Ion-exchangeable glass with low Al2O3 content for display devices

Abstract

This disclosure relates to glass having a low Al2O3 content and glass articles manufactured from glass. The glass articles include flat glass suitable for use in display devices, such as those for electronic devices including smartphones, smartwatches, and tablet computers, particularly in foldable display devices. Methods for manufacturing glass articles are also described.

Description

[Technical Field]

[0001] This disclosure relates to glass having a low Al2O3 content and glass articles manufactured from glass. The glass articles include flat glass suitable for use in display devices, such as those for electronic devices including smartphones, smartwatches, and tablet computers, particularly in foldable display devices. Methods for manufacturing glass articles are also described.

[0002] background Display devices such as smartphones and tablet computers, especially foldable displays, are becoming increasingly popular. Foldable devices combine the advantages of a large screen when unfolded with a portable size when folded. In order to use glass panels in such foldable displays, the glass panels must be extremely thin. Extremely thin glass is fragile. Nevertheless, such glass must be strong enough to withstand repeated folding and unfolding operations.

[0003] Typically, aluminosilicate glass has been used in portable electronic devices. Aluminosilicate glass possesses certain properties that make it well-suited for use as display glass, particularly in the case of display cover glass that needs to be flexible or foldable and have a thickness of less than 100 μm. However, in aluminosilicate glass, compressive stress decreases as the thickness decreases. In addition, methods to further increase the impact resistance of alkali aluminosilicate often increase the tendency to devitrify during production, reducing yield. Therefore, a solution must be found to increase compressive stress even in thin glass while maintaining devitrification stability. Furthermore, since the glass surface of a touchscreen may be exposed to the acidic conditions of the user's skin, it would be advantageous if such new glass also possessed improved acid resistance.

[0004] Having glass that overcomes the shortcomings of prior art would be advantageous.

[0005] Summary of this disclosure In the first embodiment, this disclosure includes the following components: i.SiO2, ii. Al2O3 in an amount of 0.0 to 6.0% by weight, ii. At least 8.0% by weight of ZrO2, iii. At least 12.0% by weight of Na2O, iv. 0.0~5.0% by weight of B2O3 v. 0.0~5.0 wt% Li2O, vi. 0.0~10.0% by weight of K2O, vii. Optionally, one or more components selected from P2O5 and TiO2. Including, relating to glass.

[0006] In a second embodiment, the present disclosure relates to the following components in weight %: [Table 1] Includes, optionally, dyes or colorants such as Fe2O3, CoO, and / or Cr2O3. Including, relating to glass.

[0007] The inventors have found that the glass according to the first and second embodiments provides a novel combination of desirable properties. Prior art glass has been found to have insufficient devitrification stability and impact resistance, even after chemical strengthening. Therefore, the glass of this disclosure was developed to improve impact resistance while maintaining devitrification stability.

[0008] In this disclosure, an improved packing density is achieved by significantly reducing the Al2O3 content and significantly increasing the ZrO2 content. Zirconium is octahedral coordinated in the glass network, and therefore the packing density is higher than in commonly used alkali aluminosilicates. When Al2O3 is limited to <5 wt%, high yield (devitrification stability) production is achieved. Furthermore, compared to commonly used aluminosilicates, alkali zirconium silicate has a working point (at least when viscosity is 104 Because the temperature (below dPa·s) is low, such glass can be produced at lower temperatures, thus protecting the environment and reducing energy costs.

[0009] Despite its relatively low Al2O3 content, glass exhibits a remarkably high susceptibility to chemical strengthening. This means that when glass is immersed in a salt bath for chemical hardening, it generates high compressive stress on its surface in a very short time. In some embodiments, this compressive stress susceptibility can reach as high as 800 MPa, or even 900 MPa, 1000 MPa, or 1100 MPa or more, with chemical hardening within 30 minutes. Despite this remarkable susceptibility to compressive stress, glass exhibits only ordinary thermal expansion, such as a thermal expansion coefficient of less than 9.8 ppm / K or even less than 9.0 ppm / K. This very ordinary thermal expansion allows for the production of articles with excellent dimensional properties. During the production of thin glass, for example in a down-draw process, the glass undergoes rapid cooling. Typically, the cooling rate is not exactly the same across all parts of the glass. This results in deflection within the glass article. Deflection is greater in articles made from glass with a higher thermal expansion coefficient. Because the glass of this disclosure has a low coefficient of thermal expansion, it is possible to produce glass articles with particularly small deflection.

[0010] Furthermore, the glass of this disclosure also possesses excellent chemical resistance, particularly acid resistance. Chemical resistance is extremely useful in glass for display applications. Prior art glass with considerable chemical strengthening properties typically has average or insufficient chemical resistance. In one embodiment, the acid resistance class of the glass may be Class 2 or higher, the alkali resistance class of the glass may be Class 2 or higher, and the hydrolysis resistance class of the glass may be at least Class 4 or higher.

[0011] In a third embodiment, the disclosure relates to glass articles comprising or comprising the glass described herein.

[0012] In a fourth aspect, the Disclosure relates to a glass article having a thickness of less than 1000 μm, comprising glass containing at least 40.0% by weight of SiO2, at least 12.0% by weight of Na2O, and ZrO2, wherein the ratio of the weight of ZrO2 to the sum of the weights of Al2O3 and B2O3 is at least 1.5, and the glass is subjected to a CSS of at least 700 MPa. 30μm It contains and / or 5.0 mg / dm 2 Acid resistance of less than 2.5 mg / dm 2 This relates to glass articles having acid resistance of less than 1.

[0013] In a fifth embodiment, the disclosure relates to a glass article comprising or consisting of the glass described herein, wherein one or both of the main surfaces comprises an ion-exchanged layer.

[0014] In a sixth embodiment, this disclosure relates to electronic equipment, including glass or glass articles as described herein.

[0015] In a seventh aspect, the Disclosure relates to a method for manufacturing glass or glass articles of the Disclosure.

[0016] Detailed explanation definition Coefficient of thermal expansion ( C oefficient of t Hermal e Coefficient of linear thermal expansion (CTE) is the mean coefficient of linear thermal expansion over a temperature range of 20°C to 300°C. It is determined according to DIN ISO 7991:1987.

[0017] Compressive stress susceptibility ( C oppressive s tress sUsceptibility (CSS), or "CSS score," is expressed in MPa units. It is the amount of compressive stress measured in a glass specimen under specific test conditions. For this test, the specimen may be in the form of a 200 μm or 30 μm thick plate. The specimen is subjected to ion exchange treatment in an alkaline nitrate bath (100%) for 30 minutes, where the chemical toughening time can be shortened to, for example, 15 minutes for thinner glass thicknesses (<35 μm). The temperature may be selected to obtain the highest chemical stress. The alkaline nitrate depends on the type of ion exchange treatment performed, i.e., which ions need to be exchanged. Optionally, the alkaline nitrate is KNO3 and the bath temperature is 440°C. The use of 200 μm or 30 μm thick specimens in plate form to determine the CSS does not imply a limitation to glass articles in plate form or even plates of that thickness. Rather, CSS is a property of the glass material measured in plates prepared from glass. While CSS is affected by the thermal history of glass, it is a characteristic of glass materials or articles. Notably, CSS is a characteristic of unstrengthened materials or articles, i.e., materials or articles that have not been treated by ion exchange. Different thicknesses are relevant to the CSS value, for example, the CSS of a 30 μm thick plate. 30μm It is shown as follows.

[0018] The "1000 MPa IOX time" is the ion exchange treatment time required for the glass to develop a compressive stress of at least 1000 MPa on its surface. The corresponding experiment is the same as the CSS measurement, namely, the specimen is a 200 μm thick glass plate immersed in an alkaline nitrate bath. The temperature may be selected to 380°C for the sodium nitrate bath and 440°C for the other alkaline nitrates. The "1000 MPa IOX time" is reached when the specimen has a compressive stress of at least 1000 MPa.

[0019] Compressive stress (CS) is the compression of the glass network induced after ion exchange in the surface layer of the glass. CS typically decreases from a maximum value at the surface of the glass layer (surface CS) towards the interior of the glass layer. As is customary in the art, all representations of CS in this disclosure relate to the maximum value at each surface. CS can be measured using commercially available testers such as the FSM6000LE (Orihara Manufacturing Co., Ltd.) or the SLP1000 (Orihara Corporation, Japan).

[0020] The layer depth (DoL) is the thickness of the layer at the surface of a glass article when CS is present, and is essentially the same as the thickness of the ion-exchanged layer. DoL can be measured by a waveguide mechanism using commercially available test equipment such as the FSM6000 (Lukeo Corporation, Tokyo, Japan).

[0021] "Diffusivity" (μm 2 D (in units of / h) is a material property of glass that represents the ability to form an ion-exchanged layer during chemical toughening / ion exchange. This property can be calculated by examining the depth of the ion-exchanged layer (in units of μm) after a certain ion exchange time (IET in units of hours). The higher the diffusivity, the deeper the DoL after a given ion exchange time. The corresponding formula is D = DoL 2 / (7.84 × IET). Unless otherwise indicated in this disclosure, all indications of D refer to chemical toughening with 100% alkaline nitrate for 30 minutes, where for thin glass thicknesses, the toughening time can be shortened to, for example, 15 minutes. The temperature may be selected to 380°C for sodium nitrate baths and 440°C for other alkaline nitrates. Alkali nitrates are nitrates of alkali metal ions having the following larger diameters compared to the most abundant alkali metal oxide in the glass composition: The diameters of alkali metal ions are Cs > K > Na > Li, and for example, if sodium is the most abundant alkali metal oxide in the glass, D refers to ion exchange with 100% KNO3 at 440°C for 30 minutes.

[0022] Internal tensile stress (CT): When CS is induced on one or both sides of the glass sheet, in order to balance the stress according to Newton's third law, tensile stress must be induced within the central region of the glass, which is called internal tensile stress. CT can be calculated from the measured CS and DoL.

[0023] As used herein, "surface roughness" is the average roughness R a with respect to, and is a measure of the texture of the surface. Generally, the amplitude parameter characterizes the surface based on the vertical deviation of the roughness profile from the mean line. R a is the arithmetic mean of the absolute values of these vertical deviations. It can be determined in accordance with DIN EN ISO 4287:2010-07.

[0024] Deflection is the difference between the maximum distance and the minimum distance from the reference plane to the midplane of a free glass article that is not fixed. Deflection can be measured as described in SEMI MF1390.

[0025] Total thickness variation ( t otal t hickness v ariation) (TTV) is the difference between the maximum thickness and the minimum thickness of a glass article. It can be measured as described in SEMI MF1530.

[0026] "Hydrolysis resistance" relates to the extracted Na2O equivalent. It is determined in accordance with ISO 719:2020-09. It is a measure of the extractability of basic compounds from the glass in water at 98°C. The result of the measurement is the extracted Na2O equivalent in μg per gram of glass.

[0027] "Alkali resistance" relates to the resistance of the glass to alkaline attack. It is determined in accordance with ISO 695:1991-05 using a boiling aqueous solution of sodium carbonate and sodium hydroxide. The test is carried out as described in Section 6.2, "Glass as a Material". The result is mg / dm2 This represents the mass loss per unit surface area of ​​a glass sample.

[0028] "Acid resistance" refers to the glass's resistance to acid attack. It is determined according to DIN 12116:2001-03 using a boiling aqueous solution of hydrochloric acid. The test is carried out as described in Section 6.3, "Glass as a Material." The results are expressed in mg / dm 2 This represents the mass loss per unit surface area of ​​a glass sample.

