High modulus glass, protective film, cover plate layer, display module and electronic device

Abstract

This application provides a glass, expressed as a molar percentage, comprising: 40%-70% SiO2, 7.5%-36% Al2O3, 0-11% B2O3+P2O5, 1%-10% MgO, 1%-8% CaO, 0.5%-7% Li2O, 2%-13% Na2O+K2O, 0-5% TiO2, 0-3% ZrO2, and 0-10%... The glass contains La2O3, 0-1.5% clarifying agent; 0.4 ≤ HE / LE ≤ 0.8; where HE = (Al2O3 + B2O3 + MgO + CaO + ZrO2 + TiO2 + La2O3 + Li2O); LE = (SiO2 + Na2O + K2O); Al2O3(Li2O + Na2O + K2O) ≤ 15%, 45% ≤ (SiO2 + P2O5 + B2O3) ≤ 70%. This glass has an elastic modulus of over 90 GPa without crystallization treatment. When used as a cover glass layer in flexible display modules, it can improve the flatness and impact resistance of the display module and reduce the visibility of creases.

Description

Technical Field

[0001] This application relates to the field of glass, specifically to a high-modulus glass, a protective film, a cover layer, a display module, and electronic equipment. Background Technology

[0002] Glass has played a vital role in the development of modern industry. It is also frequently found in existing electronic devices. For example, glass is used as the casing of electronic devices, such as the back panel and camera cover of mobile phones and other terminals made of glass. Glass can also be used as a cover layer for display modules. Furthermore, glass can be used as a protective film, such as the common tempered glass screen protector, which is adhered to the surface of the display modules of electronic devices such as mobile phones and laptops.

[0003] The structures obtained from processed glass need to possess a certain degree of rigidity to ensure that the glass structure maintains a stable shape and dimensions during use. For example, flexible display modules are a typical application scenario where glass serves as the cover layer. During use, flexible display modules are constantly subjected to bending and folding. If the rigidity of the cover layer is insufficient, creases and poor flatness will easily appear on the surface of the flexible display module.

[0004] The stiffness of a structure depends on its geometry and the elastic modulus of the material. Existing glass suffers from a low elastic modulus, resulting in glass structures failing to meet operational requirements in terms of stiffness. Summary of the Invention

[0005] This application provides a glass, a protective film, a cover layer, a display module, and an electronic device. The glass has a high elastic modulus, which can improve the rigidity of the structure processed from the glass.

[0006] In a first aspect, a glass is provided, expressed as a molar percentage, comprising: 40%-70% SiO2, 7.5%-36% Al2O3, 0-11% B2O3+P2O5, 1%-10% MgO, 1%-8% CaO, 0.5%-7% Li2O, 2%-13% Na2O+K2O, 0-5% TiO2, 0-3% ZrO2, 0-10%... The glass composition is as follows: % La2O3, 0-1.5% clarifying agent; 0.4 ≤ HE / LE ≤ 0.8; where HE = (Al2O3 + B2O3 + MgO + CaO + ZrO2 + TiO2 + La2O3 + Li2O); LE = (SiO2 + Na2O + K2O); (Li2O + Na2O + K2O) ≤ 15%, 45% ≤ (SiO2 + P2O5 + B2O3) ≤ 70%. In this implementation, the glass processed according to the aforementioned specific components and their contents can possess a high elastic modulus without crystallization treatment. By limiting the ratio range of HE and LE, the elastic modulus of the glass can be increased, and the viscosity-temperature characteristics of the glass can also be affected, making it easier to produce using either the float glass or the down-drawing process. Glass produced by the float glass and down-drawing processes has fewer surface defects and higher strength. The proportions of SiO2, P2O5, and B2O3 affect the glass-forming properties and elastic modulus. Too low a proportion leads to poor chemical stability, easy phase separation, and even failure to form glass. Too high a proportion results in an excessively low elastic modulus. Meanwhile, Li2O, Na2O, and K2O enable ion exchange strengthening treatment of the glass; the appropriate proportion of Al2O3 ensures a high elastic modulus and provides sufficient ion exchange channels to facilitate ion exchange and further improve glass strength.

[0007] In conjunction with the first aspect, in the first possible implementation of the first aspect, 0.5 ≤ HE / LE ≤ 0.7; or 0.6 ≤ HE / LE ≤ 0.7. This implementation, by limiting the ratio of HE to LE, can further improve the elastic modulus of the glass, while making the glass easier to produce by float glass or drop glass processes.

[0008] In conjunction with the first aspect and the first possible implementation of the first aspect, in the second possible implementation of the first aspect, (Li2O+Na2O+K2O)≥5%. This implementation, by limiting the lower limit of the proportion of Li2O+Na2O+K2O, ensures that the glass can be sufficiently strengthened after ion exchange, thereby further improving the glass strength.

[0009] In combination with the first aspect and any of the first to second possible implementations of the first aspect, in the third possible implementation of the first aspect, 7.5% ≤ Al2O3 ≤ 30%; 0.45 ≤ LT / HT ≤ 2.4; where LT = (Li2O + Na2O + K2O + B2O3); HT = (Al2O3 + ZrO2). In this implementation, the content of Al2O3 is less than or equal to 30%. Excessive LT content will lower the melting point temperature of the glass, while excessive HT content will raise the melting point temperature of the glass. By limiting the range of LT / HT, the upper limit of the Al2O3 percentage, and the range of the TiO2 + ZrO2 percentage, the melting point temperature range of the glass can be made suitable for production by float glass or pull glass methods.

