Ultrathin glass with low peripheral to center fracture ratio

Abstract

The present invention relates to a collapsible glass article having a thickness of at most 200 m and a method of making the same. The peripheral region of the glass article has a smaller thickness than the central region. The glass article has a low peripheral to center fracture ratio. In particular, in a two-point bending test, more sources of rupture originate from the central region of the glass article rather than its peripheral region. The invention also relates to the use of said glass article, in particular in consumer electronic products, such as foldable handheld devices including smartphones.

Description

Technical Field

[0001] This invention relates to a foldable glass article with a thickness of up to 200 µm and a method for manufacturing the same. The peripheral region of the glass article has a smaller thickness compared to the central region. The glass article has a low periphery-to-center breakage ratio. Specifically, in a two-point bending test, more breakage originates from the central region of the glass article than from its peripheral region. This disclosure also relates to the use of the glass article, particularly in consumer electronics products such as foldable handheld devices including smartphones. Background Technology

[0002] Due to its unique properties of flexibility, high modulus, and transparency, ultrathin glass holds immense potential for applications in consumer electronics and optics. However, despite its high flexibility, edge breakage under bending stress still poses a high risk of failure. Common methods for enhancing the edge strength of thick glass (e.g., edge grinding and polishing) are largely unsuitable for ultrathin glass. Therefore, ultrathin glass with low edge strength may crack due to repeated bending in its subsequent applications (such as cover glass for foldable electronic devices), leading to eventual (often costly) device failure.

[0003] Typically, glass manufacturers focus heavily on improving the flexural strength of foldable glass to achieve increasingly smaller minimum bending radii. While surface treatments such as chemical tempering and light etching can be applied to ultra-thin glass to easily enhance flexural strength, edge quality often remains a limiting factor. Improving the edge quality of ultra-thin glass involves edge treatments, including creating chamfered structures. However, previous edge treatment methods still have room for further improvement.

[0004] WO 2022 / 232996 A1 discloses an ultrathin glass exhibiting high edge impact resistance as determined in a pendulum swing test. However, in the corresponding disclosure, all etching steps occur prior to chemical tempering. Therefore, neither a "post-etching" step is disclosed nor implied. Furthermore, the peripheral area of ​​this disclosure is not covered in this patent document.

[0005] KR 10-1620375 B1 discloses a UTG lamination process in which UTG glass is stacked into a laminate, cut to a certain size, and subjected to edge grinding and polishing, followed by an etching step in which the laminate is rotated in an etching solution. However, instead of rotating individual glass pieces in the etching solution after tempering, the laminate is rotated before tempering. This patent document does not cover the peripheral area of ​​this disclosure.

[0006] WO 2019 / 218155 A1 discloses an ultra-thin glass with a special chamfered shape. However, it does not disclose the outer perimeter area. Summary of the Invention

[0007] The inventors of this invention have discovered that optimized thinning of the peripheral region can improve flexibility and significantly reduce such glass failure due to peripheral breakage. In particular, it has been found that bending strength can be increased to make the glass tend to break originating from its center rather than from its edges. In the commonly used two-point bending (2PB) test, glass produced by the method of this invention exhibits a breakage rate of <50%, particularly at most 45%, originating from the edges.

[0008] It has been found that in 2PB testing, the best edge strength is achieved when the width of the thinned peripheral region (measured from the edge) is about 3-5 mm and the peripheral thickness of the glass is about 99%, at least 75%, at least 85%, or at least 90% of the center thickness (particularly thinned by 1-10 µm or 1-3 µm).