[0029] "T4" has glass 10 4 This is the temperature at which the viscosity is dPa·s. T4 can be measured by methods known to those skilled in the art for determining the viscosity of glass, for example, according to ISO 7884-2:1987-12. 13 "The glass is 10 13 This is the temperature at which the viscosity is dPa·s. Similarly, T n Other temperatures shown as glass are 10 n This refers to the temperature at which a glass has a viscosity of dPa·s. For example, "T5" means that the glass is 10°C. 5 This is the temperature at which a viscosity of dPa·s is present. "Strain point" (T 14,5 Viscosity η is defined as the temperature at which all movement of glass molecules can no longer introduce any further strain into the high-temperature glass. 14.5 This is the viscosity fixed point (temperature value) in dPa·s. This limit value represents the maximum operating temperature of the glass component. g This is the transition temperature according to ISO 7884-8:1987.

[0030] Three-point bending strength is a test of the bending strength of a material. It may be determined using the method described in ASTM C1161-13. An example test setup is as follows: cylindrical steel bearing with radius 2 mm; support span 16 mm; size 28 × 28 × 0.2 mm 3 Test specimen; prepared according to standard procedure 7.2.4; loading rate of 5 mm / min.

[0031] Vickers hardness was determined using a standard Vickers indenter specified in ASTM C 1327 (2015). The following parameter was used: Force F n (Max) = 1N; Approach speed = 4μm / min; Loading speed 2N / min; Holding time 20 seconds; Release speed 6N / min.

[0032] Typically, the Vogel-Fulcher-Tammann (VFT) formula is used to calculate the temperature required to achieve a certain viscosity of glass (see ISO 7884 series standards, e.g., ISO 7884-1:1987-12, 7884-2:1987-12; 7884-3:1987-12; 7884-4:1987-12): lgη = A + {B / (T-T0)} In the VFT formula, η is viscosity, A and B are material parameters, T is temperature, and T0 is the Vogel temperature. A, B, and T0 are constant for any given glass. The representation of these constants provides further detailed information about the viscosity behavior of a particular glass composition.

[0033] The "primary surfaces" of an article are the two surfaces that have the largest surface area among all the surfaces of the article.

[0034] Where it is stated in this disclosure that glass is “component-free” or that glass is free of a particular component, this means that the component may only be present as an impurity in the glass. This means that the component is not added in substantial amounts. Substantial amounts are less than 3000 ppm (by weight), less than 2500 ppm (by weight), less than 2000 ppm (by weight), less than 1500 ppm (by weight), less than 1250 ppm (by weight), and in particular less than 750 ppm (by weight) or less than 500 ppm (by weight).

[0035] The terms "chemical toughening" and "chemical strengthening" are used interchangeably below.

[0036] Compositional characteristics Within the composition matrix of this disclosure, the disclosed compositions, ratios, and total contents have been found to achieve improved susceptibility to chemical strengthening and good chemical resistance (particularly acid resistance) while maintaining devitrification resistance. Optionally, the glass compositions disclosed herein may consist essentially of the listed oxides, i.e., may contain no other components not described herein.

[0037] In one embodiment, the glass is composed of the following components: i.SiO2, ii. Al2O3 in an amount of 0.0 to 6.0% by weight, ii. At least 8.0% by weight of ZrO2, iii. At least 12.0% by weight of Na2O, iv. 0.0~5.0% by weight of B2O3 v. 0.0~5.0 wt% Li2O, vi. 0.0~10.0% by weight of K2O, vii. Optionally, one or more components selected from P2O5 and TiO2. Includes.

[0038] Optionally, glass may consist of the following components by weight: [Table 2] It includes, optionally, dyes or colorants such as Fe2O3, CoO, and / or Cr2O3.

[0039] To achieve the desired CSS, devitrification, and acid resistance properties, it was found that ZrO2 may be present in an amount of at least 8.0 wt%, and Al2O3 should be kept below 6.0 wt%.

[0040] In one embodiment, the glass is [Table 3] Includes.

[0041] In one embodiment, the ratio of the amount of ZrO2 to the amount of Al2O3 by weight is at least 1.5. In yet another embodiment, the ratio may be at least 2, at least 3, at least 4, at least 5, at least 10, at least 20, at least 30, at least 50, at least 65, at least 75, at least 100, at least 125, or even at least 130. Optionally, this ratio may be up to 200, up to 180, up to 150, up to 125, up to 110, or up to 75. For example, this ratio may be 1.5–200, 2–150, 5–145, 10–135. This ratio may also include glasses that are substantially Al2O3-free, i.e., contain only Al2O3 impurities, or contain no Al2O3 at all, where the ratio tends towards infinity.

[0042] In one embodiment, the ratio of Al2O3 to ZrO2 by weight is less than 0.5, less than 0.25, less than 0.20, less than 0.15, less than 0.10, less than 0.05, less than 0.025, or even less than 0.015. Optionally, this ratio may be at least 0.001, at least 0.0025, at least 0.005, or at least 0.0065. For example, this ratio may be 0.001 to 0.5, 0.0025 to 0.2, 0.005 to 0.1, or 0.0065 to 0.025. This ratio may also include glasses that are substantially Al2O3-free, i.e., contain only Al2O3 impurities, or contain no Al2O3 at all, where the ratio tends towards 0.0.

[0043] In certain embodiments, the combined content of Al2O3 and ZrO2 is 8.0% to 35.0% by weight, 10.0% to 33.0% by weight, or 12.0% to 29.0% by weight. However, high proportions of both components increase the tendency to devitrify, and therefore the glass cannot be manufactured using the downdraw method. Thus, the disclosed glass may have a very low Al2O3 content or may not contain Al2O3 at all, and therefore a higher proportion of ZrO2 can be dissolved in the glass.

[0044] The glass of this disclosure may contain ZrO2, Al2O3, and B2O3. Therefore, when B2O3 is also present, the ratio of the weight of ZrO2 to the combined weight of Al2O3 and B2O3 may be at least 1.5. In yet another embodiment, the ratio may be at least 2, at least 3, at least 4, or even at least 5. Optionally, the ratio of the weight of ZrO2 in weight percent to the combined weight percent of Al2O3 and B2O3 is between 1.50 and 200.00, such as 2.00 to 180, 2.50 to 155, 3.65 to 145, or 4.75 to 135. In embodiments, this ratio is at least 1.50, at least 2.00, at least 3.50, at least 4.65, or at least 5.00. This ratio may be up to 200.00, up to 180.00, up to 150.00, up to 125.00, up to 110.00, or up to 75.00. This ratio may also include glasses that are substantially free of Al2O3 and / or B2O3, i.e., contain only Al2O3 and / or B2O3 impurities, or contain no Al2O3 and / or B2O3 at all, where the ratio tends to approach infinity.

[0045] It should be noted that conventional ZrO2-rich glass in the prior art requires a clarification step with As2O3 and / or Sb2O3, which is harmful to the environment and health. The disclosed glass can be produced without using As2O3 and / or Sb2O3 and still maintain high quality. Clarification of the disclosed glass can be carried out using CeO2, SnO2, Cl, or SO3, or any combination thereof. In one embodiment, the glass may not require clarification with a clarifying agent. Therefore, in one embodiment, clarification is carried out without using harmful substances such as As2O3 and / or Sb2O3, and therefore, in one embodiment, the glass composition is As2O3 and / or Sb2O3-free. In this case, the term "As2O3 and / or Sb2O3-free" refers to amounts of 100 ppm by weight or less, 50 ppm by weight or less, 25 ppm by weight or less, 20 ppm by weight or less, 10 ppm by weight or less, 5 ppm by weight or less, or even 1 ppm by weight or less.

[0046] In some embodiments, the glass does not contain Li2O. High Li2O content leads to increased raw material costs, which can be avoided by the disclosed glass.

[0047] In this disclosure, alkali metal oxides R2O include oxides of lithium, sodium, potassium, and cesium. In some embodiments, the glass does not contain lithium, potassium, and / or cesium. Alkaline earth metal oxides R'O include oxides of magnesium, calcium, strontium, and barium. In some embodiments, the glass does not contain magnesium, calcium, cesium, strontium, and / or barium.

[0048] In the following, R2O is the total amount of alkali metal oxides, and R'O is the total amount of all alkaline earth metal oxides. In some embodiments, the glass has a total amount of alkali metal oxides (R2O), alkaline earth metal oxides (R'O), and ZnO of 35.0% by weight or less, 34.0% by weight or less, or 33.75% by weight or less. Optionally, this total R2O + R'O + ZnO is at least 19.0% by weight, at least 20.0% by weight, or at least 21.0% by weight. For example, the total R2O + R'O + ZnO is 19.0–35.0% by weight, 20.0–34.0% by weight, or 21.0–33.75% by weight.

[0049] In the embodiment, the glass has a total amount of alkaline earth metal oxide (R'O) and ZnO of 12.5% ​​by weight or less, 12.0% by weight or less, 11.5% by weight or less, 11.0% by weight or less, 10.5% by weight or less, 10.0% by weight or less, 9.5% by weight or less, 9.0% by weight or less, 8.5% by weight or less, or 8.25% by weight or less. Optionally, this total R'O + ZnO is at least 0.1% by weight, at least 0.5% by weight, at least 0.75% by weight, at least 1.0% by weight, or at least 1.9% by weight. For example, the total R'O + ZnO is 0-12.5 wt%, 0-11.5 wt%, 0-10.5 wt%, 0-9.5 wt%, 0-8.5 wt%, 0.1-11.0 wt%, 0.5-10.0 wt%, 1.0-9.0 wt%, 1.5-8.5 wt%, or 1.9-8.25 wt%.

[0050] The glass may contain one or more alkali metal oxides (R2O). Optionally, the ratio of the second most abundant alkali metal oxide B to the most abundant alkali metal oxide A, in weight percent, is less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. The “most abundant” alkali metal oxide is the one that has the highest proportion in the glass based on weight percent. Thus, the “second most abundant” is the one that has the second highest proportion based on weight percent, etc. In one embodiment, A is Na2O and B is K2O, and in an alternative embodiment, B is Na2O and A is K2O. In certain embodiments, this ratio may be as low as 0.10 or less, 0.05 or less, or even 0.04 or less. In some cases, this ratio may be 0.

[0051] In some embodiments, the glass composition has a ratio of the weight of K2O to the total weight of Li2O and Na2O of less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. In certain embodiments, this ratio may be as low as 0.10 or less, 0.05 or less, or even 0.04 or less. In some cases, this ratio may be 0.

[0052] In alternative embodiments, the glass has a ratio of the weight of Na2O to the total weight of Li2O and K2O of less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. In certain embodiments, this ratio may be as low as 0.10 or less, 0.05 or less, or even 0.04 or less. In some cases, this ratio may be 0.

[0053] In one embodiment, the glass has a ratio of the weight of SiO2 to the sum of the weights of Li2O and Na2O of less than 4.5, optionally less than 4.25, or less than 4.0. Optionally, this ratio may be at least 2.0, at least 2.5, or at least 3.0. For example, this ratio may be in the range of 2.0–4.5, 3.0–4.25, or 3.0–4.0. The inventors have found that this ratio has a positive effect on the thermal expansion and CSS properties of the glass.

[0054] The glass contains, optionally, at least 40.0 wt%, at least 41.0 wt%, at least 43 wt%, at least 45 wt%, or at least 48 wt% of SiO2. In embodiments, the SiO2 content is up to 70.0 wt%, up to 68.0 wt%, up to 66.0 wt%, or up to 64.0 wt%. In specific embodiments, the relative amount of this component is 40.0–70.0 wt%, 41.0–68.0 wt%, 43.0–66.0 wt%, or 48.0–65.0 wt%. SiO2 helps achieve the desired thermal expansion behavior and chemical resistance properties. If the SiO2 content is too high, the viscosity increases, and the melting and high-temperature molding temperatures rise. Furthermore, SiO2 reduces ion exchangeability, which in turn reduces compressive stress on the surface.