[0010] In conjunction with the third possible implementation of the first aspect, in the fourth possible implementation of the first aspect, 0.6≤LT / HT≤2.0; or 0.8≤LT / HT≤2.0; or 1.0≤LT / HT≤2.0; or 1.0≤LT / HT≤1.8. This implementation, by further limiting the range of LT / HT, can further control the melting point temperature range of the glass to be more suitable for float glass or drop glass production.

[0011] In combination with the first aspect and any of the first to fourth possible implementations of the first aspect, in the fifth possible implementation of the first aspect, (TiO2+ZrO2)≤5%. The aforementioned proportion range of TiO2+ZrO2 can ensure that the refractive index of the glass can be adapted to the display panel while maintaining the high elastic modulus of the glass.

[0012] In conjunction with the first aspect, any of the first to fifth possible implementations of the first aspect, and in the sixth possible implementation of the first aspect, the glass further comprises, in molar percentage, at least one of ZnO, Sr2O3, BaO, Nb2O5, Na2SO4, or NaNO3; 0 < (ZnO + Sr2O3 + BaO + Nb2O5 + Na2SO4 + NaNO3) ≤ 5%. This implementation, by doping the glass raw material with one or more of ZnO, Sr2O3, BaO, Nb2O5, Na2SO4, or NaNO3, can fine-tune the viscosity-temperature characteristics of the glass, making it more suitable for float glass or drop glass production. Simultaneously, the total doping amount is controlled to be less than or equal to 5% to avoid adversely affecting the elastic modulus of the glass.

[0013] In combination with the first aspect and any of the first to sixth possible implementations of the first aspect, in the seventh possible implementation of the first aspect, the elastic modulus of the glass is greater than or equal to 90 GPa. By increasing the elastic modulus of the glass to above 90 GPa, the stiffness of the glass structure can be effectively improved in this implementation.

[0014] In conjunction with the first aspect and any of the first to seventh possible implementations of the first aspect, in the eighth possible implementation of the first aspect, the surface of the glass has a compression layer formed after ion exchange; the ion exchange includes at least one of Li-Na ion exchange, Na-K ion exchange, or Li-K ion exchange. The glass of this implementation contains Li₂O, Na₂O, or K₂O, allowing the glass to undergo ion exchange strengthening treatment; Al₂O₃ provides ion exchange channels to facilitate ion exchange. After ion exchange, larger ions enter the surface layer of the glass, thereby forming a compression layer and further improving the strength of the glass.

[0015] In conjunction with the eighth possible implementation of the first aspect, in the ninth possible implementation of the first aspect, the compressive stress of the compression layer is greater than or equal to 450 MPa.

[0016] In conjunction with the eighth or ninth possible implementation of the first aspect, and in the tenth possible implementation of the first aspect, the depth of the compression layer is greater than or equal to 6 μm. When the glass with the aforementioned compression layer depth is used as a cover glass layer in a flexible display module, it has a good effect on improving the flatness of the display module, its impact resistance, and reducing the noticeability of creases.

[0017] In conjunction with the tenth possible implementation of the first aspect, in the eleventh possible implementation of the first aspect, the ratio of the depth of the compression layer to the thickness of the glass is 20%-23%. This implementation, by limiting the thickness ratio of the compression layer to the glass, can significantly improve the strength of the glass and provide better impact resistance.

[0018] In conjunction with any of the eighth to eleventh possible implementations of the first aspect, in the twelfth possible implementation of the first aspect, the glass has a Vickers hardness value of 200 gf greater than or equal to 600 kgf / mm². 2 The glass produced by this method has an improved Vickers hardness value after ion exchange, which can reduce the probability of scratches appearing during use.

[0019] In combination with the first aspect and any one of the first to twelfth possible implementations of the first aspect, in the thirteenth possible implementation of the first aspect, 420℃≤T 4.0 -T 11.5 ≤550℃; where T 4.0 and T 11.5 These represent glass viscosities of 10 and 10, respectively. 4.0 dPa·s and 10 11.5The temperature corresponding to dPa·s. The viscosity-temperature range of the glass in this implementation is suitable for production by float glass or down-draw glass. Glass structures produced by float glass and down-draw glass have fewer surface defects.

[0020] In conjunction with the thirteenth possible implementation of the first aspect, in the fourteenth possible implementation of the first aspect, 420℃≤T 4.0 -T 11.5 ≤490℃. The viscosity-temperature range of the glass in this implementation is suitable for the down-draw process.

[0021] In conjunction with the thirteenth possible implementation of the first aspect, and in the fifteenth possible implementation of the first aspect, 460℃≤T 4.0 -T 11.5 ≤550℃. The viscosity-temperature range of the glass in this implementation is suitable for float glass production.

[0022] In conjunction with the first aspect, and any of the first to fifteenth possible implementations of the first aspect, and in the sixteenth possible implementation of the first aspect, the proportion of crystalline phase in the glass, expressed as a weight percentage, is less than 10%. In this implementation, the glass can achieve a high elastic modulus without crystallization treatment.