[0009] On one hand, this disclosure relates to a chemically tempered glass article comprising: a first main surface and a second main surface, and at least one edge surface connecting the first main surface and the second main surface. The glass article has a central region and a peripheral region, wherein the first and second main surfaces are substantially parallel to each other in the central region. The central region is composed of a portion of glass material, measured parallel to the first or second main surface, whose closest distance to the edge surface is greater than 5.0 mm. The peripheral region is composed of a portion of glass material, measured parallel to the first or second main surface, with a minimum distance of 5.0 mm to the edge surface. The average thickness of the central region is at most 200µm. The average thickness of the peripheral region is 1.0 µm to 10.0 µm less than the average thickness of the central region, such as 1.0 µm to 7.0 µm, 1.0 µm to 5.0 µm, or 1.0 µm to 3.0 µm less. The average thickness of the peripheral region is the average thickness measured parallel to the first or second main surface, along a circumferential line 2.5 mm away from the edge surface.

[0010] In particular, the length and width of the first main surface are substantially the same as the length and width of the second main surface.

[0011] The average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, is, for example, less than the average thickness of the central region by 1.0 µm to 10.0 µm, 1.0 µm to 7.0 µm, 1.0 µm to 5.0 µm, 1.0 µm to 3.0 µm, 1.2 µm to 2.8 µm, 1.5 µm to 2.5 µm, or 1.7 µm to 2.3 µm. The average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, is, for example, less than the average thickness of the central region by at least 1.0 µm, at least 1.2 µm, at least 1.5 µm, or at least 1.7 µm. The average thickness of the peripheral region, measured parallel to the first or second main surface and with a nearest distance of 2.5 mm from the edge surface, is, for example, smaller than the average thickness of the central region by at most 10.0 µm, at most 7.0 µm, at most 5.0 µm, at most 3.0 µm, at most 2.8 µm, at most 2.5 µm, or at most 2.3 µm.

[0012] Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be in the range of 75% to 99%, 80% to 99%, 85% to 99%, 90% to 98%, or 91% to 97%. Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be at least 75%, at least 80%, at least 85%, at least 90%, or at least 91%. Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be at most 99%, at most 98%, or at most 97%.

[0013] On one hand, this disclosure relates to a chemically tempered glass article comprising: a first main surface and a second main surface, and at least one edge surface connecting the first main surface and the second main surface. The glass article has a central region and a peripheral region, wherein the first and second main surfaces are substantially parallel to each other in the central region. The central region is formed by a portion of the glass article that, when measured parallel to the first or second main surface, has a nearest distance greater than 5.0 mm from the edge surface. The peripheral region is formed by a portion of glass articles, measured parallel to the first or second main surface, whose closest distance to the edge surface is at most 5.0 mm. The average thickness of the central region is at most 200µm. The ratio of the average thickness of the peripheral region to the average thickness of the central region is in the range of 75% to 99%, 80% to 99%, or 85% to 99%.

[0014] The average thickness of the peripheral region is the average thickness measured parallel to the first or second main surface, along a circumferential line 2.5 mm away from the edge surface.

[0015] In particular, the length and width of the first main surface are substantially the same as the length and width of the second main surface.

[0016] Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be in the range of 90% to 98%, or 91% to 97%. Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be at least 75%, at least 80%, at least 85%, at least 90%, or at least 91%. Specifically, the ratio of the average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the central region can be at most 99%, at most 98%, or at most 97%.

[0017] The average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, may be 1.0 µm to 10.0 µm, 1.0 µm to 7.0 µm, 1.0 µm to 5.0 µm, 1.0 µm to 3.0 µm, 1.2 µm to 2.8 µm, 1.5 µm to 2.5 µm, or 1.7 µm to 2.3 µm less than the average thickness of the central region. The average thickness of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, may be at least 1.0 µm, at least 1.2 µm, at least 1.5 µm, or at least 1.7 µm less than the average thickness of the central region. The average thickness of the peripheral region, measured parallel to the first or second main surface and with a nearest distance of 2.5 mm from the edge surface, may be at most 10.0 µm, at most 7.0 µm, at most 5.0 µm, at most 3.0 µm, at most 2.8 µm, at most 2.5 µm, or at most 2.3 µm less than the average thickness of the central region.