[0055] Using a low amount of Al2O3 can help achieve the desired acid resistance. However, an excessive Al2O3 content in the disclosed glass will lead to devitrification. Therefore, optionally, the amount of this component is at least 0.1 wt%, at least 0.25 wt%, at least 0.5 wt%, at least 0.75 wt%, at least 1.25 wt%, at least 1.5 wt%, at least 1.75 wt%, or at least 1.8 wt%. In embodiments, the Al2O3 content may be limited to a maximum of 5.0 wt%, a maximum of 4.5 wt%, a maximum of 4.0 wt%, a maximum of 3.5 wt%, a maximum of 3.0 wt%, a maximum of 2.5 wt%, or a maximum of 2.0 wt%. For example, the content of this oxide may be in the range of 0.1-5.0 wt%, 0.25-4.5 wt%, 0.5-4.0 wt%, 0.75-3.5 wt%, 1.0-3.0 wt%, 1.25-2.5 wt%, or 1.5-2.0 wt%. However, Al2O3 contributes to a decrease in the acid resistance of the glass and increases its viscosity. In addition, glass melts with high Al2O3 and high ZrO2 content tend to devitrify, and therefore, Al2O3 amounts exceeding 6.0 wt% should be avoided. In some embodiments, the glass may not contain Al2O3.

[0056] The glass may contain B2O3 in proportions of up to 5.0 wt%, up to 4.5 wt%, or up to 3.0 wt%. In some embodiments, the content of this component is as low as 0.75 wt% or less, 0.5 wt% or less, or even 0.25 wt% or less. Some embodiments contain less than 0.1 wt% of B2O3. Where present, B2O3 helps to balance any devitrification tendency that may result from the use of ZrO2. Optionally, the B2O3 content is in the range of 0–5.0 wt%, 0–4.5 wt%, or 0–3.0 wt%. In some embodiments, B2O3 is used in amounts of at least 0.25 wt%, or at least 0.5 wt%. However, too high a proportion of B2O3 impairs chemical toughening performance, especially with short incubation times, and therefore amounts of B2O3 exceeding 5.0 wt% should be avoided. In some embodiments, the glass does not need to contain B2O3.

[0057] The glass may contain a total amount of Al2O3 and / or B2O3 in the range of 0.0 to 10.0 wt%, provided that the ratio of the weight of ZrO2 to the combined weight of Al2O3 and B2O3 is at least 1.5. Optionally, the glass may contain a total amount of Al2O3 and / or B2O3 in the range of 0.0 to 9.5 wt%, 0.0 to 9.0 wt%, or 0.0 to 8.5 wt%, provided that the ratio of the weight of ZrO2 to the combined weight of Al2O3 and B2O3 is at least 1.5. In some embodiments, the combined content of Al2O3 and B2O3 is less than 9.5 wt%, less than 9.0 wt%, less than 8.5 wt%, less than 8.0 wt%, or less than 7.0 wt%. Optionally, the total content of Al2O3 and B2O3 is at least 0.5% by weight, at least 0.75% by weight, at least 1.0% by weight, at least 1.25% by weight, or at least 1.5% by weight. In some embodiments, the glass may not contain Al2O3 and B2O3.

[0058] P2O5 is an optional component. It may be used in amounts of at least 0.015% by weight, at least 0.02% by weight, at least 0.025% by weight, or at least 0.03% by weight. Suitable upper limits are 10.0% by weight, 8.0% by weight, 6.0% by weight, 5.0% by weight, 4.0% by weight, and 3.5% by weight. Optionally, P2O5 may be used in the ranges of 0–10.0% by weight, 0.02–8.0% by weight, 0.025–5.0% by weight, or 0.03–3.5% by weight.

[0059] Some embodiments include TiO2 as the glass component. It may be used in amounts of 0.0-5.0% by weight, 0.0-4.0% by weight, 0.0-3.0% by weight, 0.0-2.0% by weight, 0.0-1.5% by weight, 0.0-1.0% by weight, or less than 100 ppm.

[0060] ZrO2 is an important component in the glass composition. To achieve the desired resistance to devitrification, it has been found that ZrO2 should be present in an amount of at least 8.0% by weight, and Al2O3 should be kept below 6.0% by weight. Preferably, the amount of ZrO2 is at least 8.0% by weight, at least 9.5% by weight, at least 10.0% by weight, at least 10.5% by weight, or at least 11.0% by weight. In some embodiments, the amount of ZrO2 may be at least 8.1% by weight, at least 8.5% by weight, at least 8.8% by weight, at least 9.2% by weight, or at least 9.5% by weight. In embodiments, the amount of this component ranges up to 32.0% by weight, or up to 30% by weight. Optionally, the ZrO2 content in the glass may be in the range of 8.0–32.0 wt%, 9.5–32.0 wt%, 10.0–30.0 wt%, 10.5–20.0 wt%, 11.0–17.5 wt%, 8.1–28.0 wt%, 8.5–24.0 wt%, 8.8–23.5 wt%, or 9.5–22.5 wt%. In some embodiments, the amount of ZrO2 is at least 8.5 wt%, at least 8.7 wt%, or at least 9.0 wt%. In certain embodiments, the amount of ZrO2 may be at least 8.0 wt%, at least 9.0 wt%, or >10.0 wt%, for example, at least 10.1 wt%. Thus, in some embodiments, the amount of ZrO2 may be in the range of 8.0 wt% to 30.0 wt%. ZrO2 is an essential component that increases compressive stress on the surface after ion exchange by increasing packing density. This further improves chemical resistance and reduces CTE. However, it has been found that if the ZrO2 level is too high, mellowness deteriorates, devitrification and phase separation occur, and yields decrease.

[0061] In some embodiments, Y2O3 may be present in the glass composition. The amount of Y2O3 may be at least 5.0% by weight, at least 6.0% by weight, at least 7.0% by weight, or at least 8.5% by weight. In embodiments, the amount of this component is in the range of up to 20.0% by weight, up to 15.0% by weight, up to 10.0% by weight, or up to 5.0% by weight. Optionally, the Y2O3 content in the glass may be in the range of 0.0 to 20.0% by weight, 0.0 to 15.0% by weight, 0.0 to 10.0% by weight, or 0.0 to 5.0% by weight. In some embodiments, the glass may not contain Y2O3.

[0062] In certain embodiments, the ratio of the content of (a) ZrO2 by weight to the content of (b) SiO2 by weight is 0.10–0.75, 0.15–0.70, or 0.19–0.65. In some embodiments, this ratio is at least 0.08, at least 0.10, at least 0.15, or at least 0.19. This ratio may be in the range of up to 0.70, up to 0.68, up to 0.65, up to 0.625, or up to 0.62.

[0063] Optionally, the glass contains alkali metal oxides. The total amount of alkali metal oxides R2O may be 10.0–30.0% by weight. Optionally, this amount may be up to 25.0% by weight, up to 23.0% by weight, up to 22.0% by weight, up to 21.0% by weight, or up to 20.5% by weight. A certain amount of alkali metal oxide may be necessary for sufficient CSS properties. Therefore, the minimum amount may be 10.0% by weight, 11.0% by weight, 12.0% by weight, or even 13.0% by weight. For example, the amount of R2O may be in the range of 10.0–25.0% by weight, 11.0–24.0% by weight, 11.0–23.0% by weight, or 12.0–22.0% by weight. In certain embodiments, the total content of all alkali metal oxides R2O is less than 20.5% by weight, less than 20.25% by weight, or less than 20.15% by weight.

[0064] Optionally, the ratio of the total content of all alkali metal oxides R2O in weight percent to the content of SiO2 in weight percent (b) is 0.1 or < 0.4, 0.15 or < 0.39, 0.2 or < 0.38, or 0.25 or < 0.37.

[0065] In some embodiments, the most abundant alkali metal oxide in the glass composition is Na2O, the second most abundant alkali metal oxide is K2O in some embodiments and Li2O in others, if present, and the third most abundant alkali metal oxide is Li2O in some embodiments and K2O in others, if present. Alternatively, the most abundant alkali metal oxide may be K2O, the second most abundant alkali metal oxide may be Na2O if present, and the third most abundant alkali metal oxide may be Li2O if present. In some embodiments, Li2O is not the most abundant alkali metal oxide. Optionally, either Na2O or K2O is the most abundant alkali metal oxide. For example, Li2O may not be more abundant than Na2O and / or more abundant than K2O. Na2O is an important component that acts as a networking agent, ensuring high compressive stress after ion exchange. It further lowers the melting and high-temperature molding temperatures. However, if the Na2O content is too high, hydrolysis resistance will be dramatically reduced.

[0066] Li2O may be present in the glass in amounts of up to 5.0 wt%, up to 3.0 wt%, up to 2.5 wt%, up to 2.25 wt%, up to 2.1 wt%, up to 1.5 wt%, up to 1.0 wt%, up to 0.5 wt%, up to 0.2 wt%, or up to 0.1 wt%. High Li2O content increases the cost of raw materials due to the increasing demand for Li2O for battery production; therefore, Li2O should be kept low, and Li2O exceeding 5.0 wt% should be avoided. In some embodiments, the glass may not contain Li2O at all.

[0067] K2O may be present in the glass in amounts of up to 7.0% by weight, up to 6.0% by weight, or up to 5.0% by weight. In some embodiments, the K2O content may be at least 4.0% by weight, or at least 3.0% by weight. In some embodiments, the glass composition contains K2O in amounts of 5.0% by weight or less, 4.5% by weight or less, 4.0% by weight or less, 3.5% by weight or less, 3.0% by weight or less, 2.8% by weight or less, 2.5% by weight or less, 2.0% by weight or less, or 1.5% by weight or less. Alternatively, it may be used in amounts of at least 1.0% by weight, at least 2.0% by weight, or at least 3.0% by weight. However, too much K2O in the glass will cause the mesh to open too much, reducing its susceptibility to chemical hardening, and therefore, K2O exceeding 10.0% by weight should be avoided. In some embodiments, the glass may not contain K2O at all.

[0068] Na2O may be present in the glass in amounts of up to 22.0% by weight, up to 20.0% by weight, or up to 19.0% by weight. In some embodiments, the Na2O content may be at least 14.0% by weight, or at least 15.0% by weight.

[0069] Optionally, the total amount of Na2O and / or K2O may be in the range of 10.0–22.0% by weight, 14.0–21.0% by weight, or 15.0–20.5% by weight.

[0070] One or more oxides selected from ZnO, Li2O, Na2O, K2O, MgO, CaO, SrO, BaO, and combinations thereof may be present in the glass in a total amount ranging from 10.0 to 40.0% by weight. In most embodiments, this total amount is less than 30.0% by weight, less than 25.0% by weight, or less than 22.0% by weight.

[0071] The amount of CaO in the glass may be, for example, up to 15.0 wt%, 13.5 wt%, 12.2 wt%, 6.0 wt%, 3.0 wt%, 0.5 wt%, 0.2 wt%, or 0.1 wt%. If the CaO content is too high, it may reduce the sensitivity to chemical strengthening, and therefore, amounts of CaO exceeding 15.0 wt% should be avoided. The glass may not even contain CaO.

[0072] The amount of SrO in the glass may be, for example, up to 10.0% by weight, up to 7.0% by weight, up to 6.0% by weight, up to 5.0% by weight, up to 1.0% by weight, up to 0.5% by weight, up to 0.2% by weight, or up to 0.1% by weight. The glass may not contain SrO at all.