[0023] In conjunction with the first aspect, and any one of the first to sixteenth possible implementations of the first aspect, and in the seventeenth possible implementation of the first aspect, the optical transmittance of the glass is greater than or equal to 86% in the wavelength range of 400nm-800nm. When the glass of this implementation is used as a cover glass layer in a flexible display module, it has little impact on the brightness of the displayed image and provides a good display effect.

[0024] In conjunction with the first aspect, and in any of the first to seventeenth possible implementations of the first aspect, and in the eighteenth possible implementation of the first aspect, the clarifying agent includes at least one of SnO2, SB2O3, CeO2, or NaF. The clarifying agent in this implementation can reduce the number of bubbles in the glass and improve the optical properties of the glass.

[0025] Secondly, a protective film is provided for protecting electronic devices. This protective film includes glass as described in the first aspect and any one of the eighteenth possible implementations of the first aspect. The aforementioned glass has a high modulus of elasticity; therefore, the protective film including the aforementioned glass can be used to cover relatively fragile parts such as display modules and camera modules of electronic devices such as mobile phones, laptops, and watches. On the one hand, it provides protection; on the other hand, the protective film can be replaced individually if damaged, making it convenient and cost-effective.

[0026] Thirdly, an electronic device is provided, comprising: a housing including glass as described in the first aspect and any one of the eighteenth possible implementations of the first aspect; and a circuit board disposed within the housing. The aforementioned glass has a high modulus of elasticity; therefore, the housing including the aforementioned glass can be used to protect internal components such as the circuit board.

[0027] Fourthly, a cover layer is provided, comprising: a glass layer, including the glass in the first aspect and any one of the eighteenth possible implementations of the first aspect; and an adhesive layer, one side of which connects to the glass layer and the other side of which is used to bond to a display panel. The aforementioned glass has a high modulus of elasticity. When the glass layer, as a cover layer, is applied to a flexible display module, it can improve the flatness and impact resistance of the display module and reduce the noticeability of creases.

[0028] Fifthly, a display module is provided, comprising: a display component including a display panel and a control circuit; and a cover layer as described in the fourth aspect, the cover layer being bonded to the display panel via the adhesive layer.

[0029] In a sixth aspect, an electronic device is provided, comprising: a frame; and the display module of the fifth aspect, fixed to the frame. Attached Figure Description

[0030] Figure 1 A schematic diagram of an electronic device provided for some embodiments of this application;

[0031] Figure 2 A schematic diagram of an electronic device provided for some embodiments of this application.

[0032] Explanation of reference numerals in the attached figures:

[0033] 10-Electronic devices;

[0034] 101 - Outer casing; 102 - Circuit board; 103 - Frame; 104 - Display module;

[0035] 1041 - Display component; 1042 - Cover plate layer;

[0036] 10411 - Display panel; 10412 - Control circuit; 10421 - Glass layer; 10422 - Adhesive layer. Detailed Implementation

[0037] This application provides a glass with a high elastic modulus, which can be used, but is not limited to, as a protective material in various electronic devices, such as as a protective film, housing, or display module cover for various electronic devices.

[0038] Some embodiments of this application relate to a protective film. This protective film includes glass with a high elastic modulus as mentioned in the foregoing embodiments. The protective film may consist solely of a thin film made of the aforementioned glass, or it may consist of a thin film made of the aforementioned glass and coatings such as adhesives or oleophobic layers on the surface of the film. Along its plane, the protective film may be entirely made of the aforementioned glass, or only a portion of the plane may contain the aforementioned glass. The protective film can be used to cover relatively fragile parts such as display modules and camera modules of electronic devices such as mobile phones, laptops, and watches. On the one hand, it provides protection; on the other hand, it can be replaced individually after damage, making replacement convenient, low-cost, and without affecting the normal use of the electronic device.

[0039] Please refer to Figure 1 Some embodiments of this application relate to an electronic device 10. The electronic device 10 includes a housing 101 and a circuit board 102 disposed within the housing 101. The housing 101 includes glass with a high elastic modulus, as mentioned in the foregoing embodiments. Because the aforementioned glass has a high elastic modulus, the housing 101 including the aforementioned glass can be used to protect internal components such as the circuit board 102. The housing 101 may be entirely made of the aforementioned glass, or only a portion thereof. Optionally, the electronic device 10 may be a terminal such as a mobile phone, and the housing 101 includes a back panel of the terminal, which is made of the aforementioned glass. Optionally, the electronic device 10 may have a camera, and the housing 101 includes a camera cover, which is made of the aforementioned glass and covers the camera lens and internal photoelectric sensors, etc. Optionally, the electronic device 10 may be a vehicle, which includes various sensors such as lidar, TOF (Time of Flight) sensors, etc. The sensors include a circuit board 102, and the housing 101 includes a sensor cover, which is made of the aforementioned glass and covers the sensor's circuit board 102.

