Laminated glass and method, apparatus and use for its production

Abstract

The present application relates to the field of glass, and discloses a kind of laminated glass and its preparation method, preparation device and application, the laminated glass includes glass layer I and glass layer II in the direction of thickness laminated combination, with the total molar amount of glass layer I as benchmark, glass layer I includes 1mol.%-3.5mol.% of light-absorbing material, the light-absorbing material is Sm2O3 and Ho2O3, and the content of Ho2O3 in the light-absorbing material is not less than the content of Sm2O3, the thermal expansion coefficient CTE2 of glass layer II is greater than the thermal expansion coefficient CTE1 of glass layer I, the visible light transmittance of glass layer II is not less than 90% under the condition that thickness is 0.7mm.The laminated glass provided by the present application has excellent comprehensive performance, has good anti-blue light effect, at the same time, visible light transmittance is high, surface layer compression stress is moderate, glass strength is large, and is not easy to produce warping risk.

Description

Technical Field

[0001] This invention relates to the field of glass, and more specifically to a laminated glass, its preparation method, preparation apparatus, and applications. Background Technology

[0002] With the rapid development of 5G communication technology, consumer electronics products, including mobile phones, computers, and tablet displays, now mostly use cover glass as their surface protection. Meanwhile, considering that some glass products incorporate touch functionality, meaning they are frequently touched by users' fingers or styluses, these glass products need to have sufficient strength to withstand frequent external contact or accidental impacts without damage.

[0003] Considering that enhancing the strength of glass products through chemical ion exchange or thermal tempering requires additional processing steps to achieve subsequent treatment of the glass products, this not only increases the manufacturing cost of the process, but also increases the risk of damage to the glass products during the processing.

[0004] Recent studies have found that displays in electronic products such as mobile phones, computers, and tablets emit blue light. Short-wavelength blue light in the 400nm-450nm range has high energy. Prolonged exposure to this wavelength can lead to the production of numerous free radicals in the retina, causing the death of retinal pigment epithelial cells and ultimately resulting in a lack of nutrients for photoreceptor cells, leading to vision damage. Therefore, reducing the harmful effects of short-wavelength blue light from electronic products on the eyes is a key focus for researchers.

[0005] In addition, the surface of ordinary cover glass will reflect light to a certain extent (generally about 4% reflection on one side), which will have an adverse effect on the clarity, saturation and color vibrancy of the image. Summary of the Invention

[0006] The purpose of this invention is to overcome the problem of poor overall performance of cover glass in the prior art.

[0007] To achieve the above objectives, a first aspect of the present invention provides a laminated glass comprising a glass layer I and a glass layer II stacked together along the thickness direction. Based on the total molar amount of the glass layer I, the composition of the glass layer I comprises: 65 mol.% to 75 mol.% SiO2, 3 mol.% to 8 mol.% Al2O3, 7 mol.% to 12 mol.% B2O3, 5 mol.% to 10 mol.% Na2O, and 1 mol.% to 3.5 mol.% light-absorbing material.

[0008] The light-absorbing materials are Sm2O3 and Ho2O3, and the content of Ho2O3 in the light-absorbing materials is not less than the content of Sm2O3. Based on the total molar amount of the glass layer I, the content of Sm2O3 is not less than 0.5 mol.%.

[0009] Within the temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE2 of glass layer II is greater than the coefficient of thermal expansion CTE1 of glass layer I;

[0010] The visible light transmittance of the glass layer II is not less than 90% when the thickness is 0.7 mm.

[0011] Preferably, based on the total molar amount of the glass layer I, the content of the light-absorbing material is 1 mol.% to 3 mol.%.

[0012] Preferably, the glass layer I is opposite to the surface of the glass layer II, and the compressive stress is 100MPa to 150MPa.

[0013] Preferably, within a temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE1 of glass layer I and the coefficient of thermal expansion CTE2 of glass layer II satisfy: 1.0 × 10⁻⁶ -6 / ℃≤CTE2-CTE1≤2.0×10 -6 / ℃.

[0014] More preferably, within a temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE1 of the glass layer I is 4×10⁻⁶. -6 / ℃~6×10 -6 / ℃; the coefficient of thermal expansion CTE2 of the glass layer II is 5×10⁻⁶. -6 / ℃~8×10 -6 / ℃.

[0015] Preferably, based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 2 mol.% of MgO.

[0016] Preferably, based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 4 mol.% of P2O5.

[0017] Preferably, the glass layer II is at least one of potassium aluminum silicate glass, potassium borosilicate glass, and potassium aluminum borosilicate glass.

[0018] More preferably, based on the total molar amount of the glass layer II, the composition of the glass layer II comprises: 70 mol.% to 80 mol.% SiO2, 5 mol.% to 10 mol.% Al2O3, 4 mol.% to 8 mol.% B2O3, 7 mol.% to 12 mol.% K2O, and 3 mol.% to 5 mol.% alkaline earth metal oxides, wherein the alkaline earth metal oxides are at least one of CaO, SrO, and BaO.

[0019] Preferably, the thickness of glass layer I is 0.05mm to 0.15mm, and the thickness of glass layer II is 0.5mm to 0.9mm.