[0018] Specifically, the average thickness of the central region and the average thickness of the peripheral region are measured in the following manner.

[0019] Peripheral region: Using a micrometer, measure the thickness along a line 2.5 mm from the center of the contour. Take a measurement every 1 cm of the contour. Then calculate the average thickness based on the measurements. The average thickness at 2.5 mm from the edge is a reasonable measure of the average thickness of the peripheral region because the increase in thickness can be approximately linear from the peripheral region to the center region.

[0020] Central area: Using a micrometer, measure the thickness in the area greater than 5 mm from the profile along the direction towards the center. For each 1 cm... 2 A measurement is taken in the area. Then, the average thickness is calculated based on the measurement.

[0021] In particular, the chemically tempered glass articles of this disclosure are foldable glass articles. Therefore, optionally, the glass articles of this disclosure can be folded about a folding axis.

[0022] In this disclosure, the expression "measured parallel to the first or second principal surface" refers to a direction parallel to the portion of the first or second principal surface, in which the first and second principal surfaces are substantially parallel to each other.

[0023] The first and second main surfaces are substantially parallel to each other in the central region, but this does not preclude the central region from also including areas with minimal deviations from the parallel orientation of the first and second main surfaces. In particular, this disclosure also includes partially thinned glass (LSG). Partially thinned glass refers to glass having a thinned region around its folding axis and a thicker unfolded region. In such glass, the first and second main surfaces are substantially parallel to each other, particularly in the thicker unfolded region and the portion corresponding to the minimum thickness of the thinned region. However, there are regions between these areas where the thickness decreases from the edge to the center. In the transition region between the thicker unfolded region and the thinned region with the minimum thickness, the first and second main surfaces are not parallel to each other compared to the remainder of the central region.

[0024] Specifically, the average thickness of the central region is in the range of 15µm to 200µm, 15µm to 150µm, 15µm to 120µm, 15µm to 100µm, 20µm to 80µm, 25µm to 75µm, or 30µm to 70µm. Specifically, the average thickness of the central region is at least 15µm, at least 20µm, at least 25µm, or at least 30µm. Specifically, the average thickness of the central region is at most 200µm, at most 150µm, at most 120µm, at most 100µm, at most 80µm, at most 75µm, or at most 70µm.

[0025] The glass articles disclosed herein are chemically tempered glass articles. Specifically, the surface compressive stress at the first and / or second main surfaces is in the range of 300 MPa to 1500 MPa, such as 400 MPa to 1200 MPa, 500 MPa to 1000 MPa, 600 MPa to 900 MPa, or 700 MPa to 850 MPa. Specifically, the surface compressive stress at the first and / or second main surfaces is at least 300 MPa, at least 400 MPa, at least 500 MPa, at least 600 MPa, or at least 700 MPa. Specifically, the surface compressive stress at the first and / or second main surfaces is at most 1500 MPa, at most 1200 MPa, at most 1000 MPa, at most 900 MPa, at most 800 MPa, or at most 750 MPa.

[0026] Specifically, the layer depth at the first and / or second main surface is in the range of 0.5µm to 40µm, such as 1.0µm to 20µm, 2.0µm to 15µm, or 5.0µm to 10µm. Specifically, the layer depth at the first and / or second main surface is at least 0.5µm, at least 1.0µm, at least 2.0µm, or at least 5.0µm. Specifically, the layer depth at the first and / or second main surface is at most 40µm, at most 20µm, at most 15µm, or at most 10µm.

[0027] Specifically, the layer depth at the first and / or second main surfaces is in the range of 1.0% to 40% of the average thickness of the central region, such as 2.0% to 20%, or 5.0% to 10%. Specifically, the layer depth at the first and / or second main surfaces is at least 1.0%, at least 2.0%, or at least 5.0% of the average thickness of the central region. Specifically, the layer depth at the first and / or second main surfaces is at most 40%, at most 20%, or at most 10% of the average thickness of the central region.