[0040] Please refer to Figure 2Some embodiments of this application relate to an electronic device 10. The electronic device 10 includes a frame 103 and a display module 104 fixed to the frame 103. The display module 104 includes a display component 1041 and a cover layer 1042. The display component 1041 includes a display panel 10411 and a control circuit 10412. The display panel 10411 can be a rigid display panel or a flexible display panel. It is understood that a rigid display panel can be a rigid liquid crystal display panel (LCD), a rigid organic light-emitting diode (OLED) panel, etc., and a flexible display panel can be a flexible liquid crystal display panel (LCD), a flexible organic light-emitting diode (OLED) panel, etc. However, this embodiment does not specifically limit the type of display panel 10411; that is, those skilled in the art can adjust its type according to actual conditions, as long as the display panel 10411 can display image information. The cover layer 1042 is attached to the side of the display panel 10411 that displays the image. Optionally, the cover layer 1042 can be directly attached to the display panel 10411; other structures, such as polarizers or touch layers, can also exist between the cover layer 1042 and the display panel 10411. Specifically, the cover layer 1042 includes a glass layer 10421 and an adhesive layer 10422. The adhesive layer 10422 is connected to the glass layer 10421 and is used to bond to the display panel 10411. Optionally, the adhesive layer 10422 can be an optical clear adhesive (OCA). OCA has an adhesive effect and is light-transmitting, which can reduce the adverse effects on the display effect of the display panel 10411. It is understood that the cover layer 1042 can also have other structures, such as a polyethylene terephthalate (PET) layer, etc. The PET layer is located on the outer surface of the glass layer 10421, and the PET layer and the glass layer 10421 can be bonded together by OCA. Optionally, when the display panel 10411 is a flexible display panel, the glass layer 10421 can be ultra-thin glass (UTG) to achieve better bending performance.

[0041] The cover layer 1042 of the existing flexible display module has insufficient rigidity, resulting in insufficient support of the cover layer 1042 for the display module 104, and the surface of the display module 104 is not smooth enough with obvious creases.

[0042] When other structures of the cover layer 1042 are ignored (such as adhesive layer 10422, PET, etc.), the stiffness D of the cover layer and the elastic modulus E of the glass layer 10421 have the following relationship:

[0043]

[0044] Where t is the thickness of glass layer 10421, and v is the Poisson's ratio of glass layer 10421.

[0045] Therefore, by increasing the elastic modulus E of the glass layer 10421, the stiffness D of the cover layer 1042 can be increased, thereby improving the flatness of the display module 104.

[0046] In addition, increasing the elastic modulus of the glass layer 10421 can reduce the strain of the display panel 10411 when subjected to the same impact, thereby better protecting the display panel 10411.

[0047] In this embodiment, the glass layer 10421 includes the glass with a high elastic modulus mentioned in the previous embodiments. Therefore, the cover layer 1042 with the glass layer 10421 can protect the display panel 10411 and improve its impact resistance. When the display panel 10411 is a flexible display panel, the cover layer 1042 with the glass layer 10421 can also improve the flatness of the display module 104 and reduce the visibility of creases.

[0048] In some embodiments of this application, the glass comprises, in molar percentage: 40%-70% SiO2, 7.5%-36% Al2O3, 0-11% B2O3+P2O5, 1%-10% MgO, 1%-8% CaO, 0.5%-7% Li2O, 2%-13% Na2O+K2O, 0-5% TiO2, 0-3% ZrO2, 0-10% La2O3, and 0-1.5% clarifying agent. 0.4 ≤ HE / LE ≤ 0.8; where HE = (Al2O3+B2O3+MgO+CaO+ZrO2+TiO2+La2O3+Li2O); LE = (SiO2+Na2O+K2O); (Li2O+Na2O+K2O) ≤

[0049] 15%, (TiO2+ZrO2)≤5%, 45%≤(SiO2+P2O5+B2O3)≤70%.

[0050] In this embodiment, the molar percentage of SiO2 is typically, but not limited to, 40%, 43%, 45%, 48%, 50%, 52%, 56%, 59%, 63%, 67%, or 70%.

[0051] In this embodiment, the molar percentage of B2O3+P2O5 is typically, but not limited to, 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, or 11%.

[0052] In this embodiment, the molar percentage of MgO is typically, but not limited to, 1%, 1.5%, 2%, 4%, 5%, 6%, 8%, 9%, or 10%.

[0053] In this embodiment, the molar percentage of CaO is typically, but not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%.

[0054] In this embodiment, the molar percentage of Li2O is typically, but not limited to, 0.5%, 1%, 2%, 2.5%, 4%, 5%, 6%, or 7%.

[0055] In this embodiment, the molar percentage of Na2O+K2O is typically, but not limited to, 2%, 3%, 4%, 5%, 7%, 9%, 11%, or 13%.

[0056] In this embodiment, the molar percentage of TiO2 is typically, but not limited to, 0.1%, 0.5%, 1%, 2%, 3%, 3.5%, 4%, or 5%.

[0057] In this embodiment, the molar percentage of ZrO2 is typically, but not limited to, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%.

[0058] In this embodiment, the molar percentage of La2O3 is typically, but not limited to, 0.1%, 0.5%, 1%, 3%, 4%, 5%, 7%, 9%, or 10%.

[0059] In this embodiment, the molar percentage of the clarifying agent is typically, but not limited to, 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.2%, or 1.5%.