[0020] Preferably, the laminated glass further comprises an antireflective film, which is bonded to the surface of glass layer I opposite to glass layer II.

[0021] More preferably, the antireflective film comprises at least one layer of TiO2 stacked alternately in sequence. x Single film and at least one layer of SiO y A single membrane, wherein 1.5 < x < 1.9, 1.2 < y < 1.8.

[0022] More preferably, the TiO x Single film and the SiO y Each single membrane consists of 1 to 3 independent layers.

[0023] Preferably, the TiO x The thickness of the single film is 60 nm to 220 nm, and the refractive index is 2.0 to 2.2; the SiO y The thickness of the single film is 90nm to 310nm, and the refractive index is 1.42 to 1.48; the refractive index of the glass layer I is 1.58 to 1.72.

[0024] A second aspect of the present invention provides a method for preparing the laminated glass provided in the first aspect, comprising the following steps:

[0025] S1: Precursor composition I for forming glass layer I and precursor composition II for forming glass layer II are respectively subjected to melt clarification treatment to obtain glass melt I and glass melt II respectively;

[0026] S2: On the surface of the molten metal, the glass liquid II is spread and thinned II to obtain the glass layer II;

[0027] S3: On the surface of the glass layer II that is away from the molten metal, the molten glass I is flattened and thinned I to form glass layer I on the surface of the glass layer II, thereby obtaining the laminated glass;

[0028] The glass transition temperature Tg2 of the glass melt II is greater than the glass transition temperature Tg1 of the glass melt I.

[0029] Preferably, in step S1, the melt clarification process involves first performing a melt treatment, and then performing a clarification treatment.

[0030] The conditions for the melting treatment are each independently selected from: a temperature of 1500℃~1700℃ and a treatment time of 4h~8h; the conditions for the clarification treatment are each independently selected from: a temperature of 1350℃~1550℃ and a treatment time of 2h~6h.

[0031] In step S2, the target thickness of the glass layer II obtained by the flattening and thinning treatment II is 0.5 mm to 0.9 mm;

[0032] In step S3, the target thickness of the glass layer I obtained by the flattening and thinning process I is 0.05 mm to 0.15 mm.

[0033] Preferably, the glass transition temperature Tg1 of the molten glass I is 800℃~850℃, and the glass transition temperature Tg2 of the molten glass II is 850℃~900℃.

[0034] Preferably, step S3 further includes:

[0035] After the glass layer I is formed, an anti-reflective film is deposited online on the surface of the glass layer I opposite to the glass layer II using a CVD process to obtain the laminated glass with anti-reflective function.

[0036] A third aspect of the present invention provides a laminated glass preparation apparatus, comprising:

[0037] A forming tank for containing molten metal and forming laminated glass on the surface of the molten metal; and

[0038] At least two sets of melting and refining assemblies, each comprising a melter, a refiner, and a guide pipe connected in sequence, wherein the guide pipe is used to guide molten glass into the forming tank.

[0039] Preferably, the laminated glass preparation apparatus further includes a coating machine, which is located above the forming tank and is used to deposit an anti-reflective film on the upper surface of the laminated glass online.

[0040] The fourth aspect of the present invention provides the application of the laminated glass described in the first aspect in glass cover plates.

[0041] The laminated glass provided by this invention has excellent overall performance, with good blue light protection, high visible light transmittance, moderate surface compressive stress, high glass strength, and is not prone to warping.

[0042] The method for preparing laminated glass provided by this invention uses the float glass process, which is simple to prepare, easy to control parameters, and produces laminated glass with excellent comprehensive performance and long service life.

[0043] The laminated glass preparation apparatus provided by this invention can realize the preparation and coating of laminated glass, simplify the preparation and coating process of laminated glass, improve the preparation efficiency of coated laminated glass, and produce laminated glass with excellent comprehensive performance.

[0044] The laminated glass provided by this invention can be used as a glass cover to effectively filter blue light. When used in electronic products, it can ensure the clarity, saturation, and color vibrancy of the screen display, and can also effectively reduce the damage of short-wave blue light from electronic products to the human eye. Attached Figure Description

[0045] Figure 1 This is a schematic diagram of the structure of laminated glass provided by the present invention according to a preferred embodiment;

[0046] Figure 2 This is a schematic diagram of the structure of laminated glass provided by the present invention according to a preferred embodiment;

[0047] Figure 3 This is a schematic diagram of the structure of the antireflective film provided by the present invention according to a preferred embodiment;

[0048] Figure 4 This is a schematic diagram of the structure of a laminated glass preparation apparatus provided by the present invention according to a preferred embodiment.

