase portion. The crystalline phase portion is one or more of the following: lithium silicate, lithium titanate, lithium aluminosilicate, and mullite.

[0037] The optimal procedure and steps for the manufacturing method of the high-hardness electronic glass of the present invention are as follows. 1) Calculate the required weight of raw materials based on the mass percentage of the oxide and weigh them accurately. 2) The weighed raw materials are uniformly mixed in a mixer, poured into a platinum crucible, and placed in a high-temperature experimental furnace. The temperature is raised to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours. After that, the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is then placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling. 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw. These 1.3 mm thick thin sheets are then ultrasonically cleaned sequentially with alcohol and pure water, and dried in an oven at 105°C. After that, they are polished on a polishing machine using vacuum suction, and the thickness is measured with a screw micrometer to obtain an average thickness of 1.1 mm. After cleaning and drying, they are polished on a polisher using vacuum suction, and the thickness is measured again with a screw micrometer to obtain an average thickness of 1.0 mm. After cleaning and drying, a transparent substrate glass sheet (matrix glass sheet) is obtained. 4) Based on the expansion and softening point and glass transition temperature of the substrate glass (matrix glass), appropriate nucleation and crystallization processes are set, the substrate glass sheet is placed in an annealing furnace, and heat treatment is performed according to the process to obtain high-hardness electronic glass containing crystalline and glass phases.

[0038] (Example 1) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 59.62%, Al2O3: 24.58%, B2O3: 1.95%, Li2O: 2.12%, Na2O: 2.88%, K2O: 1.83%, TiO2: 0%, ZrO2: 3.99%, P2O5: 3.03%. Calculate the weight of the required raw materials and weigh them accurately.

[0039] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0040] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in an oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, and the thickness is measured with a screw micrometer to achieve an average thickness of 1.1 mm. After cleaning and drying, it is polished on a polisher using vacuum suction, and the thickness is measured with a screw micrometer to achieve an average thickness of 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0041] 4) Place the substrate glass sheet in an dilatometer and measure the glass transition temperature at 706°C and the expansion softening point at 823°C. Then, calculate the thermal expansion coefficient from 30 to 380°C as 35.8 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is determined to be 2.392 g / cm³ using a densimeter. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 90.3%. The Vickers hardness value of the substrate glass was measured using a Vickers hardness tester and was 572 kgf / mm². 2 And measure it.

[0042] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 780°C for 1 hour and the crystallization treatment to 880°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the temperature is lowered by furnace cooling to obtain the heat-treated glass sheet.

[0043] 6) The Vickers hardness of the heat-treated glass was measured to 630 kgf / mm² using a Vickers hardness tester. 2 The following measurements were taken. The glass was crushed into powder, and XRD was used to confirm that it contained lithium silicate and lithium aluminosilicate, which are other phases distinct from the glass phase.

[0044] (Example 2) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 60.69%, Al2O3: 23.02%, B2O3: 5.02%, Li2O: 2.16%, Na2O: 1.89%, K2O: 0.36%, TiO2: 3.30%, ZrO2: 3.56%, P2O5: 0%. Calculate the weight of the required raw materials and weigh them accurately.

[0045] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0046] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in a drying oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, and the thickness is measured with a screw micrometer to achieve an average thickness of 1.1 mm. After cleaning and drying, it is polished on a polisher using vacuum suction, and the thickness is measured again with a screw micrometer to achieve an average thickness of 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0047] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion to be 36.1 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is determined to be 2.432 g / cm³ using a densimeter. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 85.2%. The Vickers hardness value of the substrate glass was determined to be 610 kgf / mm² using a Vickers hardness tester. 2 And measure it.

[0048] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 760°C for 1 hour and the crystallization treatment to 860°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is raised to 880°C at a rate of 5°C / min and held for 1 hour, after which the temperature is lowered by furnace cooling to obtain the heat-treated glass sheet.