[0060] In this embodiment, the ratio of HE to LE ranges from 0.4 to 0.8. Specifically, the ratio of HE to LE can typically, but not limited to, be 0.4, 0.44, 0.47, 0.5, 0.55, 0.58, 0.6, 0.63, 0.67, 0.68, 0.7, 0.74, 0.78, or 0.8.

[0061] By limiting the aforementioned range of the HE / LE ratio, the elastic modulus of the glass can be increased, and its viscosity-temperature characteristics can also be affected, making the glass easier to produce using either the float glass or down-drawing process. Preferably, 0.5 ≤ HE / LE ≤ 0.7 further increases the elastic modulus of the glass. More preferably, 0.6 ≤ HE / LE ≤ 0.7 further increases the elastic modulus of the glass. Through the aforementioned progressively optimized HE / LE range, the elastic modulus of the glass can be gradually increased, while simultaneously making the glass easier to produce using either the float glass or down-drawing process.

[0062] It's important to note that other flat glass manufacturing processes besides float glass and down-draw glass, such as casting and rolling, require grinding and polishing before chemical etching. The polished glass surface contains numerous micro-defects, which are amplified during chemical etching. When used in display module cover glass, this can negatively impact the cover glass's strength and the display panel's performance. Taking UTG production via float glass and down-draw glass as examples, a thicker glass sheet (70μm-300μm) can be produced first. This sheet has fewer structural defects, resulting in a UTG with fewer defects after subsequent chemical etching to a thickness of 30μm-50μm. Alternatively, a 30μm-50μm UTG can be directly drawn using the down-draw method, also resulting in a UTG with minimal structural defects. Therefore, glass produced using either float glass or down-draw glass exhibits fewer surface defects and higher strength, leading to a superior visual experience when used in display modules.

[0063] In this embodiment, the molar percentage of SiO2+P2O5+B2O3 is 45%-75%. Specifically, the molar percentage of SiO2+P2O5+B2O3 is typically, but not limited to, 45%, 48%, 52%, 55%, 60%, 65%, 68%, 73%, and 75%.

[0064] The proportion of SiO2+P2O5+B2O3 affects the glass-forming properties and elastic modulus. Too low a proportion leads to poor chemical stability, easy phase separation, and even failure to form glass. Too high a proportion results in an excessively low elastic modulus. The aforementioned range of SiO2+P2O5+B2O3 molar percentages ensures both glass formation and a high elastic modulus.

[0065] In this embodiment, the molar percentage of Li₂O + Na₂O + K₂O is less than or equal to 15%. Specifically, the molar percentage of Li₂O + Na₂O + K₂O can typically, but is not limited to, being 1%, 3%, 5%, 6%, 7%, 9%, 11%, 13%, 14%, or 15%.

[0066] Li₂O, Na₂O, and K₂O allow glass to undergo at least one of the following ion exchange strengthening treatments: Li-Na ion exchange, Na-K ion exchange, or Li-K ion exchange, thereby increasing the glass's strength. However, the molar percentage of Li₂O + Na₂O + K₂O cannot be too high, otherwise the glass's elastic modulus will be too low. The aforementioned range of the molar percentage of Li₂O + Na₂O + K₂O ensures that the glass can be strengthened to a certain extent, improving its strength, while also giving it a relatively high elastic modulus.

[0067] Preferably, in some embodiments, the molar percentage of Li₂O + Na₂O + K₂O is greater than or equal to 5%. This embodiment can provide sufficient exchangeable ions so that the glass can be sufficiently strengthened after ion exchange, further improving the glass strength, while also giving the glass a high elastic modulus.

[0068] In this embodiment, the molar percentage of Al2O3 is greater than or equal to 7.5% and less than or equal to 36%. Specifically, the molar percentage of Al2O3 can typically, but not limited to, be 7.5%, 8%, 10%, 14%, 17%, 20%, 23%, 26%, 28%, 30%, 34%, or 36%.

[0069] The aforementioned molar percentage range of Al2O3 can ensure the high elastic modulus of the glass, while also providing sufficient ion exchange channels to facilitate Li-Na ion exchange, Na-K ion exchange, or Li-K ion exchange, thereby further improving the strength of the glass.

[0070] In this embodiment, the glass processed according to the specific components and content of each component of the aforementioned glass has an elastic modulus of 90 GPa or higher without crystallization treatment. When this glass is used as the cover glass layer 10421 in a flexible display module, it can improve the flatness and impact resistance of the display module and reduce the noticeability of creases.

[0071] In some implementations, 7.5% ≤ Al2O3 ≤ 30%; 0.45 ≤ LT / HT ≤ 2.4; where LT = (Li2O + Na2O + K2O + B2O3); HT = (Al2O3 + ZrO2).

[0072] In this embodiment, the ratio of LT to HT ranges from 0.45 to 2.4. Specifically, the ratio of LT to HT can typically, but not limited to, be 0.45, 0.55, 0.6, 0.7, 0.9, 1.0, 1.3, 1.5, 1.7, 1.8, 2.0, 2.2, or 2.4.

[0073] Excessive LT content leads to a lower melting point temperature and a longer glass lifespan; excessive HT content leads to a higher melting point temperature and a shorter glass lifespan. Furthermore, the proportion of Al2O3 also affects the melting point temperature. By limiting the aforementioned range of LT to HT ratios and the upper limit of Al2O3 proportion, the melting point temperature range of the glass can be made suitable for production using either the float glass or the down-draw glass process.