[0049] Explanation of reference numerals in the attached figures

[0050] 1. Glass layer; 2. Anti-reflective coating;

[0051] 11. Glass layer I; 12. Glass layer II;

[0052] 21. First layer TiO x Single film, 22, first layer SiO x Single film, 23, second TiO2 layer x Single film, 24, second layer SiO x Single membrane;

[0053] 301. Melting tank II; 302. Molten glass II; 303. Clarifier II; 304. Flow tube II; 305. Melting tank I; 306. Molten glass I; 307. Clarifier I; 308. Flow tube I; 309. Coating tank I; 310. Coating tank II; 311. Coating tank III; 312. Coating tank IV; 313. Molten tin; 314. Forming tank. Detailed Implementation

[0054] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0055] To achieve the above objectives, a first aspect of the present invention provides a laminated glass comprising a glass layer I and a glass layer II stacked together along the thickness direction. Based on the total molar amount of the glass layer I, the composition of the glass layer I comprises: 65 mol.% to 75 mol.% SiO2, 3 mol.% to 8 mol.% Al2O3, 7 mol.% to 12 mol.% B2O3, 5 mol.% to 10 mol.% Na2O, and 1 mol.% to 3.5 mol.% light-absorbing material.

[0056] The light-absorbing materials are Sm2O3 and Ho2O3, and the content of Ho2O3 in the light-absorbing materials is not less than the content of Sm2O3. Based on the total molar amount of the glass layer I, the content of Sm2O3 is not less than 0.5 mol.%.

[0057] Within the temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE2 of glass layer II is greater than the coefficient of thermal expansion CTE1 of glass layer I;

[0058] The visible light transmittance of the glass layer II is not less than 90% when the thickness is 0.7 mm.

[0059] The glass layer I provided by this invention contains blue light-absorbing materials Sm2O3 and Ho2O3. These materials effectively absorb short-wavelength blue light and convert it into visible light of other wavelengths, thus achieving the blue light filtering effect of laminated glass. The laminated glass provided by this invention exhibits excellent overall performance, providing good blue light protection. Simultaneously, it boasts high visible light transmittance, moderate surface compressive stress, high glass strength, and is less prone to warping.

[0060] In some preferred embodiments of the present invention, based on the total molar amount of the glass layer I, the content of the light-absorbing material is 1 mol.% to 3 mol.%, resulting in better blue light protection and higher visible light transmittance of the laminated glass.

[0061] In some preferred embodiments of the present invention, the glass layer I is away from the surface of the glass layer II, and the compressive stress is 100MPa to 150MPa. The glass layer I has high strength and can withstand frequent external contact or accidental impacts without being damaged. At the same time, the laminated glass has low warpage.

[0062] In some preferred embodiments of the present invention, within a temperature range of 20°C to 300°C, the coefficient of thermal expansion CTE1 of glass layer I and the coefficient of thermal expansion CTE2 of glass layer II satisfy: 1.0 × 10⁻⁶. -6 / ℃≤CTE2-CTE1≤2.0×10 -6 / ℃. On the one hand, by mismatching the coefficients of thermal expansion between glass layer I and glass layer II, the compressive stress on the surface of glass layer I away from glass layer II can be appropriately increased, thereby achieving the purpose of improving the mechanical properties of laminated glass; on the other hand, controlling the mismatch force generated by the coefficients of thermal expansion between glass layer I and glass layer II to prevent it from being too large avoids excessive warping risk in laminated glass.

[0063] In some more preferred embodiments of the present invention, the coefficient of thermal expansion CTE1 of the glass layer I is 4 × 10⁻⁶ within a temperature range of 20°C to 300°C. -6 / ℃~6×10 -6 / ℃; the coefficient of thermal expansion CTE2 of the glass layer II is 5×10⁻⁶. -6 / ℃~8×10 -6 / ℃. Under these conditions, laminated glass exhibits superior mechanical properties, with a low risk of warping and minimal warping.

[0064] In some preferred embodiments of the present invention, based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 2 mol.% MgO. In this case, the overall performance of the laminated glass is even better.

[0065] In some preferred embodiments of the present invention, based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 4 mol.% of P2O5. In this case, the overall performance of the laminated glass is even better.

[0066] It should be noted that the present invention does not have special requirements for the composition and content of glass layer II, as long as the following two requirements are met: (1) In the temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE2 of glass layer II is greater than the coefficient of thermal expansion CTE1 of glass layer I; (2) Under the condition that the thickness of glass layer II is 0.7mm, the visible light transmittance is not less than 90%. For example, glass layer II is selected from at least one of potassium aluminum borosilicate glass, potassium borosilicate glass, and potassium aluminum borosilicate glass.

[0067] In some preferred embodiments of the present invention, based on the total molar amount of the glass layer II, the composition of the glass layer II comprises: 70 mol.% to 80 mol.% SiO2, 5 mol.% to 10 mol.% Al2O3, 4 mol.% to 8 mol.% B2O3, 7 mol.% to 12 mol.% K2O, and 3 mol.% to 5 mol.% alkaline earth metal oxides, wherein the alkaline earth metal oxides are at least one selected from CaO, SrO, and BaO.

[0068] In some preferred embodiments of the present invention, the thickness of glass layer I is 0.05 mm to 0.15 mm, and the thickness of glass layer II is 0.5 mm to 0.9 mm.

[0069] In some preferred embodiments of the present invention, such as Figure 1 As shown, the laminated glass comprises glass layer I11 and glass layer II12 that are stacked together along the thickness direction.