[0049] 6) The Vickers hardness of the heat-treated glass was measured to 680 kgf / mm² using a Vickers hardness tester. 2 The following measurements were taken. The glass was crushed into a powder, and XRD was used to confirm that it contained lithium titanate, a phase different from the glass phase.

[0050] (Example 3) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 62.12%, Al2O3: 24.61%, B2O3: 3.11%, Li2O: 4.21%, Na2O: 0.92%, K2O: 1.39%, TiO2: 0%, ZrO2: 3.64%, P2O5: 0%. Calculate the weight of the required raw materials and weigh them accurately.

[0051] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0052] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in a drying oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0053] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion as 36.2 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is measured with a densimeter and found to be 2.415 g / cm³. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 89.2%. The Vickers hardness value of the substrate glass was measured using a Vickers hardness tester and was 601 kgf / mm². 2 And measure it.

[0054] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 770°C for 1 hour and the crystallization treatment to 870°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Subsequently, the temperature is raised to 880°C at a rate of 5°C / min and held for 1 hour, after which it is cooled by furnace cooling to obtain the heat-treated glass sheet.

[0055] 6) The Vickers hardness of the heat-treated glass was measured using a Vickers hardness tester, and the result was 660 kgf / mm². 2 The glass was crushed and measured by XRD, confirming that it contained mullite, a phase different from the glass phase.

[0056] (Example 4) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 60.36%, Al2O3: 23.88%, B2O3: 4.0%, Li2O: 3.15%, Na2O: 1.59%, K2O: 1.95%, TiO2: 2.99%, ZrO2: 0%, P2O5: 2.08%. Calculate the weight of the required raw materials and weigh them accurately.

[0057] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0058] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in a drying oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0059] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion as 34.8 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is determined to be 2.355 g / cm³ using a densimeter. 3 The following measurements were taken: A haze meter was used to measure the transmittance at visible light wavelengths, and the average visible light transmittance of the substrate glass was obtained as 87.6%. A Vickers hardness tester was used to determine the Vickers hardness of the substrate glass at 557 kgf / mm². 2 And measure it.

[0060] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 780°C for 1 hour and the crystallization treatment to 880°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the heat-treated glass sheet is obtained by furnace cooling.

[0061] 6) The Vickers hardness of the heat-treated glass was measured to 594 kgf / mm² using a Vickers hardness tester. 2 The following measurements were taken. The glass was crushed into a powder, and XRD was used to confirm that it contained lithium titanate, a phase different from the glass phase.

[0062] (Example 5) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 61.78%, Al2O3: 24.47%, B2O3: 4.09%, Li2O: 3.20%, Na2O: 0%, K2O: 2.29%, TiO2: 0%, ZrO2: 0%, P2O5: 4.17%. Calculate the weight of the required raw materials and weigh them accurately.

[0063] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0064] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in an oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0065] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion to be 35.2 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is determined to be 2.336 g / cm³ using a densimeter. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 91.0%. The Vickers hardness value of the substrate glass was determined to be 550 kgf / mm² using a Vickers hardness tester. 2 And measure it.

[0066] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 780°C for 1 hour and the crystallization treatment to 880°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the heat-treated glass sheet is obtained by furnace cooling.

[0067] 6) The Vickers hardness of the heat-treated glass was measured to 580 kgf / mm² using a Vickers hardness tester. 2 The following measurements were taken. The glass was crushed into a powder, and XRD was used to confirm that it contained lithium silicate, a phase different from the glass phase.

[0068] (Example 6) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 58.30%, Al2O3: 24.03%, B2O3: 3.86%, Li2O: 2.07%, Na2O: 0.86%, K2O: 1.31%, TiO2: 2.21%, ZrO2: 3.42%, P2O5: 3.94%. Calculate the weight of the required raw materials and weigh them accurately.

[0069] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0070] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in an oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0071] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion as 35.7 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is determined to be 2.410 g / cm³ using a densimeter. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 86.8%. The Vickers hardness value of the substrate glass was measured using a Vickers hardness tester and was 564 kgf / mm². 2 And measure it.