[0073] The amount of BaO in the glass may be, for example, up to 10.0% by weight, up to 7.0% by weight, up to 5.0% by weight, up to 2.0% by weight, up to 1.0% by weight, up to 0.5% by weight, up to 0.2% by weight, or up to 0.1% by weight. The glass may not contain BaO at all.

[0074] The total amount of CaO, SrO, and BaO in the glass may be, for example, up to 20.0% by weight, up to 15.0% by weight, up to 13.0% by weight, up to 12.0% by weight, up to 11.0% by weight, up to 5.0% by weight, up to 2.0% by weight, or up to 1.0% by weight. In some embodiments, the glass may not contain CaO, SrO, and BaO.

[0075] The amount of ZnO in the glass may be in the range of 0.0 to 5.0 wt%, 0.0 to 4.0 wt%, 0.0 to 3.0 wt%, or 0.0 to 2.0 wt%. Some embodiments contain less than 100 ppm of ZnO. In certain embodiments, the amount of ZnO may be in the range of 0.5 to 5.0 wt%, or 1.0 to 4.0 wt%. In some embodiments, the glass may not contain ZnO at all.

[0076] The total amount of ZnO added to the alkaline earth metal oxide may be 0-15.0% by weight, 0.0-10.0% by weight, 0.0-9.0% by weight, or 0.0-8.0% by weight, or 0.0-7.0% by weight, or 0.0-5.0% by weight.

[0077] Optionally, the amount of alkaline earth metal oxide R'O is less than 10.0% by weight, less than 6.0% by weight, less than 4.0% by weight, or less than 2.0% by weight. Alternatively, it may be used in proportions of at least 1.0% by weight, at least 2.0% by weight, or at least 3.0% by weight.

[0078] In one embodiment, the ratio of the total content of all alkaline earth metal oxides R'O in weight percent to the content of SiO2 in weight percent (b) is 0.00 to <0.06, 0.01 to <0.3, <0.2, <0.1, <0.05, or <0.025. Optionally, this ratio may be >0.01, >0.02, or >0.03. For example, this ratio may be >0.01 to <0.3, or >0.02 to <0.2.

[0079] In some embodiments, the glass may contain MgO in amounts of 0.0–9.0 wt%, 0.1–8.5 wt%, or 0.5–8.0 wt%. Optionally, the amount of MgO is at least 0.1 wt%, at least 0.5 wt%, or at least 1.0 wt%, for example, at least 1.5 wt%, at least 2.0 wt%, or at least 3.0 wt%. MgO may be advantageous with respect to devitrification resistance. MgO also acts as a networking agent, improving meltability. It further increases packing density, thus improving compressive stress on the surface after ion exchange. However, if the MgO content is too high, devitrification may occur, particularly due to reactions with refractive materials. Furthermore, excessively high MgO content can lead to phase separation. However, in some embodiments, the glass does not contain MgO.

[0080] Optionally, the combined content of MgO and the second most abundant alkali metal oxide in weight percent is less than 10.0% by weight, less than 9.5% by weight, or less than 9.0% by weight. In some embodiments, MgO may be used in proportions of at least 1.5% by weight, at least 2.0% by weight, or at least 3.0% by weight. For example, the combined content of MgO and CaO may be at least 1.5% by weight, at least 5.0% by weight, at least 7.5% by weight, at least 15.0% by weight, or at least 20% by weight.

[0081] The optional glass of this disclosure comprises the following components in weight %,: [Table 4] Includes.

[0082] The optional glass of this disclosure comprises the following components in weight %,: [Table 5] Includes.

[0083] The optional glass of this disclosure comprises the following components in weight %,: [Table 6] Includes.

[0084] The optional glass of this disclosure comprises the following components in weight %,: [Table 7] Includes.

[0085] The optional glass of this disclosure comprises the following components in weight %,: [Table 8] Includes.

[0086] The optional glass of this disclosure comprises the following components in weight %,: [Table 9] Includes.

[0087] The optional boron-containing glass of this disclosure comprises the following components by weight %,: [Table 10] Includes.

[0088] The optional non-boron-containing glass of this disclosure comprises the following components by weight %,: [Table 11] Includes.

[0089] The optional Al2O3-containing glass of this disclosure comprises the following components by weight %,: [Table 12] Includes.

[0090] The optional low-Al2O3 glass of this disclosure comprises the following components by weight %: [Table 13] Includes.

[0091] The optional P2O5-containing glass of this disclosure comprises the following components by weight %,: [Table 14] Includes.

[0092] The optional glass of this disclosure having a relatively high amount of K2O contains the following components by weight: [Table 15] Includes.

[0093] The optional glass of this disclosure having a relatively high amount of ZrO2 contains the following components by weight: [Table 16] Includes.

[0094] The optional glass of this disclosure having a relatively high amount of CaO contains the following components by weight: [Table 17] Includes.

[0095] The optional glass of this disclosure having a relatively high amount of MgO contains the following components by weight: [Table 18] Includes.

[0096] Another optional glass of this disclosure having a relatively high ZrO2 content is composed of the following components by weight: [Table 19] Includes.

[0097] The glass may contain one or more fining agents such as CeO2, SnO2, Cl, and SO3. Fe2O3 may be used as a fining aid at an optional rate. Therefore, the glass may optionally contain Fe2O3. It is desirable to avoid the toxic fining agents arsenic and antimony, and therefore the total amount of arsenic and antimony may be less than 100 ppm. Due to toxicity concerns, the total amount of lead and bismuth may be less than 100 ppm. In embodiments, the glass may contain less than 1% by weight of F.

[0098] In one embodiment, the glass may contain coloring ions as dyes and / or colorants, such as iron, cobalt, chromium, copper, vanadium, nickel, manganese, neodymium, erbium, europium, molybdenum, or combinations thereof. They may be used in their various oxidation states.

[0099] In one embodiment, B2O3, K2O, MgO and / or CaO may be used to further improve the melting properties in this glass system.

[0100] parameters The coefficient of thermal expansion of glass is 9.8 × 10⁻⁶. -6 K -1 Less than 9.7 × 10 -6 K -1 Less than or 9.6 × 10 -6 K -1 It may be less than 10.0 × 10. In exceptional embodiments, the coefficient of thermal expansion is a maximum of 10.0 × 10. -6 K -1 , up to 9.5×10 -6 K -1 , or up to 9.2 × 10 -6 K -1 The coefficient of thermal expansion is, optionally, at least 7.0 × 10⁻⁶. -6 K -1 , at least 7.5 × 10 -6 K -1 , or at least 8.0 × 10 -6 K -1 , or at least 8.2 × 10 -6 K -1 In this embodiment, the thermal expansion coefficient of the glass is 7.0 × 10 -6 K -1 ~9.8×10 -6 K -1 , 7.5×10 -6 K -1 ~9.7×10 -6 K -1 , or 8.0×10 -6 K -1 ~9.6×10 -6 K -1 , or 8.2 × 10 -6 K -1 ~9.6×10 -6 K -1 This is within the range. In a particular embodiment, the coefficient of thermal expansion is 9.59 × 10 -6 K -1 Less than or 9.58 × 10 -6 K -1 It is less than.

[0101] The glass may have a Young's modulus of at least 74 GPa, at least 75 GPa, at least 76 GPa, or at least 77 GPa. Optionally, the Young's modulus is up to 90 GPa, up to 88 GPa, or up to 86 GPa. In embodiments, the Young's modulus of the glass is in the range of 74 GPa to 90 GPa, 75 GPa to 88 GPa, or 76 GPa to 86 GPa. In certain embodiments, the Young's modulus is at least 76 GPa or even more at least 77 GPa. The glass of this disclosure may have an excellent Young's modulus (in GPa units) between 70 and 90.

[0102] Generally, a higher Young's modulus increases the tensile stress at the glass surface when bent. This also reduces the tendency of glass articles to crease in the bent region. Higher compressive stress at the surface can offset the tensile stress when bent. The disclosed glass exhibits improved sensitivity to chemical strengthening, and therefore can have higher CSS and CS, and a higher Young's modulus. This has the advantage of significantly reducing the tendency for creases to form in the bent region of a display, particularly in the case of a foldable display cover. Therefore, in one embodiment, the disclosed glass is particularly suitable for a foldable display cover.

[0103] In one embodiment, the glass has a Poisson's ratio of 0.220–0.270, 0.225–0.265, or 0.230–0.260. Optionally, the Poisson's ratio may be less than 0.260, less than 0.259, or less than 0.258. In an embodiment, the Poisson's ratio is at least 0.220, at least 0.225, or at least 0.230.

[0104] Optionally, glass has a weight of 2.530-2.850 g / cm³. 3 , 2.580~2.830 g / cm³ 3 , or 2,600~2,780 g / cm³ 3 It has a density of at least 2.530 g / cm³. 3 at least 2.580 g / cm³ 3Or at least 2,600 g / cm³ 3 It may be so. In the embodiment, the density is a maximum of 2.850 g / cm³. 3 , up to 2.830g / cm 3 , up to 2.790g / cm 3 Or up to 2,780 g / cm³ 3 It will become.

[0105] In some embodiments, the glass has a packing density of 0.44–0.58, 0.48–0.56, or 0.50–0.54. The density may be at least 0.44, at least 0.48, or at least 0.50. In embodiments, the density may be up to 0.58, up to 0.56, up to 0.54, or up to 0.53.

[0106] In one embodiment, the glass has a glass transition temperature T of at least 545°C, at least 550°C, or at least 555°C. g It may have. In certain embodiments, T g The temperature may further be at least 560°C or at least 561°C, while certain embodiments may further exceed 565°C. g It may have a value. Optionally, T g The temperature may be less than 680°C or less than 675°C. In the embodiment, T g The range is 545°C to 680°C, 550°C to 675°C, or 553°C to 630°C. g This enables high temperatures during ion exchange processing. g Glass having this property allows stress induced by ion exchange at higher temperatures to be reduced to lower T g Glass with certain properties does not relax as much. Higher temperatures accelerate the ion exchange process, and therefore, ion exchange becomes more economical.

[0107] In some embodiments, the glass may have strain points at at least 500°C, at least 525°C, at least 540°C, at least 550°C, or at least 560°C. In certain embodiments, the strain point may further be at least 543°C or at least 573°C, while in certain embodiments, the strain point may further exceed 580°C. Optionally, the strain point may be less than 700°C or less than 675°C. In embodiments, the strain point is in the range of 500°C to 700°C, 525°C to 685°C, or 540°C to 675°C. A high strain point allows for higher temperatures during ion exchange processing. Glass with a high strain point does not relieve the stress induced by ion exchange at higher temperatures as much as glass with a lower strain point. Higher temperatures accelerate the ion exchange process, and therefore ion exchange becomes more economical.

[0108] Optionally, the glass composition is: Temperature T4 of at least 1065°C, at least 1075°C, at least 1080°C, at least 1085°C, at least 1095°C or at least 1100°C. Temperature T3 of at least 1180°C, at least 1200°C, at least 1225°C, at least 1250°C, at least 1310°C, or at least 1330°C. • VFT constant A < 0.00, optionally between -5.00 and -2.00. · >5,000℃, with an optional VFT constant B between 5,800℃ and 8,000℃, and VFT constant T0 for 140-450°C, e.g., 145-300°C, or up to 255°C. Show one or more of the following.

[0109] The glass of this disclosure may have a remarkably steep slope in its temperature-viscosity curve. The steepness of the curve is due to the difference between temperatures T4 and T4. 7.6 This can be quantified as the difference between two temperatures. For the glass of this disclosure, this difference may be at least 250K, at least 265K, at least 280K, or at least 285K. Optionally, this value may not exceed 380K, 360K, or 340K. For example, between temperatures T4 and T4. 7.6The difference between them may be in the range of 250-380K, 265-260K, or 280-340K.