[0070] In some preferred embodiments of the present invention, the laminated glass further includes an anti-reflective coating bonded to the surface of glass layer I facing away from glass layer II. The anti-reflective coating reduces light reflection from the glass surface, thereby increasing the transmittance of visible light.

[0071] In some preferred embodiments of the present invention, the antireflection film comprises at least one layer of TiO2 stacked alternately in sequence. x Single film and at least one layer of SiO y A single film, wherein 1.5 < x < 1.9, 1.2 < y < 1.8. This is achieved by alternating layers of high-refractive-index TiO₂. x Single-film and low-refractive-index SiO y A single film can effectively reduce the reflectivity of visible light and increase the visible light transmittance of laminated glass.

[0072] In some preferred embodiments of the present invention, the TiO x Single film and the SiO y Each single film consists of 1 to 3 independent layers. In this case, laminated glass has a good anti-reflection effect. At the same time, the preparation process is simple and the production cost is low.

[0073] In some preferred embodiments of the present invention, such as Figure 2 As shown, the laminated glass comprises a glass layer 1 and an antireflective coating 2, wherein the glass layer 1 comprises glass layer I11 and glass layer II12; the specific structure of the antireflective coating 2 is as follows. Figure 3 As shown, it includes a first layer of TiO2. x Single film 21, first layer SiO xSingle film 22, second layer TiO x Single film 23 and second layer SiO x Single membrane 24.

[0074] In some specific embodiments of the present invention, the TiO x The thickness of the single film is 60 nm to 220 nm, and the refractive index is 2.0 to 2.2; the SiO y The thickness of the single film is 90 nm to 310 nm, and the refractive index is 1.42 to 1.48; the refractive index of the glass layer I is 1.58 to 1.72. In this case, the laminated glass has a better anti-reflection effect and the visible light transmittance can be improved significantly.

[0075] A second aspect of the present invention provides a method for preparing the laminated glass provided in the first aspect, comprising the following steps:

[0076] S1: Precursor composition I for forming glass layer I and precursor composition II for forming glass layer II are respectively subjected to melt clarification treatment to obtain glass melt I and glass melt II respectively;

[0077] S2: On the surface of the molten metal, the glass liquid II is spread and thinned II to obtain the glass layer II;

[0078] S3: On the surface of the glass layer II that is away from the molten metal, the molten glass I is flattened and thinned I to form glass layer I on the surface of the glass layer II, thereby obtaining the laminated glass;

[0079] The glass transition temperature Tg2 of the glass melt II is greater than the glass transition temperature Tg1 of the glass melt I.

[0080] Currently, laminated glass products are generally manufactured using the melt-drawing method. However, this method places high demands on the liquidus viscosity of the molten glass, typically requiring a viscosity of at least 100 kilopoise. The inventors of this invention have discovered that adding rare earth elements to the precursor composition of the laminated glass can reduce the viscosity of the molten glass. Therefore, this invention proposes a float glass process for manufacturing laminated glass products. This process does not have specific requirements for the liquidus viscosity of the molten glass; it only requires that the glass transition temperature of the lower glass layer be higher than that of the upper glass layer. The process is simple, parameters are easy to control, and the resulting laminated glass exhibits excellent overall performance.

[0081] It should be noted that the present invention does not have special requirements for the specific components of precursor composition I and precursor composition II, as long as the following conditions are met: (1) the components and contents of glass layer I and glass layer II as described in the first aspect of the present invention can be provided respectively; (2) the glass transition temperature Tg2 of the glass melt II is greater than the glass transition temperature Tg1 of the glass melt I. For example, the glass transition temperature Tg1 of the glass melt I is 800℃~850℃, and the glass transition temperature Tg2 of the glass melt II is 850℃~900℃. In this case, when the glass melt I is injected into the surface of the glass layer II, the glass melt II has been partially or completely transformed into the glass layer II, which can ensure that the glass melt I does not melt with the glass melt II, thereby forming mutually bonded glass layer I and glass layer II.

[0082] It should also be noted that the present invention does not have any special requirements on the type of molten metal liquid. Molten metal liquid of commonly used glass preparation methods can be used. For example, the molten metal liquid used in the present invention is molten tin.

[0083] In some preferred embodiments of the present invention, in step S1, the melt clarification treatment involves first performing a melt treatment and then a clarification treatment. The conditions for each melt treatment are independently selected from: a temperature of 1500℃ to 1700℃ and a treatment time of 4h to 8h; the conditions for each clarification treatment are independently selected from: a temperature of 1350℃ to 1550℃ and a treatment time of 2h to 6h. In this case, precursor composition I and precursor composition II can be converted into glass melt I and glass melt II respectively, and impurity gases in glass melt I and glass melt II are fully removed, resulting in laminated glass that is less prone to bubble formation.

[0084] In some preferred embodiments of the present invention, in step S2, the target thickness of the glass layer II obtained by the flattening and thinning treatment II is 0.5 mm to 0.9 mm. It should be noted that the target thickness refers to the thickness of the formed glass layer; in step S2, the target thickness refers to the thickness of the formed glass layer II. The present invention does not have special requirements for the flattening and thinning treatment II. While the molten glass II is being injected onto the surface of the molten metal, the molten glass II on the surface of the molten metal is flattened and thinned under the action of gravity and the edge-pulling machine. When the thickness of the molten glass II is close to or equal to the target thickness of 0.5 mm to 0.9 mm, the injection of molten glass II is stopped. After the molten glass II is completely flattened and thinned, glass layer II is formed.