[0072] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 780°C for 1 hour and the crystallization treatment to 880°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the heat-treated glass sheet is obtained by furnace cooling.

[0073] 6) The Vickers hardness of the heat-treated glass was measured to 613 kgf / mm² using a Vickers hardness tester. 2 The following measurements were taken. The glass was crushed into a powder, and XRD was used to confirm that it contained lithium titanate, a phase different from the glass phase.

[0074] (Example 7) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 62.93%, Al2O3: 25.94%, B2O3: 4.17%, Li2O: 2.24%, Na2O: 2.34%, K2O: 0%, TiO2: 2.38%, ZrO2: 0%, P2O5: 0%. Calculate the weight of the required raw materials and weigh them accurately.

[0075] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1000°C at a rate of 10°C / min and held for 30 minutes. Then, the temperature is raised to 1350°C at a rate of 5°C / min and held for 1 hour. Furthermore, the temperature is raised to 1650°C at a rate of 5°C / min and held for 4 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 600°C and cooled to room temperature by furnace cooling.

[0076] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in a drying oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polisher using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0077] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion as 35.7 × 10⁻⁶. ー7 The temperature is determined to be / ℃. The density of the substrate glass is measured with a densimeter and found to be 2.370 g / cm³. 3 The following measurements were taken: The transmittance at visible light wavelengths was measured using a haze meter, and the average visible light transmittance of the substrate glass was obtained as 88.4%. The Vickers hardness value of the substrate glass was measured using a Vickers hardness tester and was 587 kgf / mm². 2 And measure it.

[0078] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 750°C for 1 hour and the crystallization treatment to 850°C for 1 hour. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the heat-treated glass sheet is obtained by furnace cooling.

[0079] 6) The Vickers hardness of the heat-treated glass was measured to 644 kgf / mm² using a Vickers hardness tester. 2 The glass was crushed into a powder and measured using XRD, confirming that it contained lithium titanate, a phase different from the glass phase.

[0080] Table 1 shows the glass composition, basic performance, and type of second phase (crystalline phase portion) of Examples 1 to 7 provided by the present invention. [Table 1]

[0081] (Example 8) 1) The composition of the high-hardness electronic glass, calculated by mass percentage, is as follows: SiO2: 59.62%, Al2O3: 24.58%, B2O3: 1.95%, Li2O: 2.12%, Na2O: 2.88%, K2O: 1.83%, TiO2: 0%, ZrO2: 3.99%, P2O5: 3.03%. Calculate the weight of the required raw materials and weigh them accurately.

[0082] 2) The weighed raw materials are uniformly mixed in a mixer and poured into a platinum crucible. This is placed in a high-temperature experimental furnace and heated to 1100°C at a rate of 15°C / min, and held for 45 minutes. Then, the temperature is raised to 1400°C at a rate of 7°C / min and held for 2 hours. Furthermore, the temperature is raised to 1645°C at a rate of 8°C / min and held for 5 hours, after which the molten glass is poured into a preheated mold to form block-shaped glass with a regular shape. This is placed in an annealing furnace heated to 650°C and cooled to room temperature by furnace cooling.

[0083] 3) The annealed glass block is cut into 1.3 mm thick thin sheets using a wire saw, then ultrasonically cleaned sequentially with alcohol and pure water, and dried in a drying oven at 105°C. After that, it is polished on a polishing machine using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.1 mm. After cleaning and drying, it is polished on a polisher using vacuum suction, the thickness is measured with a screw micrometer, and the average thickness is adjusted to 1.0 mm. After cleaning and drying, a transparent substrate glass sheet is obtained.

[0084] 4) Place the substrate glass sheet in an dilatometer, measure the glass transition temperature and expansion / softening point, and determine the coefficient of thermal expansion. Measure the density of the substrate glass with a densimeter and measure the transmittance at visible light wavelengths with a haze meter to obtain the average visible light transmittance of the substrate glass. Measure the Vickers hardness of the substrate glass with a Vickers hardness tester.