[0110] All of these parameters describe the viscosity behavior of the glass. The glass of this disclosure has a considerably high characteristic temperature, allowing for the use of high temperatures during ion exchange, thereby accelerating the ion exchange process.

[0111] A key property of the glass disclosed herein is its ability to generate high compressive stress in a very short time. This property is quantified by a CSS score—or simply "CSS"—which is equivalent to the compressive stress formed in a test specimen. A further index used indicates the glass thickness used to measure the CSS. The glass compositions disclosed herein exhibit remarkable CSS values ​​at thin glass thicknesses.

[0112] Optionally, the glass of this disclosure may have a CSS of at least 800 MPa, at least 950 MPa, at least 1000 MPa, at least 1050 MPa, or even at least 1070 MPa. 200μm It possesses an extremely pronounced compressive stress sensitivity, which allows for the introduction of extremely high compressive stress into the glass in a short time. Optionally, CSS 200μm The range is up to 1700 MPa, up to 1500 MPa, or up to 1400 MPa. In the embodiment, CSS 200μm These ranges from 800 MPa to 1700 MPa, 1000 MPa to 1500 MPa, or 1050 MPa to 1400 MPa. Prior art glass compositions only reach such high compressive stresses after much longer ion exchange times. Often, prior art glass compositions will only reach a compressive stress of 1000 MPa after more than 4 hours of ion exchange, or not reach it at all.

[0113] Optionally, the glass of this disclosure may have a CSS of at least 600 MPa, at least 700 MPa, at least 800 MPa, at least 850 MPa, or even at least 900 MPa. 30μm It has. Optionally, CSS 30μmis in the range of up to 1200 MPa, up to 1100 MPa, or up to 1000 MPa. In an embodiment, the CSS 30μm is in the range of 600 MPa to 1200 MPa, 700 MPa to 1100 MPa, or 800 MPa to 1000 MPa. In one embodiment, the CSS 30μm score refers to the CSS 30μm . Prior art glass compositions do not reach such high compressive stresses at such thin thicknesses.

[0114] Another way to represent a notable property of this glass that accepts compressive stress is the 1000 MPa IOX time, i.e., the time of ion exchange treatment in an alkali nitrate bath required for a glass specimen to reach a compressive stress of 1000 MPa at its surface. Optionally, the 1000 MPa IOX time of the glass of the present disclosure is less than 60 minutes, less than 30 minutes or even less than 20 minutes. In one embodiment, the 1000 MPa IOX time refers to the IOX time in a potassium nitrate bath.

[0115] The notable ability of this glass to be chemically strengthened is further illustrated by reference to its diffusion rate. A high diffusion rate means that the glass can accept a compressive stress layer of sufficient depth within a short time, making the glass production process more economical. In certain embodiments, the glass of the present disclosure has a diffusion rate of at least 8 μm 2 / h, 10 μm 2 / h, 12 μm 2 / h, 14 μm 2 / h, or 16 μm 2 / h. Optionally, this value may be in the range of up to 45 μm 2 / h, 40 μm 2 / h, or 35 μm 2 / h. In certain embodiments, the diffusion rate is 8 - 45 μm 2 / h, 9 - 40 μm 2 / h, or 10 - 35 μm 2 / h.

[0116] The glass of the present disclosure (a) Hydrolysis tolerance values ​​of less than 320, or less than 300, or less than 280, or less than 250, or less than 225, or less than 210 μg / g sodium equivalent units; (b) mg / dm less than 25, or less than 22, or less than 20, or less than 18 2 Alkali resistance value per unit of weight loss; (c) mg / dm less than 5.0, or less than 2.5, or less than 2.0, or less than 1.0 2 Acid resistance value of weight loss units It may have chemical resistance characterized by one or more of the following.

[0117] Optionally, the hydrolysis resistance value in μg / g sodium equivalent units may be at least 15, at least 50, or at least 100. In one embodiment, mg / dm 2 The alkali resistance value of the weight loss unit is at least 1, at least 5, or at least 8. In further embodiments, mg / dm 2 The acid resistance value of the weight loss unit may be at least 0.1, at least 0.2, or at least 0.3.

[0118] The glass of this disclosure exhibits remarkable compressive stress susceptibility in MPa units to the total content of alkali metal oxides R2O and alkaline earth metal oxides R'O in weight percent of CSS 200μm This represents / ([R2O]+[R'O]). Prior art glasses require extremely large amounts of alkali metal oxides or alkaline earth metal oxides to achieve compressive stress during ion exchange. In contrast, the compositions described herein produce high compressive stress despite moderate proportions of alkali metals and alkaline earth metals. Optionally, CSS 200μm / ([R2O]+[R'O]) is at least 25, at least 30, at least 40, at least 50, or at least 60. In some embodiments, CSS 200μm / ([R2O]+[R'O]) is at least 70, at least 80, or at least 90. Optionally, CSS 200μm / ([R2O]+[R'O]) is in the range of a maximum of 100, a maximum of 75, or a maximum of 50. In some embodiments, CSS 200μm The value of / ([R2O]+[R'O]) is 25-100, 30-75, or 35-65. The units (MPa / weight%) of this parameter are not shown for readability.

[0119] In one embodiment, the disclosure provides a CSS in MPa for a coefficient of thermal expansion in ppm / K in a temperature range of 20 to 300°C. 200μm CSS 200μm The glass relates to glass whose CTE is at least 85, at least 100, at least 110, at least 120, or at least 130. Prior art glass compositions often have a CTE of 9.0 × 10 -6 K -1 It has the disadvantage of high thermal expansion exceeding [a certain value]. The glass composition disclosed herein has low CTE and high CSS 200μm For example, give CSS values ​​of 100-250, 110-220, or 120-200. 200μm It has / CTE. For example, CSS 200μm / CTE may be in the range of a maximum of 250, a maximum of 220, or a maximum of 200. The units of this parameter (MPa·K / ppm) are not shown for readability.

[0120] To limit reflectivity, the refractive index of the glass used in the display should not be too high. Optionally, the refractive index n of the glass of this disclosure d The refractive index is less than 1.600, less than 1.550, or even less than 1.540. In certain embodiments, the refractive index is in the range of 1.520 to 1.600, or 1.530 to 1.550.

[0121] In one embodiment, the glass is particularly (10 4 It does not devitrify at the working point (at a viscosity of dPa·s). This is useful because the glass can be produced by a downdraw process. In some embodiments, the glass can be produced by a downdraw process such as slot downdraw or overflow fusion downdraw. 10 4It is desirable that there is no devitrification at all at the working point of dPa·s. However, at slightly higher viscosities, especially 10 5 At a viscosity of dPa·s, a small crystal growth rate can be tolerated, 10 5 Glass with a viscosity of dPa·s and a crystal growth rate of 0.5 μm / min or less is generally suitable for production by downdraw.

[0122] Therefore, in this disclosure, the resistance to devitrification is 10 5 The crystal growth rate may be expressed in terms of the crystalline growth rate at a viscosity of dPa·s. A lower crystal growth rate results in higher resistance to devitrification and, consequently, higher yield. The measurement of the crystallization rate is well known. The crystallization rate is measured along the formed crystal, i.e., at its maximum elongation. In particular, the crystallization rate is determined when the glass is gradient annealed (e.g., using a gradient furnace).

[0123] The so-called lower devitrification temperature (LDT) is the temperature at which devitrification begins in the temperature rise method. Above the liquidus temperature (also called the upper devitrification temperature (UDT)), crystallization will not occur even after a long period of time. The LDT and UDT values ​​generally differ between different glasses. The terms "crystallization" and "devitrification" are used synonymously in this specification unless otherwise specified.

[0124] Crystallization occurs at temperatures above the lower devitrification temperature (LDT) and below the upper devitrification temperature (UDT), and ultimately within the range between the LDT and UDT. Generally, different temperatures are tested to determine the crystal growth rate at different viscosities. This also allows for the determination of the LDT and UDT, which represent the lower and upper limits, respectively, of the temperature range in which crystallization occurs.

[0125] The crystal growth rate may be determined by heat-treating the glass in a gradient furnace for 16 hours using the temperature rise method. A gradient furnace is a furnace that has different heating zones, and therefore different temperature zones. The temperature rise method means that the temperature of the glass is lower than the temperature of any zone in the furnace before it is placed in it. Therefore, the temperature of the glass rises as it is placed in the furnace, regardless of which zone of the furnace it is placed in. Thus, devitrification can be measured by heat-treating the glass for 16 hours in a (preheated) gradient furnace that has different temperature zones. Since a gradient furnace is divided into different temperature locations or zones, it is a location-based gradient, not a time-based gradient.

[0126] A furnace divided into several heating zones allows for simultaneous testing of different temperatures (and thus different viscosities). This is a particular advantage of gradient furnaces. The temperature should be chosen so that the crystallization rate can be determined at different temperatures (and thus different viscosities) within the range between LDT and UDT. If LDT and UDT are unknown, it is useful to test a relatively wide range of temperatures to enable their determination. For example, the lowest temperature in the gradient furnace may be chosen to be approximately 350K lower than the glassworking temperature (working point). The working point is 10 4 Corresponds to viscosity in dPa·s.

[0127] As mentioned above, 10 5 A crystal growth rate at a viscosity of dPa·s is appropriate in terms of productivity by the downdraw process. Optionally, since the glass of the present invention has extremely high devitrification resistance, the crystal growth rate is 10, especially when the glass is heat-treated in a gradient furnace for 16 hours using the temperature rise method. 5 The viscosity is dPa·s and the flow rate is up to 0.5 μm / min, up to 0.4 μm / min, up to 0.3 μm / min, up to 0.2 μm / min, up to 0.1 μm / min, up to 0.05 μm / min, up to 0.02 μm / min, or up to 0.01 μm / min. In one embodiment, devitrification is 10 5 It does not occur at all at a viscosity of dPa·s. Importantly, devitrification occurs at 10 5 If it does not occur at all with a viscosity of dPa·s, 105 The crystal growth rate at dPa·s cannot be determined. 10 5 The absence of devitrification at a viscosity of dPa·s can also be expressed as a crystal growth rate of 0 μm / min.

[0128] Optionally, the crystallization rate is determined using glass grains, particularly those with a diameter of approximately 2 mm to 3 mm. Such glass grains are placed on a carrier, such as a platinum carrier for gradient annealing. For example, the carrier may have recesses for receiving the glass grains and holes at the bottom of each recess, thus allowing for microscopic determination of the crystallization rate. In view of the size of the glass grains, the recesses may each have a diameter of 2 mm, and the holes may each have a diameter of 0.9 mm.

[0129] After heat treatment, it is possible to microscopically determine the temperature range (and consequently, the viscosity) at which crystal growth rates occurred. 10 5 The crystal growth rate at a viscosity of dPa·s is determined based on a known correlation between temperature and viscosity. Based on the glass composition, the corresponding viscosities at different temperatures are known. LDT and UDT may be determined as the lower and upper limits, respectively, of the temperature range in which crystallization occurs. Since the temperature at each position in the furnace during heat treatment and the position of each glass particle in the furnace are known, different glass particles can be easily assigned to different temperatures in a gradient furnace.