[0085] In some preferred embodiments of the present invention, in step S3, the target thickness of the glass layer I obtained by the flattening and thinning treatment I is 0.05 mm to 0.15 mm. It should be noted that the target thickness refers to the thickness of the formed glass layer; in step S3, the target thickness refers to the thickness of the formed glass layer I. The present invention does not have special requirements for the flattening and thinning treatment I. While the molten glass I is injected into the surface of the glass layer II, the molten glass I on the surface of the glass layer II is flattened and thinned under the action of gravity and the edge-pulling machine. When the thickness of the molten glass I is close to or equal to the target thickness of 0.05 mm to 0.15 mm, the injection of molten glass I is stopped. After the molten glass I is completely flattened and thinned, the glass layer I is formed.

[0086] In some preferred embodiments of the present invention, step S3 further includes: after the glass layer I is formed, a laminated glass intermediate is obtained; the laminated glass intermediate is then annealed to obtain laminated glass. Preferably, in a temperature range where the temperature of the laminated glass intermediate is above 200°C, the cooling rate of the annealing treatment is controlled at ≤180°C / h; and in a temperature range where the temperature of the laminated glass intermediate is below 200°C, the cooling rate is controlled at ≤300°C / h. Controlling the cooling rate of the annealing treatment makes the overall properties of the obtained laminated glass more stable.

[0087] In some preferred embodiments of the present invention, step S3 further includes: after the glass layer I is formed, a laminated glass intermediate is obtained, and an anti-reflective film is deposited online on the surface of the glass layer I opposite to the glass layer II using a CVD process to obtain the laminated glass with anti-reflective function.

[0088] Current anti-reflective coating products are generally deposited on glass surfaces using offline magnetron sputtering technology. However, the durability and subsequent processing of coated glass products obtained by offline coating technology have certain problems. The inventors of this invention propose to combine online CVD coating technology with float glass forming technology to produce blue light filtering laminated glass with anti-reflective function. The anti-reflective film deposited on the laminated glass surface using online CVD coating technology can form chemical bonds with the laminated glass surface, thereby making the bonding force between the anti-reflective film and the laminated glass stronger, and improving wear resistance and chemical oxidation resistance. The laminated glass with excellent comprehensive performance provided by this invention can be mass-produced industrially using the above method.

[0089] In some preferred embodiments of the present invention, after the antireflective coating is deposited, an annealing treatment is performed to obtain the laminated glass with antireflective function that has more stable overall properties.

[0090] In some preferred embodiments of the present invention, TiO2 is plated. x The precursors used for the single-film deposition were isopropyl titanate and O2, and SiO2 was deposited. yThe precursors used for the single-film deposition were silane and O2, and the deposition temperature was 500℃~600℃. The preparation of TiO2... x The flow rate of isopropyl titanate used in the single-film reactor was controlled at 15 ml / min to 30 ml / min, and the flow rate of O2 was controlled at 300 ml / min to 500 ml / min; SiO2 was prepared. y The flow rate of silane used in the single membrane is controlled at 25 ml / min to 40 ml / min, and the flow rate of O2 is controlled at 150 ml / min to 300 ml / min.

[0091] A third aspect of the present invention provides a laminated glass preparation apparatus, comprising:

[0092] A forming tank for containing molten metal and forming laminated glass on the surface of the molten metal; and

[0093] At least two sets of melting and refining components are provided. Each melting and refining component includes a melter, a clarifier, and a guide pipe connected in sequence. The melter is used to melt the precursor composition to obtain molten glass. The clarifier is used to clarify the molten glass to obtain clarified molten glass. The guide pipe is used to guide the clarified molten glass into the forming tank.

[0094] In some preferred embodiments of the present invention, the laminated glass preparation apparatus further includes a coating device, which is disposed above the forming tank and is used to deposit an anti-reflective coating on the upper surface of the laminated glass online.

[0095] In some specific embodiments of the present invention, such as Figure 4 and Figure 3 As shown, the laminated glass manufacturing apparatus includes:

[0096] A forming tank 314 is used to contain molten tin 313 and form laminated glass on the surface of the molten tin 313.

[0097] The molten clarification assembly I includes a melter I305, a clarifier I307, and a guide pipe I308 connected in sequence. The melter I305 is used to melt the precursor composition I to form molten glass I306. The clarifier I307 is used to clarify the molten glass I306. The guide pipe I308 is used to guide the clarified molten glass I306 into the forming tank 314.

[0098] The molten clarification assembly II includes a melter II 301, a clarifier II 303, and a guide pipe II 304 connected in sequence. The melter II 301 is used to melt the precursor composition II to form molten glass II 302. The clarifier II 303 is used to clarify the molten glass II 302. The guide pipe II 304 is used to guide the clarified molten glass II 302 into the forming tank 314.