[0085] 5) Based on the measured glass transition temperature and expansion softening point, the nucleation treatment is set to 780°C for 0.5 hours and the crystallization treatment to 880°C for 0.5 hours. Then, the substrate glass sheet is placed in an annealing furnace and heated to 780°C at a rate of 5°C / min and held for 1 hour. Next, the temperature is heated to 880°C at a rate of 5°C / min and held for 1 hour, after which the heat-treated glass sheet is obtained by furnace cooling.

[0086] 6) The Vickers hardness of the heat-treated glass was measured using a Vickers hardness tester. The glass was then crushed into a powder and measured by XRD to confirm the presence of other phases distinct from the glass phase.

[0087] The above is for the purpose of explaining the technical concept of the present invention and does not limit the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed by the present invention are included in the claims of the present invention.

Claims

1. A method for manufacturing electronic glass for electronic equipment, Calculated by mass percentage, SiO of 58.3 to 62.93% ２ , ２ , ５ , ２ , ２ , Al of 23.02 to 25.94% ２ O ３ , B of 1.95 to 5.02% ２ O ３ , Li of 2.07 to 4.21% ２ O, Na of 0 to 2.88% ２ , K of 0 to 2.29% ２ O, TiO of 0 to 3.30% ２ , ZrO of 0 to 3.99% ２ , and P of 0 to 4.17% ２ O ５ Using the raw material of the electronic glass containing the components of Step S1 involves mixing the raw materials for the electron glass, melting them, casting them, and performing an annealing treatment to obtain a molded glass block. Step S2 involves slicing the molded glass block, polishing it, and performing other steps to obtain a substrate glass sheet. Step S3 involves heat-treating the aforementioned substrate glass sheet to obtain an electron glass including a crystalline phase portion and a glass phase portion. Includes, In step S2, the average transmittance of the substrate glass sheet within the visible light range exceeds 85%. The Vickers hardness value of the aforementioned electron glass is 580 to 680 kgf / mm². A method for manufacturing electronic glass, characterized by the following:

2. In step S1, the melting process involves raising the temperature to a first set temperature at a first heating rate, holding the first set temperature for a first set time, then raising the temperature to a second set temperature at a second heating rate, holding the second set temperature for a second set time, then raising the temperature to a third set temperature at a third heating rate, and holding the third heating rate for a third set time; A method for manufacturing an electron glass according to claim 1, wherein the first heating rate is 10 to 15°C / min, the first set temperature is 1000 to 1100°C, and the first set time is 30 to 45 minutes; the second heating rate is 5 to 7°C / min, the second set temperature is 1350 to 1400°C, and the second set time is 1 to 2 hours; and the third heating rate is 5 to 8°C / min, the third set temperature is 1645 to 1650°C, and the third set time is 4 to 5 hours.

3. The method for manufacturing electron glass according to claim 1, wherein in step S1, the temperature of the annealing treatment is 600 to 650°C.

4. In step S2, the Vickers hardness value of the substrate glass sheet is 550 to 610 kgf / mm ２ The method for manufacturing an electronic glass according to claim 1.

5. The method for producing an electron glass according to claim 1, wherein in step S3, the crystalline phase portion is one or more of lithium silicate, lithium titanate, lithium aluminosilicate, and mullite.

6. The method for manufacturing electron glass according to claim 1, wherein in step S3, the heat treatment includes a nucleation treatment and a crystallization treatment performed sequentially, the temperature of the nucleation treatment being 750 to 780°C and the duration of the nucleation treatment being 0.5 to 1 hour, and the temperature of the crystallization treatment being 850 to 880°C and the duration of the crystallization treatment being 0.5 to 1 hour.

7. An application of electronic glass, characterized in that the high-hardness electronic glass described in claim 1 is used as a protective layer in mobile electronic equipment.

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