[0074] Preferably, 0.6 ≤ LT / HT ≤ 2.0 allows for further control of the glass's melting point temperature range. More preferably, 0.8 ≤ LT / HT ≤ 2.0 allows for even further control of the glass's melting point temperature range. Still preferably, 1.0 ≤ LT / HT ≤ 2.0 allows for even further control of the glass's melting point temperature range. More preferably, 1.0 ≤ LT / HT ≤ 1.8 allows for even further control of the glass's melting point temperature range. Through the aforementioned progressively optimized LT / HT ranges, the glass can be made easier to produce using either the float glass or the down-draw glass process.

[0075] In some embodiments, the molar percentage of (TiO2 + ZrO2) is less than or equal to 5%. Specifically, the molar percentage of TiO2 + ZrO2 can typically, but not limited to, be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.

[0076] The aforementioned molar percentage range of (TiO2+ZrO2) can further control the melting point temperature of the glass while ensuring that the glass has a high elastic modulus, making the glass more suitable for production by float glass or down-draw glass. At the same time, it can also make the refractive index of the glass compatible with the display panel, avoiding too many adverse effects on the display effect of the display panel.

[0077] In some embodiments, the glass further comprises, in molar percentage, at least one of ZnO, Sr2O3, BaO, Nb2O5, Na2SO4, or NaNO3; 0 < (ZnO + Sr2O3 + BaO + Nb2O5 + Na2SO4 + NaNO3) ≤ 5%.

[0078] In this embodiment, the molar percentage of ZnO+Sr2O3+BaO+Nb2O5+Na2SO4+NaNO3 is less than or equal to 5%. Specifically, the molar percentage of (ZnO+Sr2O3+BaO+Nb2O5+Na2SO4+NaNO3) is typically, but not limited to, 0.1%, 0.5%, 1%, 1.3%, 1.6%, 2%, 2.5%, 3%, 3.4%, 3.7%, 4%, 4.5%, and 5%.

[0079] By doping glass raw materials with one or more of ZnO, Sr2O3, BaO, Nb2O5, Na2SO4 or NaNO3, the viscosity-temperature characteristics of the glass can be finely adjusted to make the glass more suitable for float glass or drop glass production. At the same time, the total doping amount should be controlled to be less than or equal to 5% to avoid adverse effects on the elastic modulus of the glass.

[0080] In some embodiments, the components and proportions in the aforementioned embodiments are controlled so that the glass satisfies: 420℃≤T 4.0 -T 11.5 ≤550℃; where T 4.0 and T 11.5 These represent glass viscosities of 10 and 10, respectively. 4.0 dPa·s and 10 11.5 The temperature corresponding to dPa·s. In this embodiment, the viscosity temperature range of the glass is suitable for production by float glass or pull glass.

[0081] In some alternative implementations, 420℃≤T 4.0 -T 11.5 Glass with a viscosity temperature range of ≤490℃ is suitable for production using the pull-down process, which can reduce structural defects in the glass and achieve a better appearance when used as a cover for display modules.

[0082] In some alternative implementations, 460℃≤T 4.0 -T 11.5 Glass with a viscosity temperature range of ≤550℃ is suitable for float glass production, which can reduce structural defects in the glass and achieve a better appearance when used as a cover for display modules.

[0083] In some embodiments, the glass surface has a compression layer formed after ion exchange; the ion exchange includes at least one of Li-Na ion exchange, Na-K ion exchange, or Li-K ion exchange. The glass of this embodiment contains Li₂O, Na₂O, or K₂O, allowing the glass to undergo ion exchange strengthening treatment; Al₂O₃ provides ion exchange channels to facilitate ion exchange. After ion exchange, larger ions enter the glass surface layer, thereby forming a compression layer and further improving the strength of the glass. Preferably, the compressive stress of the compression layer is greater than or equal to 450 MPa.

[0084] Optionally, the depth of the compression layer is greater than or equal to 6 μm. The thickness of UTG is typically 30 μm-50 μm. When UTG with this compression layer depth is used as a glass layer 10421 in flexible display modules, it has a good effect on improving the flatness of the display module, its impact resistance, and reducing the visibility of creases.

[0085] Optionally, the ratio of the depth of the compression layer to the thickness of the glass is 20%-23%. This implementation significantly improves the strength of the glass by limiting the ratio of the thickness of the compression layer to the thickness of the glass, thus giving the glass better impact resistance when applied in other scenarios, such as protective films and electronic device housings.

[0086] Optionally, the ion-exchange chemically strengthened glass has a Vickers hardness value of 200 gf greater than or equal to 600 kgf / mm. 2 Specifically, after ion exchange, the Vickers hardness of glass having the components and proportions of any of the aforementioned embodiments is improved and can reach 600 kgf / mm². 2 The above measures can reduce the probability of scratches appearing on the glass during use.

[0087] In some embodiments, the proportion of crystalline phase in the glass is less than 10% by weight. In this embodiment, the glass has not undergone crystallization treatment, so the proportion of crystalline phase is less than 10%. However, since the glass of this embodiment has the composition and proportions of the glass in any of the aforementioned embodiments, it can still achieve a high elastic modulus, and there is no need to worry about the problem of reduced light transmittance caused by crystallization.