[0099] The coating machine I309 is used to deposit the first layer of TiO2 on the surface of laminated glass. x Single membrane 21;

[0100] Coating machine II310 is used to deposit the first layer of SiO2 on the surface of laminated glass. x Single membrane 22;

[0101] Coating machine III311 is used to deposit a second layer of TiO2 on the surface of laminated glass. x Single membrane 23; and

[0102] The IV312 coating machine is used to deposit a second layer of SiO2 on the surface of laminated glass. x Single membrane 24.

[0103] The fourth aspect of the present invention provides the application of the laminated glass described in the first aspect in glass cover plates.

[0104] The laminated glass provided by this invention can be used as a glass cover to effectively filter blue light. When used in electronic products, it can ensure the clarity, saturation, and color vibrancy of the screen display, and can also effectively reduce the damage of short-wave blue light from electronic products to the human eye.

[0105] The present invention will be described in detail below through embodiments. In the following embodiments, unless otherwise specified, room temperature refers to 25°C.

[0106] In the following examples, the components of precursor composition I and precursor composition II are selected from the analytical grade of the respective substances according to the components in glass layer I and glass layer II of the laminated glass prepared in Table 1.

[0107] In the following examples, the ratio of precursor composition I and precursor composition II was calculated based on the content of each component in glass layer I and glass layer II of the laminated glass prepared in Table 1.

[0108] In the following embodiments, the thickness of glass layer I is 0.1 mm and the thickness of glass layer II is 0.9 mm.

[0109] In the following embodiments, the laminated glass is prepared using the following methods: Figure 4 The laminated glass preparation apparatus shown is used.

[0110] Example 1: Laminated Glass

[0111] S1: The precursor composition I for forming glass layer I is melted in melter I to obtain glass melt I; the precursor composition II for forming glass layer II is melted in melter II to obtain glass melt II; the glass melt I is clarified in clarifier I to obtain clarified glass melt I; the glass melt II is clarified in clarifier II to obtain clarified glass melt II.

[0112] The melting treatment was carried out at a temperature of 1650℃ for 5 hours; the clarification treatment was carried out at a temperature of 1500℃ for 3 hours.

[0113] S2: The glass liquid II is introduced into the surface of the molten tin in the forming tank through the guide pipe II. At this time, the glass liquid II is flattened and thinned under its own gravity and the combined action of the edge pulling machine II. When the thickness of the glass liquid II is close to 0.9mm, the injection of the glass liquid II is stopped. After the glass liquid II is evenly flattened, glass layer II is obtained.

[0114] S3: The molten glass I is introduced into the surface of the glass layer II in the forming tank through the guide pipe I. At this time, the molten glass I is flattened and thinned under its own gravity and the combined action of the edge pulling machine. When the thickness of the molten glass I is close to 0.1mm, the injection of the molten glass I is stopped. After the molten glass I is evenly flattened, the glass layer I is formed, and the laminated glass intermediate is obtained.

[0115] The laminated glass intermediate is annealed. In the temperature range where the temperature of the laminated glass is above 200°C, the cooling rate of the annealing process is controlled at 180°C / h. In the temperature range where the temperature is below 200°C, the cooling rate is controlled at 300°C / h. The annealing process is carried out until the temperature of the laminated glass intermediate is room temperature, thus obtaining laminated glass B1. The performance parameters of laminated glass B1 are shown in Table 1.

[0116] Examples 2-4: Laminated Glass

[0117] By changing the composition ratio of precursor composition I and precursor composition II respectively, and keeping the other steps and parameters the same as in Example 1, laminated glasses B2, B3 and B4 were obtained respectively.

[0118] Comparative Example 1: Laminated Glass

[0119] By changing the component ratios of precursor composition I and precursor composition II respectively, while keeping the other step parameters the same as in Example 1, laminated glass DB1 was obtained.

[0120] In laminated glass DB1, the Sm2O3 content in glass layer I is less than 0.5 mol%.

[0121] Comparative Example 2: Laminated Glass

[0122] By changing the composition ratios of precursor composition I and precursor composition II respectively, while keeping the other step parameters the same as in Example 1, laminated glass DB2 was obtained.

[0123] In laminated glass DB2, the content of Sm2O3 in glass layer I is higher than that of Ho2O3.

[0124] Table 1

[0125]

[0126] According to Table 1, it can be seen from Example 1 and Comparative Example 1 that when the content of Sm2O3 in glass layer I is less than 0.5 mol.%, the effect of the laminated glass in blocking blue light is reduced. Therefore, the present invention controls the content of Sm2O3 to be not less than 0.5 mol.%.

[0127] As can be seen from Example 2 and Comparative Example 2, when the content of Ho2O3 in glass layer I is higher than the content of Sm2O3, the effect of the laminated glass in blocking blue light is better than when the content of Sm2O3 in glass layer I is higher than the content of Ho2O3. Therefore, the present invention controls the sum of the contents of Sm2O3 and Ho2O3 to be not less than 1 mol.%.