[0130] Strengtheningable articles The glass articles of this disclosure may have a thickness of less than 1000 μm, contain at least 40.0% by weight of SiO2, at least 12.0% by weight of Na2O, further containing ZrO2, with a ratio of at least 1.5 of the weight of ZrO2 to the sum of the weights of Al2O3 and B2O3, and have a CSS of at least 700 MPa. 30μm It contains and / or 5.0 mg / dm 2 Acid resistance of less than 2.5 mg / dm 2 Includes glass with acid resistance of less than 1.

[0131] The glass articles of this disclosure may have a thickness of 1000 μm or less and may include or consist of the glass described herein. Generally, articles may be called thin glass articles or glass plates. They may have a thickness of less than 850 μm, less than 500 μm, less than 300 μm, less than 200 μm, or less than 100 μm. In some embodiments, the thickness may be as thin as 80 μm or less, or 70 μm or less. Some articles have a thickness of 50 μm or less, or 40 μm or less. Such thin glass articles have the property of being bendable and / or foldable. For such flexible or foldable cover glass, the desired thickness may be less than 100 μm, less than 80 μm, less than 60 μm, or less than 40 μm. A minimum thickness will be required for the article to have sufficient impact resistance. The minimum thickness may be at least 5 μm, at least 10 μm, or at least 15 μm.

[0132] Thanks to its outstanding properties, including a low CTE and other desirable characteristics, glass articles can be manufactured with deflections of less than 3.0 mm, less than 2.0 mm, or less than 1.0 mm. Generally, glass articles can be manufactured by a stretching process, where temperature differences between different parts of the glass cause deflection. The glass of this disclosure has a low CTE and other desirable properties, such as good viscosity properties, so articles with small deflections can be obtained. In certain embodiments, the deflection is at least 5 μm, at least 10 μm, at least 100 μm, or at least 250 μm.

[0133] Optionally, the article may have a total thickness variation of less than 15 μm, less than 10 μm, less than 7 μm, or less than 5 μm. In some embodiments, the TTV may reach 1 μm to 10 μm. In some embodiments, the TTV is ±10.0%, ±5.0%, or ±3.0% of the glass article thickness.

[0134] The article must be at least 10 cm 2 at least 15cm 2 , or at least 20cm 2It may have an area of ​​10,000 cm². In this embodiment, the article has an area of ​​10,000 cm². 2 Less than 1000cm 2 Less than 200cm 2 It may have an area less than a certain value.

[0135] The article has a surface roughness R of 5.0 nm or less, 3.0 nm or less, or 1.5 nm or less on one or both of its main surfaces. a It may have such extremely low roughness. Such very low roughness can be obtained through the downdraw process.

[0136] The article may have significant chemical resistance on one or both of its main surfaces. Chemical resistance is, (a) Hydrolysis tolerance values ​​of less than 320, or less than 300, or less than 280, or less than 250, or less than 225, or less than 210 μg / g sodium equivalent units; (b) mg / dm less than 25, or less than 22, or less than 20, or less than 18 2 Alkali resistance value per unit of weight loss; (c) mg / dm less than 5.0, or less than 2.5, or less than 2.0, or less than 1.0 2 Acid resistance value of weight loss units It may be characterized as one or more of the following.

[0137] Glass articles may have a Vickers hardness of at least 580, at least 590, or at least 600. Optionally, the Vickers hardness may be in the range of 580–800, 590–700, or 600–630.

[0138] In one embodiment, the glass article has excellent three-point bending strength, exhibiting a three-point bending strength of at least 100 MPa, at least 200 MPa, or at least 300 MPa. It is noteworthy that such strength can be achieved without ion exchange strengthening. The strength of the article after ion exchange is even more noteworthy because it has such high strength from the outset. Optionally, the three-point bending strength may be in the range of 100 MPa to 600 MPa, 200 MPa to 500 MPa, or 300 MPa to 400 MPa.

[0139] Reinforced articles The glass article may include an ion-exchanged layer on one or both of its main surfaces. The ion-exchanged layer provides high strength to the glass article. Optionally, the article may have a compressive stress of at least 500 MPa, at least 600 MPa, at least 700 MPa, or at least 800 MPa on one or both of its main surfaces. In embodiments, the compressive stress may be in the range of up to 1800 MPa, up to 1600 MPa, up to 1500 MPa, or up to 1400 MPa. For example, the compressive stress may be in the range of 400 MPa to 1800 MPa, 700 MPa to 1600 MPa, or 800 MPa to 1400 MPa.

[0140] In one embodiment, the glass article has a thickness of 20 to 40 μm, for example, 25 to 35 μm, and has a compressive stress of at least 600 MPa, at least 700 MPa, at least 800 MPa, at least 850 MPa, or at least 900 MPa on one or both of its main surfaces.

[0141] Optionally, the glass article exhibits a DoL of 6–12 μm or 7–11 μm on one or both of its main surfaces. For example, the DoL may be at least 6 μm, at least 7 μm, or at least 8 μm. Alternatively or additionally, the DoL may be in the range of up to 15 μm, up to 13 μm, up to 12 μm, or up to 11 μm.

[0142] In one embodiment, DoL is 15–25% of the article thickness, or 16–20% of the article thickness. In another embodiment, DoL is at least 15% of the article thickness, at least 16%, or at least 17%. DoL may be up to 33%, up to 25%, or up to 20% of the article thickness. In this context, DoL refers to the depth of a single compressive stress layer. The total DoL of all compressive stress layers may be greater.

[0143] One of the remarkable properties of the articles of this disclosure is that extremely high compressive stress can be achieved even in thin articles. In embodiments, a glass article has a ratio of compressive stress in MPa units to article thickness in μm units of at least 4.0 MPa / μm, at least 5.0 MPa / μm, at least 6.0 MPa / μm, or at least 10.0 MPa / μm on one or both of its main surfaces. In embodiments, this value may reach up to 40.0 MPa / μm, up to 35.0 MPa / μm, or up to 30.0 MPa / μm. Optionally, the ratio of compressive stress in MPa units to article thickness in μm units is up to 10.0 MPa / μm, up to 8.0 MPa / μm, or up to 7.0 MPa / μm. In certain embodiments, the ratio of compressive stress in MPa units to article thickness in μm units is in the range of 4.0 MPa / μm to 40.0 MPa / μm, 5.0 MPa / μm to 35.0 MPa / μm, 5.0 MPa / μm to 30.0 MPa / μm, or 10.0 MPa / μm to 29.0 MPa / μm. In certain embodiments, this value is in the range of 20.0 MPa / μm to 30.0 MPa / μm. In some embodiments, the ratio of compressive stress in MPa units to article thickness is at least 20.0 MPa / μm, or at least 25.0 MPa / μm.

[0144] Optionally, the article may have a ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units on one or both of its main surfaces, at least 50 MPa / μm, at least 75 MPa / μm, or at least 90 MPa / μm. In some embodiments, this value is further at least 100 MPa / μm, at least 120 MPa / μm, or at least 140 MPa / μm. For example, the ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units may be in the range of 50–400 MPa / μm, 75–300 MPa / μm, or 90–200 MPa / μm. In certain embodiments, the ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units is up to 400 MPa / μm, up to 300 MPa / μm, or up to 200 MPa / μm.

[0145] In one embodiment, the disclosure relates to a glass article exhibiting a three-point bending strength of at least 400 MPa, at least 500 MPa, or at least 600 MPa.

[0146] In one embodiment, the glass article has excellent three-point bending strength, exhibiting a three-point bending strength of at least 400 MPa, at least 500 MPa, or at least 600 MPa. It is noteworthy that such strength can be achieved. Optionally, the three-point bending strength may be in the range of 400 MPa to 1200 MPa, 500 MPa to 1000 MPa, or 600 MPa to 800 MPa.

[0147] electronic equipment Glass and / or glass articles may be used in electronic devices, such as portable computers, smartphones, tablet computers, and other handheld or wearable devices. Glass and / or glass articles may be part of a display.

[0148] Therefore, the electronic devices described herein may include glass or glass articles described herein. The electronic devices may include a display, wherein the display includes glass and / or glass articles described herein. The glass articles may be cover glass of the electronic devices.

[0149] The electronic device may be a flexible and / or foldable device, such as a flexible and / or foldable smartphone or tablet computer.

[0150] Manufacturing method The glass may be produced by melting a batch of raw materials suitable for obtaining the composition of the present disclosure. For example, the glass may be melted in a platinum crucible. After melting, the glass molten material may be clarified using one or more clarifying agents to remove air bubbles. Instead of using chemical clarifying agents, physical clarification methods such as vacuum clarification may be used.

[0151] On an industrial scale, glass articles may be prepared by float or downdraw processes such as slot downdraw or overflow fusion downdraw. Slot downdraw is preferred because it allows for extremely thin thicknesses.

[0152] After molding, the articles may be strengthened by ion exchange (also known as "chemical strengthening"). Strengthening may involve immersing the articles in a bath of molten salt. The salt is selected based on the desired ion exchange process. In preferred embodiments, the salt is an alkaline salt, such as an alkaline nitrate. In specific embodiments, the salt bath contains potassium nitrate, optionally about 100% KNO3.

[0153] It is well known to those skilled in the art that glass articles can be chemically strengthened by ion exchange. The strengthening process may be carried out by immersing the glass article in a salt bath containing monovalent ions that exchange for alkali ions inside the glass. The monovalent ions in the salt bath are alkali ions inside the glass, for example, Na + , K + , and / or Cs+ It has a larger radius than . Due to the larger ions that penetrate the glass network, compressive stress is generated in the glass after ion exchange. After ion exchange, the strength of the glass is significantly improved. In addition, the CS induced by chemical strengthening improves the bending properties of the strengthened glass article and improves the scratch resistance of the glass article. Typical salts used for chemical strengthening are, for example, K + It contains molten salt or a mixture of salts. Optional salt baths for chemical hardening include Na + Contains and / or K + The solution is a molten salt bath containing or a mixture thereof. Optional salts include NaNO3, KNO3, CsNO3, NaCl, KCl, CsCl, Na2SO4, K2SO4, Cs2SO4, Na2CO3, K2CO3, Cs2CO3, and K2Si2O5. Additives such as NaOH, KOH, and other sodium or potassium salts are also used to better control the ion exchange rate for chemical strengthening. Ion exchange may be carried out in KNO3 at temperatures in the range of 300°C to 480°C or 340°C to 480°C, particularly 340°C to 450°C or 390°C to 450°C. Optionally, during ion exchange, the temperature of the salt bath is T g -400~T g -100℃, or T g -250~T g The temperature will be within the -150℃ range.

[0154] Chemical strengthening is not limited to a single step. It can involve multiple steps in one or more salt baths containing varying concentrations of alkali metal ions and / or different ions to achieve better toughening performance. Thus, chemically toughened glass articles can be toughened in one step or in several steps, for example, two steps. Two-step chemical toughening is particularly applicable to Li2O-containing glass, as lithium may be exchanged for both sodium and potassium ions.

[0155] The inventors have found that glass exhibits extremely rapid ion exchange and achieves high compressive stress in a short time. The immersion time of the article in the molten salt bath at the indicated temperature may be in the range of 20 minutes to 12 hours, 25 minutes to 4 hours, or 30 minutes to 2 hours. Optionally, the time is at least 20 minutes, at least 25 minutes, or at least 30 minutes. In some embodiments, the ion exchange time is 2 hours or less, or 1 hour or less.

[0156] In one embodiment, the method is • To obtain the glass according to this disclosure, the raw material batch may be melted as needed. • To form glass articles such as the glass articles described in this specification, • Strengthening articles through ion exchange treatment in an ion exchange bath. Includes.

[0157] Items of this disclosure Each of the following items represents a specific embodiment of the glass, glass articles, and other embodiments of the present disclosure described in detail above.