[0088] In some embodiments, the optical transmittance of the glass is greater than or equal to 86% in the wavelength range of 400nm-800nm. When the glass layer 10421 of this embodiment is used as a cover layer in a flexible display module, it has little impact on the brightness of the displayed image and provides a good display effect.

[0089] In some embodiments, the clarifying agent in the glass material includes at least one of SnO2, SB2O3, CeO2, or NaF. These clarifying agents can reduce the number of bubbles in the glass and improve its optical properties.

[0090] The embodiments of the present invention will be further described below through specific examples.

[0091] According to the glass raw material components and molar ratios listed in Table 1 for each embodiment and comparative example, the weight ratio of the glass raw material components was calculated to prepare various raw materials. After thorough mixing, the weighed raw material powder was placed in a mixer and mixed evenly. Glass melting was then carried out using a platinum crucible: the evenly mixed raw material powder was placed in the platinum crucible, and the crucible was then placed in a high-temperature furnace at 1450℃~1650℃ for 2 hours. The molten glass was poured into a stainless steel mold and cooled to form the shape. Finally, the formed glass block was quickly transferred to an annealing furnace and annealed at 650℃ for 12 hours, then cooled to room temperature. The resulting glass block was transparent. It was then cut into 0.8mm thick sheets using multi-wire cutting, and then ground and polished to produce transparent glass sheets with a thickness of 0.6mm or 0.03mm.

[0092] Table 1

[0093]

[0094]

[0095] For transparent glass sheets that have not yet undergone chemical strengthening, the elastic modulus (E) of the glass was tested using a UMS ultrasonic measurement system; the viscosity-temperature curve of the glass was tested using a high-temperature rotational viscometer, and then the temperature (T) was obtained by fitting the glass using the Vogel-Fulcher-Tammann (VFT) equation. 4.0 and T 11.5 Temperature; transmittance of the glass was tested using a spectrophotometer; crystallinity of the glass was tested using an X-ray diffractometer (XRD).

[0096] The aforementioned transparent glass sheets with a thickness of 0.6 mm or 0.03 mm were subjected to salt bath chemical strengthening using 100% molten KNO3 at a strengthening temperature of 390 °C for 40 min. After the salt bath, the glass sheets were cooled to room temperature and then ultrasonically cleaned.

[0097] For chemically strengthened transparent glass sheets, the surface stress (Cs) and stress layer depth (DOL) were tested using an FSM stress tester; the Vickers hardness (Hv) of the glass was tested using a Vickers hardness tester with a load of 200 gf.

[0098] The corresponding test parameters are shown in Table 2.

[0099] Table 2

[0100]

[0101]

[0102] As can be seen from the data in Tables 1 and 2, changing the composition of the glass raw materials can affect the elastic modulus of the glass. In Examples 1 to 13 of this application, by controlling the HE / LE value and the proportions of Al2O3, (Li2O+Na2O+K2O), (TiO2+ZrO2), and (SiO2+P2O5+B2O3), the elastic modulus of the glass was made to be above 90 GPa. More preferably, Examples 3, 7, and 8 controlled the HE / LE value to be between 0.6 and 0.7, resulting in an elastic modulus of the glass above 105 GPa. The HE / LE value of Comparative Example 1 was 0.23, outside the HE / LE range of 0.4-0.8 of this application; the proportion of (Li2O+Na2O+K2O) was 16.38, exceeding the upper limit of 15% for (Li2O+Na2O+K2O) in this application, and the final elastic modulus of the obtained glass was 73 GPa, far lower than the elastic modulus of the glass in Examples 1 to 13 of this application. This demonstrates that the HE / LE ratio and the upper limit of the (Li2O+Na2O+K2O) ratio affect the elastic modulus of the glass. The high elastic modulus glass described in Embodiments 1 to 13 of this application can be used as a protective material in various electronic devices. When the glass in each embodiment is used as the cover glass layer 10421 in a flexible display module, it can improve the flatness and impact resistance of the display module and reduce the visibility of creases.

[0103] As can be seen from the data in Table 2, after chemical strengthening, the glass of Examples 1 to 13 of this application all have a compression layer depth of more than 6 μm, a compressive stress of more than 450 MPa, and a Vickers hardness of 600 kgf / mm² at 200 gf. 2 The glass in Examples 1 to 13 above has good impact resistance. When the glass layer used as a cover layer is applied to a flexible display module, it can improve the flatness and impact resistance of the display module and reduce the visibility of creases.

[0104] As can be seen from the data in Table 2, the T of the glass in Embodiments 1 to 13 of this application 4.0 -T 11.5 Both are in the range of 420℃-550℃, suitable for production by float glass or drop glass, which can reduce glass structure defects. When the 10421 glass layer is used as a cover glass layer in flexible display modules, it can achieve a better visual experience.

[0105] As can be seen from the data in Table 2, the average transmittance of the glass in Examples 1 to 13 of this application is above 86% in the wavelength range of 400nm-800nm, and the crystallinity (i.e. the proportion of crystalline phase expressed as a weight percentage) is less than 10%. When the glass layer used as a cover layer is applied to a flexible display module, it has little impact on the brightness of the display screen and has a good display effect.