[0128] It can be clearly seen from Examples 3 and 4 that when the content of Sm2O3 and Ho2O3 in glass layer I exceeds 3 mol.% and reaches 3.5 mol.%, the effect of the laminated glass in blocking blue light is not further improved. On the contrary, the visible light transmittance will decrease. Therefore, the content of Sm2O3 and Ho2O3 in this invention is preferably no more than 3 mol.%.

[0129] Furthermore, as can be seen from Table 1, when the difference between the thermal expansion coefficient CTE2 of glass layer II and the thermal expansion coefficient CTE1 of glass layer I is greater than 1.0 × 10⁻⁶, -6 At a temperature of / ℃, the surface compressive stress of glass layer I can be increased to a certain extent, provided the difference in their coefficients of thermal expansion is less than 1.0 × 10⁻⁶. -6 At / ℃ (as in Comparative Example 1), it can be seen that the compressive stress value of the surface layer of glass layer I is significantly reduced, and the glass strength is weakened; as the difference between the thermal expansion coefficient CTE2 of glass layer II and the thermal expansion coefficient CTE1 of glass layer I exceeds 2.0×10 -6 / ℃ reaches 2.5×10 -6 At a temperature of / ℃, the compressive stress generated on the surface of glass layer I is too large, which may cause the laminated glass to warp.

[0130] Examples 5-7: Laminated glass with antireflective coating

[0131] In Example 1, the surface of glass layer I of the laminated glass intermediate is opposite to that of glass layer II. An anti-reflective film is deposited online using CVD process. After annealing, laminated glasses B11, B12, and B13 with anti-reflective function are obtained.

[0132] The specific steps are as follows: TiO2 is deposited alternately in sequence. x Single film and SiO y Single film, in which TiO x Single film and SiO y The refractive index and thickness of each single film are shown in Table 2. (TiO2 deposition) x The precursors used for the single-film deposition were isopropyl titanate and O2, and SiO2 was deposited. y The precursors used for the single-film deposition were silane and O2, and the deposition temperature was 550℃. The preparation of TiO2... x The flow rate of isopropyl titanate used in the single-film reactor was controlled at 15 ml / min to 30 ml / min, and the flow rate of O2 was controlled at 300 ml / min to 500 ml / min; SiO2 was prepared. y The flow rate of silane used in the single membrane was controlled at 25 ml / min to 40 ml / min, and the flow rate of O2 was controlled at 150 ml / min to 300 ml / min. The performance parameters of the laminated glasses B11, B12, and B13 with anti-reflection function are shown in Table 2.

[0133] Examples 8-10: Laminated glass with antireflective coating

[0134] In Example 2, the surface of glass layer I of the laminated glass intermediate is opposite to that of glass layer II. An anti-reflective film is deposited online using CVD process. After annealing, laminated glasses B21, B22, and B23 with anti-reflective function are obtained.

[0135] The specific steps and parameter control are the same as in Examples 5 to 7. The performance parameters of the laminated glasses B21, B22, and B23 with anti-reflection function are shown in Table 2.

[0136] Examples 11-13: Laminated glass with antireflective coating

[0137] In Example 3, the surface of glass layer I of the laminated glass intermediate is opposite to that of glass layer II. An anti-reflective film is deposited online using CVD process. After annealing, laminated glasses B31, B32, and B33 with anti-reflective function are obtained.

[0138] The specific steps and parameter control are the same as in Examples 5 to 7. The performance parameters of the laminated glasses B31, B32, and B33 with anti-reflection function are shown in Table 2.

[0139] Table 2

[0140]

[0141]

[0142] It should be noted that T1 indicates that the antireflection film is a single layer of TiO2. x Single film and 1 layer of SiO y In the case of a single film, the overall transmittance of the laminated glass; T2 indicates that the antireflective coating consists of two alternating layers of TiO2. x Single film and two-layer SiO y The overall transmittance of laminated glass in the case of a single film.

[0143] As shown in Tables 2 and 1, the visible light transmittance of the laminated glass coated with the anti-reflective coating is significantly improved compared to the laminated glass without the anti-reflective coating. Furthermore, the higher the refractive index of glass layer I in the laminated glass, the greater the increase in visible light transmittance after coating with the anti-reflective coating. In addition, compared to offline coated anti-reflective coatings, the anti-reflective coating of this invention, deposited through the CVD online coating process, has stronger adhesion to glass layer I, better wear and scratch resistance, and a longer service life.

[0144] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A laminated glass, characterized in that, The material comprises glass layer I and glass layer II, which are stacked together along the thickness direction. Based on the total molar amount of glass layer I, the composition of glass layer I includes: 65 mol.%~75 mol.% SiO2, 3 mol.%~8 mol.% Al2O3, 7 mol.%~12 mol.% B2O3, 5 mol.%~10 mol.% Na2O, and 1 mol.%~3.5 mol.% light-absorbing material. The light-absorbing materials are Sm₂O₃ and Ho₂O₃, and the content of Ho₂O₃ in the light-absorbing materials is not less than the content of Sm₂O₃. Based on the total molar amount of glass layer I, the content of Sm₂O₃ is not less than 0.5 mol%.%. Within a temperature range of 20℃ to 300℃, the coefficient of thermal expansion (CTE2) of glass layer II is greater than that of glass layer I (CTE1), and the coefficients of thermal expansion (CTE1) of glass layer I and glass layer II satisfy: 1.0 × 10⁻⁶. -6 / ℃≤CTE2-CTE1≤2.0×10 -6 / ℃; Within a temperature range of 20℃ to 300℃, the coefficient of thermal expansion CTE1 of the glass layer I is 4×10⁻⁶. -6 / ℃~6×10 -6 / ℃; the coefficient of thermal expansion CTE2 of the glass layer II is 5×10⁻⁶. -6 / ℃~8×10 -6 / ℃; The visible light transmittance of the glass layer II is not less than 90% when the thickness is 0.7 mm.