[0158] The first item is, i.SiO2, ii. Al2O3 in an amount of 0.0 to 6.0% by weight, ii. At least 8.0% by weight of ZrO2, iii. At least 12.0% by weight of Na2O, iv. 0.0~5.0% by weight of B2O3 v. 0.0~5.0 wt% Li2O, vi. 0.0~10.0% by weight of K2O, vii. Optionally, one or more components selected from P2O5 and TiO2. This relates to a glass composition that includes [a certain component].

[0159] The second item is the following components in weight %, [Table 20] Relates to a glass composition containing, optionally, a dye or colorant such as Fe2O3, CoO, and / or Cr2O3.

[0160] The third item is the following components in weight %:

Table 21

[0161] The fourth item is the following components in weight %:

Table 22

[0162] The fifth item is the following components in weight %:

Table 23

[0163] The sixth item is the following components in weight %:

Table 24

[0164] The seventh item is the following components in weight %:

Table 25

[0165] The eighth item is the following components in weight %:

Table 26

[0166] The ninth item is the following components in weight %:

Table 27

[0167] Item 10 is the following components by weight%:

Table 28

[0168] Item 11 is the following components by weight%:

Table 29

[0169] Item 12 is the following components by weight%:

Table 30

[0170] Item 13 is the following components by weight%:

Table 31

[0171] Item 14 is the following components by weight%:

Table 32

[0172] Item 15 is the following components by weight%:

Table 33

[0173] Item 16 is the following components by weight%:

Table 34

[0174] Item 17 consists of the following components in weight percent: [Table 35] This relates to glass containing a relatively large amount of MgO.

[0175] Item 18 consists of the following components in weight percent: [Table 36] This relates to glass containing a relatively large amount of ZrO2.

[0176] Item 19 relates to a glass composition according to any one of items 1 to 18, comprising SiO2, ZrO2, Al2O3, and B2O3, wherein the ratio of the weight of ZrO2 to the total weight of Al2O3 and B2O3 is at least 1.5.

[0177] Item 20 relates to any one of items 1 to 19, which does not contain As2O3 and / or Sb2O3.

[0178] Item 21 relates to any one of items 1 to 20, wherein the amount of Al2O3, B2O3, Li2O, K2O, SrO, ZnO, SO3, Fe2O3, TiO2, SnO2, and / or Cl, if present, is less than 0.1% by weight, less than 500 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, or even about 0.0% by weight.

[0179] Item 22 is 15.0 × 10 in the temperature range of 20 to 300°C. -6 K -1 Less than 12.0 × 10 -6 K -1 Less than 10.0 × 10 -6 K -1 Less than 9.8 × 10 -6 K-1 The present invention relates to a glass composition according to any one of items 1 to 21, having a coefficient of thermal expansion of less than .

[0180] Item 23 is CSS 200μm The present invention relates to a glass composition according to any one of items 1 to 22, wherein the compressive stress susceptibility, defined as the score, is at least 900 MPa.

[0181] Item 24 relates to any one of items 1 to 23, wherein the amount of ZrO2 is at least 10.0%, or at least 12.0% by weight.

[0182] Item 25 relates to a glass composition according to any one of items 1 to 24, wherein the ratio of the amount of ZrO2 to the amount of Al2O3 by weight is at least 2.0 or at least 3.0.

[0183] Item 26 relates to any one of items 1 to 25 having a 1000 MPa IOX time of less than 60 minutes or less than 30 minutes.

[0184] Item 27 specifies a glass transition temperature T of at least 540°C, at least 550°C, or at least 564°C. g The present invention relates to a glass composition according to any one of items 1 to 26, having the following characteristics.

[0185] Item 28 is glass, temperature T4 and T260-350K. 7.6 The present invention relates to a glass composition according to any one of items 1 to 27, having a steep temperature-viscosity curve characterized by the difference between and .

[0186] Item 29 states that the glass must be at least 10 μm thick. 2 / h, or at least 15μm 2 The present invention relates to a glass composition according to any one of items 1 to 28, having a diffusivity of / h.

[0187] Item 30 relates to a glass composition according to any one of items 1 to 29, wherein the glass has a total amount of alkaline earth metal oxides and ZnO of 15.0% by weight or less.

[0188] Item 31 states that when glass is heat-treated in a gradient furnace for 16 hours using the temperature rise method, the crystal growth rate is 10 5 The present invention relates to a glass composition according to any one of items 1 to 30, having a viscosity of dPa·s and a maximum flow rate of 0.5 μm / min.

[0189] Item 32 relates to any one of items 1 to 31, wherein the DoL is between 5 and 12 μm.

[0190] Item 33 relates to any one of items 1 to 32, wherein the Young's modulus (in GPa units) is between 70 and 90.

[0191] Item 34 relates to a glass composition according to any one of items 1 to 33, comprising one or more clarifying agents such as CeO2, SnO2, Cl, SO3, or Fe2O3.

[0192] Item 35 is 7.0 × 10 -6 K -1 ~9.8×10 -6 K -1 The present invention relates to a glass composition according to any one of items 1 to 34, having a coefficient of thermal expansion of glass.

[0193] Item 36 relates to any one of items 1 to 35, having a Young's modulus of 74 GPa to 90 GPa.

[0194] Item 37 relates to any one of items 1 to 36, having a Poisson's ratio of 0.220 to 0.270.

[0195] Item 38 is 2.530~2.900 g / cm³ 3The present invention relates to a glass composition according to any one of items 1 to 37, having a density of the specified density.

[0196] Item 39 relates to any one of items 1 to 38, having a packing density of 0.44 to 0.58.

[0197] Item 40 is the glass transition temperature T between 550°C and 700°C. g The present invention relates to a glass composition according to any one of items 1 to 39, having the following characteristics.

[0198] Item 41 relates to a glass composition according to any one of items 1 to 40, having a strain point of at least 550°C to 670°C.

[0199] Item 42 is, Temperature T4 of at least 960°C, at least 970°C, at least 1005°C, at least 1010°C, at least 1050°C or at least 1070°C. Temperature T3 of at least 1180°C, at least 1200°C, at least 1225°C, at least 1250°C, at least 1310°C, or at least 1330°C. • <0.00, optional VFT constant A between -5.00 and -2.00. · >5,000℃, optionally, VFT constant B between 5,800℃ and 8,000℃, and VFT constant T0 for 140-450°C, e.g., 145-300°C, or up to 255°C. The present invention relates to a glass composition described in any one of items 1 to 41, which exhibits one or more of the following characteristics.

[0200] Item 43 is glass, temperature T4 and T 7.6 The present invention relates to a glass composition according to any one of items 1 to 42, having a steep temperature-viscosity curve characterized by the difference between and .

[0201] Item 44 is glass, temperature T4 and T250-380K. 7.6The present invention relates to a glass composition according to any one of items 1 to 43, having a steep temperature-viscosity curve characterized by the difference between and .

[0202] Item 45 is CSS for 800MPa~1700MPa 200μm The present invention relates to a glass composition according to any one of items 1 to 44, having the following characteristics.

[0203] Item 46 is CSS for 600MPa~1200MPa 30μm The present invention relates to a glass composition according to any one of items 1 to 45, having the following characteristics.

[0204] Item 47 is 10-80 μm 2 The present invention relates to a glass composition according to any one of items 1 to 46, having a diffusivity of / h.

[0205] Item 48 is, (a) Hydrolysis tolerance values ​​of less than 320, or less than 300, or less than 280, or less than 250, or less than 225, or less than 210 μg / g sodium equivalent units; (b) Less than 25, or less than 22, or less than 20, or less than 18 mg / dm 2 Alkali resistance value per unit of weight loss; (c) mg / dm less than 5.0, or less than 2.5, or less than 1.0 2 Acid resistance value of weight loss units The present invention relates to a glass composition according to any one of items 1 to 47, having chemical resistance characterized by one or more of the following.

[0206] Item 49 is the compressive stress susceptibility CSS in MPa units for the total content of alkali metal oxides R2O and alkaline earth metal oxides R'O in weight percent. 200μm This relates to a glass composition according to any one of items 1 to 48, wherein / ([R2O]+[R'O]) is between 25 and 100.

[0207] Item 50 is the CSS in MPa for the coefficient of thermal expansion in ppm / K within a temperature range of 20-300°C. 200μm CSS 200μm The present invention relates to any one of the glass compositions described in item 1 to 49, wherein the CTE is between 100 and 250.

[0208] Item 51 is the refractive index n from 1.520 to 1.600. d The present invention relates to a glass composition according to any one of items 1 to 50, having the following characteristics.

[0209] Item 52 is 10 4 This relates to any one of the glass compositions described in item 1 to 51, which exhibit no devitrification at a working point of dPa·s.

[0210] Item 53 is 10 5 The present invention relates to a glass composition according to any one of items 1 to 52, wherein the crystal growth rate at a viscosity of dPa·s is up to 0.5 μm / min.

[0211] Item 54 is, [Table 37] Including, relating to glass.

[0212] Item 55 relates to the glass composition described in Item 54, having a CTE of 8.0 ppm / K to 9.0 ppm / K; or about 8.8 ppm / K.

[0213] Item 56 relates to the glass compositions described in item 54 or 55, having a Young's modulus of 70 GPa to 85 GPa, or about 78 GPa.

[0214] Item 57 relates to any one of items 54 to 56, having a Poisson constant of 0.245 to 0.255, or about 0.250.

[0215] Item 58 is T at 600°C to 625°C, or approximately 611°C. gThe present invention relates to a glass composition having the characteristics described in any one of items 54 to 57.

[0216] Item 59 is 2,600 g / cm³. 3 ~2.725g / cm 3 , or approximately 2.644 g / cm³ 3 The present invention relates to a glass composition having a density as described in any one of items 54 to 58.

[0217] Item 60 relates to any one of items 54 to 59, having a packing density of 0.440 to 0.580 or 0.50 to 0.54.

[0218] Item 61 relates to any one of items 54 to 60, having a VFT A of -3.200 to -3.450, or about -3.375.

[0219] Item 62 relates to any one of items 54 to 61, having a VFT B of 6700°C to 6850°C, or about 6776°C.

[0220] Item 63 relates to any one of items 54 to 62, having a VFT T0 of 200°C to 250°C, or about 213°C.

[0221] Item 64 is T at 580°C to 600°C, or approximately 593°C. 14.5 The present invention relates to a glass composition according to any one of items 54 to 63, having the following characteristics.

[0222] Item 65 is T at 615°C to 640°C, or approximately 627°C. 13 The present invention relates to a glass composition according to any one of items 54 to 64, having the following characteristics.

[0223] Item 66 is T at 815°C to 845°C, or approximately 831°C. 7.6. The present invention relates to a glass composition according to any one of items 54 to 65, having the following characteristics.

[0224] Item 67 relates to any one of items 54 to 66, having a T4 of 1100°C to 1200°C, or about 1132°C.

[0225] Item 68 relates to any one of items 54 to 67, having a T3 of 1200°C to 1300°C, or about 1276°C.

[0226] Item 69 relates to any one of items 54 to 68, having a T2 of 1400°C to 1500°C, or about 1474°C.

[0227] Item 70 is CSS for 800MPa to 1700MPa 200μm The present invention relates to a glass composition according to any one of items 54 to 69, having the following characteristics.

[0228] Item 71 is CSS for 600MPa~1200MPa 30μm The present invention relates to a glass composition according to any one of items 54 to 70, having the following characteristics.

[0229] Item 72 is 10-80 μm 2 The present invention relates to a glass composition according to any one of items 54 to 71, having a diffusivity of / h.