[0106] It should be noted that, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions. Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions. Unless otherwise specified, the components involved or their preferred components can be combined to form new technical solutions. In this application, unless otherwise specified, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "6~22" means that all real numbers between "6~22" have been listed herein, and "6~22" is merely an abbreviation of these numerical combinations. In this application, unless otherwise specified, the formula "a≤b" means: a is less than b, or a equals b; the formula "a≥b" means: a is greater than b, or a equals b. The "range" disclosed in this application can be in the form of a lower limit and an upper limit, and may be one or more lower limits and one or more upper limits, respectively. In this application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reactions or operation steps herein are performed sequentially.

[0107] The above are merely specific embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A type of glass, characterized in that, The glass, expressed as a molar percentage, comprises: 40%-70% SiO2, 7.5%-36% Al2O3, 0-11% B2O3+P2O5, 1%-10% MgO, 1%-8% CaO, 0.5%-7% Li2O, 2%-13% Na2O+K2O, 0-5% TiO2, 0-3% ZrO2, 0-10% La2O3, and 0-1.5% clarifying agent; 0.4≤HE / LE≤0.8; in, HE=(Al2O3+B2O3+MgO+CaO+ZrO2+TiO2+La2O3+Li2O); LE = (SiO2 + Na2O + K2O); (Li₂O+Na₂O+K₂O)≤15%, 45%≤(SiO2+P2O5+B2O3)≤70%.

2. The glass as described in claim 1, characterized in that, 0.5 ≤ HE / LE ≤ 0.7; or 0.6≤HE / LE≤0.

7.

3. The glass according to any one of claims 1-2, characterized in that, (Li₂O + Na₂O + K₂O) ≥ 5%.

4. The glass according to any one of claims 1-3, characterized in that, 7.5% ≤ Al2O3 ≤ 30%; 0.45≤LT / HT≤2.4; in, LT = (Li₂O + Na₂O + K₂O + B₂O₃); HT = (Al2O3 + ZrO2).

5. The glass as described in claim 4, characterized in that, 0.6 ≤ LT / HT ≤ 2.0; or 0.8 ≤ LT / HT ≤ 2.0; or 1.0 ≤ LT / HT ≤ 2.0; or 1.0≤LT / HT≤1.

8.

6. The glass according to any one of claims 1-5, characterized in that, (TiO2+ZrO2)≤5%.

7. The glass according to any one of claims 1-6, characterized in that, The glass, expressed as a mole percentage, further comprises at least one of ZnO, Sr2O3, BaO, Nb2O5, Na2SO4, or NaNO3; 0<(ZnO+Sr2O3+BaO+Nb2O5+Na2SO4+NaNO3)≤5%.

8. The glass according to any one of claims 1-7, characterized in that, The elastic modulus of the glass is greater than or equal to 90 GPa.

9. The glass according to any one of claims 1-8, characterized in that, The surface of the glass has a compression layer formed after ion exchange; The ion exchange includes at least one of Li-Na ion exchange, Na-K ion exchange, or Li-K ion exchange.

10. The glass as claimed in claim 9, characterized in that, The compressive stress of the compression layer is greater than or equal to 450 MPa.

11. The glass as claimed in claim 9 or 10, characterized in that, The depth of the compression layer is greater than or equal to 6 μm.

12. The glass as claimed in claim 11, characterized in that, The ratio of the depth of the compression layer to the thickness of the glass is 20%-23%.

13. The glass according to any one of claims 9-12, characterized in that, The glass has a Vickers hardness value of 200 gf greater than or equal to 600 kgf / mm². 2 .

14. The glass according to any one of claims 1-13, characterized in that, 420℃≤T 4.0 -T 11.5 ≤550℃; Among them, T 4.0 and T 11.5 These represent glass viscosities of 10 and 10, respectively. 4.0 dPa·s and 10 11.5 The temperature corresponding to dPa·s.

15. The glass as claimed in claim 14, characterized in that, 420℃≤T 4.0 -T 11.5 ≤490℃。 16. The glass as claimed in claim 14, characterized in that, 460℃≤T 4.0 -T 11.5 ≤550℃。 17. The glass according to any one of claims 1-16, characterized in that, The crystalline phase in the glass comprises less than 10% by weight.

18. The glass according to any one of claims 1-17, characterized in that, Within the wavelength range of 400nm-800nm, the optical transmittance of the glass is greater than or equal to 86%.

19. A protective film for protecting electronic devices, characterized in that, The protective film includes the glass as described in any one of claims 1-18.

20. An electronic device, characterized in that, include: The housing, comprising the glass as described in any one of claims 1-18; The circuit board is disposed within the housing.

21. A cover plate layer, characterized in that, The cover plate layer includes: A glass layer, comprising the glass as described in any one of claims 1-18; An adhesive layer, one side of which connects to the glass layer, and the other side is used to bond to the display panel.

22. A display module, characterized in that, include: Display components, including display panel and control circuitry; The cover plate layer as claimed in claim 21, wherein the cover plate layer is bonded to the display panel by the adhesive layer.

23. An electronic device, characterized in that, include: Frame; The display module as described in claim 22 is fixed to the frame.

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