2. The laminated glass according to claim 1, characterized in that, Based on the total molar amount of glass layer I, the content of the light-absorbing material is 1 mol.% to 3 mol.%; The glass layer I is separated from the surface of the glass layer II, and the compressive stress is 100MPa~150MPa.

3. The laminated glass according to claim 1, characterized in that, Based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 2 mol.% of MgO; And / or, based on the total molar amount of glass layer I, glass layer I further contains 0.01 mol.% to 4 mol.% of P2O5.

4. The laminated glass according to claim 1, characterized in that, The glass layer II is at least one of potassium aluminum silicate glass, potassium borosilicate glass, and potassium aluminum borosilicate glass.

5. The laminated glass according to claim 4, characterized in that, Based on the total molar amount of the glass layer II, the composition of the glass layer II includes: 70 mol.%~80 mol.% SiO2, 5 mol.%~10 mol.% Al2O3, 4 mol.%~8 mol.% B2O3, 7 mol.%~12 mol.% K2O, and 3 mol.%~5 mol.% alkaline earth metal oxides, wherein the alkaline earth metal oxides are at least one of CaO, SrO and BaO.

6. The laminated glass according to any one of claims 1 to 5, characterized in that, The thickness of glass layer I is 0.05mm to 0.15mm, and the thickness of glass layer II is 0.5mm to 0.9mm.

7. The laminated glass according to claim 1, characterized in that, The laminated glass also includes an anti-reflective coating, which is bonded to the surface of glass layer I opposite to glass layer II.

8. The laminated glass according to claim 7, characterized in that, The antireflective film comprises at least one layer of TiO2 stacked alternately in sequence. x Single film and at least one layer of SiO y A single membrane, wherein 1.5 < x < 1.9, 1.2 < y < 1.

8.

9. The laminated glass according to claim 8, characterized in that, The TiOx single film and the SiOy single film each consist of 1 to 3 layers independently; The TiO x The thickness of the single film ranges from 60 nm to 220 nm, and the refractive index ranges from 2.0 to 2.

2. The SiO y The thickness of the single film is 90nm~310nm, and the refractive index is 1.42~1.48; The refractive index of the glass layer I is 1.58~1.

72.

10. A method for preparing laminated glass according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1: Precursor composition I for forming glass layer I and precursor composition II for forming glass layer II are respectively subjected to melt clarification treatment to obtain glass melt I and glass melt II respectively; S2: On the surface of the molten metal, the glass liquid II is spread and thinned II to obtain the glass layer II; S3: On the surface of the glass layer II that is away from the molten metal, the molten glass I is flattened and thinned I to form glass layer I on the surface of the glass layer II, thereby obtaining the laminated glass; The glass transition temperature Tg2 of the glass melt II is greater than the glass transition temperature Tg1 of the glass melt I.

11. The preparation method according to claim 10, characterized in that, In step S1, the melt clarification process involves first performing a melt treatment, followed by a clarification treatment. The conditions for the melting treatment are each independently selected from: a temperature of 1500℃~1700℃ and a treatment time of 4h~8h; the conditions for the clarification treatment are each independently selected from: a temperature of 1350℃~1550℃ and a treatment time of 2h~6h. In step S2, the target thickness of the glass layer II obtained by the flattening and thinning treatment II is 0.5 mm to 0.9 mm; In step S3, the target thickness of the glass layer I obtained by the flattening and thinning process I is 0.05 mm to 0.15 mm; The glass transition temperature Tg1 of the glass melt I is 800℃~850℃, and the glass transition temperature Tg2 of the glass melt II is 850℃~900℃.

12. The preparation method according to claim 10 or 11, characterized in that, Step S3 also includes: After the glass layer I is formed, an anti-reflective film is deposited online on the surface of the glass layer I opposite to the glass layer II using a CVD process to obtain the laminated glass with anti-reflective function.

13. A laminated glass preparation apparatus, characterized in that, include: A forming tank is used to contain molten metal and form laminated glass on the surface of the molten metal. as well as At least two sets of melting and refining assemblies, each set comprising a melter, a refiner, and a guide pipe connected in sequence, wherein the guide pipe is used to guide molten glass into the forming tank; The laminated glass is the laminated glass according to any one of claims 1 to 9.

14. The apparatus according to claim 13, characterized in that, It also includes a coating machine, which is located above the forming tank and is used to deposit an anti-reflective coating on the upper surface of the laminated glass online.

15. The use of the laminated glass according to any one of claims 1 to 9 in a glass cover.

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