[0230] Item 73 is, (a) Hydrolysis tolerance values ​​of less than 210 μg / g sodium equivalent units; (b) mg / dm² less than 18 2 Alkali resistance value per unit of weight loss; (c) mg / dm less than 2.5 or less than 1.0 2 Acid resistance value of weight loss units The present invention relates to a glass composition according to any one of items 54 to 72, having chemical resistance characterized by one or more of the following.

[0231] Item 74 is the compressive stress susceptibility in MPa units for the total content of alkali metal oxides R2O and alkaline earth metal oxides R'O in weight percent (CSS). 200μm This relates to a glass composition according to any one of items 54 to 73, wherein / ([R2O]+[R'O]) is between 25 and 100.

[0232] Item 75 is the CSS in MPa for the coefficient of thermal expansion in ppm / K within the temperature range of 20-300°C. 200μm CSS 200μm The present invention relates to a glass composition according to any one of items 54 to 74, wherein the CTE is between 100 and 250.

[0233] Item 76 relates to glass articles comprising any one of items 1 to 75 having a thickness of less than 1000 μm, less than 100 μm, less than 80 μm, less than 60 μm, or less than 40 μm.

[0234] Item 77 is optional, a glass article comprising a glass composition described in any one of items 1 to 75, having a thickness of less than 1000 μm, wherein the article comprises glass containing at least 40.0% by weight of SiO2, at least 12.0% by weight of Na2O, and ZrO2, wherein the ratio of the weight of ZrO2 to the sum of the weights of Al2O3 and B2O3 is at least 1.5, and the glass is subjected to a CSS of at least 700 MPa. 30μm It contains and / or 5.0 mg / dm 2 Less than 2.5 mg / dm 2 This relates to glass articles having acid resistance of less than 1.

[0235] Item 78 relates to the glass articles described in items 76 or 77, which include an ion-exchanged layer on one or both of the main surfaces and have a compressive stress of at least 400 MPa, at least 700 MPa, or at least 800 MPa.

[0236] Item 79 relates to any one of items 76 to 78, wherein the ratio of compressive stress in MPa units to article thickness in μm units on one or both of the main surfaces is at least 4.0 MPa / μm, at least 5.0 MPa / μm, at least 10.0 MPa / μm, or at least 20.0 MPa / μm.

[0237] Item 80 relates to any one of items 76 to 79, wherein the ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units is at least 50 MPa / μm, at least 75 MPa / μm, or at least 90 MPa / μm.

[0238] Item 81 relates to glass articles described in any one of items 76 to 80, having a thickness of 1000 μm or less.

[0239] Item 82 relates to glass articles described in any one of items 76 to 81, having a deflection of less than 3.0 mm.

[0240] Item 83 relates to glass articles described in any one of items 76 to 82, having a total thickness variation of less than 15.0 μm.

[0241] Item 84 is surface roughness R of 5.0 nm or less. a relating to glass articles as described in any one of items 76 to 83, having the following characteristics.

[0242] Item 85 is, (a) Hydrolysis tolerance values ​​of less than 320, or less than 300, or less than 280, or less than 250, or less than 225, or less than 210 μg / g sodium equivalent units; (b) mg / dm less than 25, or less than 22, or less than 20, or less than 18 2 Alkali resistance value per unit of weight loss; (c) mg / dm less than 5.0, or less than 2.5, or less than 1.0 2 Acid resistance value of weight loss units The glass articles described in any one of items 76 to 84, which have outstanding chemical resistance characterized by one or more of the following:

[0243] Item 86 relates to glass articles as described in any one of items 76 to 85, having a Vickers hardness of at least 580.

[0244] Item 87 relates to glass articles described in any one of items 76 to 86, having a three-point bending strength of 300 MPa to 400 MPa.

[0245] Item 88 relates to glass articles described in any one of items 76 to 87, having a compressive stress of at least 400 MPa.

[0246] Item 89 relates to glass articles having a thickness of 20 to 40 μm, as described in any one of items 76 to 88.

[0247] Item 90 relates to any one of items 76 to 89, which has a DoL of 6 to 11 μm on one or both of its main surfaces.

[0248] Item 91 relates to glass articles as described in any one of items 76 to 90, having a DoL of 15 to 25% of the article thickness.

[0249] Item 92 relates to any one of items 76 to 91, wherein the ratio of compressive stress in MPa units to article thickness in μm units is at least 4.0 MPa / μm.

[0250] Item 93 relates to a glass article according to any one of items 76 to 92, wherein the ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units on one or both of the main surfaces is at least 50.

[0251] Item 94 relates to glass articles described in any one of items 76 to 93, having a three-point bending strength of at least 400 MPa.

[0252] Item 95 relates to electronic equipment, including glass compositions described in any one of items 1 through 75, and / or glass articles described in any one of items 76 through 94.

[0253] Examples Exemplary glass compositions according to the present invention were prepared by melting suitable glass raw materials. The following table summarizes the composition and properties of these glasses. Note that the values ​​in the table have been rounded to one decimal place. Therefore, small rounding errors may occur in the derivation and summation of the values.

[0254] 1. Compositions considered [Table 38]

[0255] [Table 39]

[0256] [Table 40]

[0257] The packing density of the glass is determined by dividing the ionic volume by the molar volume, where the ionic volume is the volume occupied by 1 mole of ions constituting the glass, and the molar volume is the quotient of the molar weight of the glass and the measured density. To calculate the volume of each type of ion, Shannon's effective ionic radius is used along with the coordination number calculated using Pauling's rule.

[0258] 2. Ion exchange treatment Thin glass sheets were prepared from compositions 1 to 7. The sheet thickness was 200 μm. Subsequently, the sheets were subjected to ion exchange treatment in a 100% KNO3 salt bath at 440°C for 30 minutes. The resulting compressive stress and the depth (DoL) of the ion-exchanged layer are shown in the table below.

[0259] [Table 41]

[0260] 3. Chemical resistance Chemical resistance was tested on glass No. 2. Hydrolysis resistance was tested according to ISO 719. Alkali resistance was measured according to ISO 695, and acid resistance was tested according to DIN 12116. The results were: ·Hydrolysis resistance [μg / g]: 172, • Alkali resistance [mg / dm 2 ]:15, ·Acid resistance [mg / dm 2 ]:0.7 That is the case.

[0261] 4.Devitrification Devitrification resistance is 10 for compositions 1, 2, 3, and 7. 5 The crystal growth rate (in μm / min) at a viscosity of dPa·s was determined. Lower crystal growth rates indicate higher resistance to devitrification. The measurement of crystal growth rate is well-known. The crystal growth rate is measured along the formed crystal, i.e., at its maximum elongation.

[0262] In short, the crystal growth rate was determined by heat-treating the glass in a gradient furnace for 16 hours using the temperature rise method. Importantly, the devitrification rate was 10 5 If it does not occur at all with a viscosity of dPa·s, 10 5 The crystal growth rate at dPa·s cannot be determined. The absence of devitrification is 10 5 It can also be expressed as a crystal growth rate of 0 μm / min in dPa·s.

[0263] The crystallization rate was determined using glass grains with a diameter of approximately 2 mm to 3 mm. The glass grains were placed on a platinum carrier for gradient annealing. The carrier had recesses for receiving the glass grains and holes at the bottom of each recess for optical inspection, thus allowing for microscopic determination of the crystal growth rate. Each recess had a diameter of 2 mm, and each hole had a diameter of 0.9 mm.

[0264] The results are shown in the table below.

[0265] [Table 42]

Claims

1. The following ingredients: i.SiO ２ 、 ii. 0.0 to 6.0% by weight of Al ２ O ３ , ii. At least 8.0% by weight of ZrO ２ , iii. At least 12.0% by weight of Na ２ O, iv. 0.0–5.0% by weight of B ２ O ３ v. 0.0 to 5.0% by weight of Li ２ O, vi. 0.0 to 10.0% by weight of K ２ O, vii. Optionally, P ２ O ５ and TiO ２ One or more ingredients selected from Glass, including.

2. The following components are listed by weight: Table 1 Includes, optionally, Fe ２ O ３ , CoO, and / or Cr ２ O ３ The glass according to claim 1, comprising a dye or coloring agent such as the above.

3. As ２ O ３ and / or Sb ２ O ３ The glass according to claim 1 or 2, which does not contain the glass.

4. 15.0 × 10 in a temperature range of 20 to 300°C －６ K －１ Less than 12.0 x 10 －６ K －１ Less than 10.0 x 10 －６ K －１ Less than 9.8 x 10 －６ K －１ A glass according to any one of claims 1 to 3, having a coefficient of thermal expansion of less than .

5. CSS ３０μｍ The glass according to any one of claims 1 to 4, wherein the compressive stress susceptibility, defined as the score, is at least 700 MPa.

6. ZrO ２ The glass according to any one of claims 1 to 5, wherein the amount of is >10.0% by weight.

7. Al by weight % ２ O ３ ZrO ２ The glass according to any one of claims 1 to 6, wherein the ratio of the amounts is at least 1.5 or at least 2.

0.

8. The glass according to any one of claims 1 to 7, having a 1000 MPa IOX time of less than 60 minutes.

9. Glass transition temperature T of at least 540°C, at least 550°C, or at least 560°C ｇ A glass having one or more of the features described in any one of claims 1 to 8.

10. Temperature T between 250 and 350 K ４ and T ７．６ A glass according to any one of claims 1 to 9, having a steep temperature-viscosity curve characterized by the difference between and .

11. at least 8 μm ２ / h, or at least 10 μm ２ A glass having a diffusivity of / h, according to one or more of claims 1 to 10.

12. mg / dm ２ A glass according to any one of claims 1 to 11, wherein the acid resistance value of the weight loss unit is less than 5.

0.

13. When the glass is heat-treated in a gradient furnace for 16 hours using the temperature rise method, the crystal growth rate is 10 ５ A glass according to any one or more of claims 1 to 12, having a viscosity of dPa·s and a maximum flow rate of 0.5 μm / min.

14. A glass according to any one of claims 1 to 13, wherein the Young's modulus is between 70 and 90 GPa.

15. A glass article, optionally, a glass according to any one of claims 1 to 15, having a thickness of less than 1000 μm, and the article contains at least 40.0% by weight of SiO ２ , at least 12.0% by weight of Na ２ O, and furthermore, ZrO ２ Includes glass containing Al ２ O ３ and B ２ O ３ ZrO for the total weight of ２ The weight ratio is at least 1.5, and the glass is at least 700 MPa CSS ３０μｍ It contains and / or 5.0 mg / dm ２ Acid resistance of less than 2.5 mg / dm ２ Glass articles with acid resistance of less than 100%.

16. The glass article according to claim 15, having a thickness of less than 100 μm, less than 80 μm, less than 60 μm, or less than 40 μm.

17. A glass article according to at least one of claims 15 to 16, comprising an ion-exchanged layer on one or both of the main surfaces.

18. The glass article according to claim 17, wherein one or both of the main surfaces have a compressive stress of at least 400 MPa, at least 700 MPa, or at least 800 MPa.

19. The glass article according to claim 17 or 18, wherein on one or both of the main surfaces, the ratio of compressive stress in MPa units to article thickness in μm units is at least 4.0 MPa / μm, at least 5.0 MPa / μm, at least 10.0 MPa / μm, at least 15.0 MPa / μm, or at least 20.0 MPa / μm.

20. The glass article according to at least one of claims 17 to 19, wherein on one or both of the main surfaces, the ratio of compressive stress in MPa units to the depth of the ion-exchanged layer in μm units is at least 50 MPa / μm, at least 75 MPa / μm, or at least 90 MPa / μm.

21. Electronic device comprising glass according to any one of claims 1 to 14, and / or a glass article according to any one of claims 15 to 20.

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