[0028] In some embodiments, the central region may include a folded region and a non-folded region, wherein the average thickness of the central region in the folded region is less than the average thickness of the central region in the non-folded region. Similarly, the peripheral region may include a folded region and a non-folded region, wherein the average thickness of the peripheral region in the folded region is less than the average thickness of the peripheral region in the non-folded region. In such embodiments, the average thickness of the folded region of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, may be, for example, 1.0 µm to 3.0 µm less than the average thickness of the folded region of the central region, for example, 1.2 µm to 2.8 µm, 1.5 µm to 2.5 µm, or 1.7 µm to 2.3 µm less. Similarly, the ratio of the average thickness of the folded region of the peripheral region, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, to the average thickness of the folded region of the central region may be in the range of 85% to 99%, such as 90% to 98%, or 91% to 97%.

[0029] In some embodiments, the thickness of the peripheral region is reduced and uniformly distributed around the entire peripheral region compared to the central region of the glass. Specifically, the deviation between the thickness of the peripheral region at any given location parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, and the average thickness of the peripheral region at a nearest distance of 2.5 mm from the edge surface, can be less than 2.0%, 1.0%, 0.5%, or 0.2% of the average thickness of the peripheral region at a nearest distance of 2.5 mm from the edge surface, as measured parallel to the first or second main surface. For example, if the average thickness of the peripheral region at a nearest distance of 2.5 mm from the edge surface, as measured parallel to the first or second main surface, is 50 µm, and the thickness of the peripheral region at any given location parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, is in the range of >49 µm to <51 µm, then the aforementioned deviation will be less than 2%. Even in embodiments where the thickness reduction in the peripheral region is uniformly distributed, the deviation between the thickness of the peripheral region at any given location, measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, and the average thickness of the peripheral region measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface, can be at least 0.01%, at least 0.02%, or at least 0.05% of the average thickness of the peripheral region measured parallel to the first or second main surface and at a nearest distance of 2.5 mm from the edge surface.

[0030] In some embodiments, the thickness reduction of the peripheral region compared to the central region of the glass is non-uniformly distributed around the entire peripheral region. For example, in some embodiments, the peripheral region of the glass may include one or more regions with a reduced thickness compared to the central region and one or more regions with no reduced thickness compared to the central region. In some embodiments, the segment of the peripheral region parallel to the longitudinal axis of the glass article may have a reduced thickness compared to the central region, while the segment of the peripheral region perpendicular to the longitudinal axis may not have a reduced thickness compared to the central region.

[0031] The sections parallel to the longitudinal axis can also be referred to as the long sides of the glass article. Typically, it is these long sides that bend during the folding process of the glass article. In contrast, the short sides usually do not bend during folding. Therefore, it is particularly advantageous that the sections in the peripheral region, parallel to the longitudinal axis of the glass article, have a reduced thickness compared to the central region.

[0032] Optionally, the glass article described in this disclosure is axially symmetric. In other words, optionally, the glass article includes one or more axes of symmetry. Therefore, the glass article may include one or two axes of symmetry. For example, if the glass article is rectangular (the length y of the glass article is greater than the width z), there may be a first axis of symmetry parallel to the long side of the glass article and a second axis of symmetry parallel to the short side of the glass article. In embodiments where the glass article is square (length y equals width z), there may be a first axis of symmetry parallel to two opposite sides of the glass article and a second axis of symmetry parallel to the other two sides of the glass article. In such embodiments, the term "long side" of the glass article may refer to the two opposite sides of the glass article, while the term "short side" of the glass article may refer to the remaining two sides perpendicular to the long side.

[0033] Therefore, although the long and short sides are of equal length in a square glass article, the corresponding terminology used in this disclosure refers not only to a rectangular glass article but also to a square glass article, in order to distinguish the two opposite sides of one side and the two sides perpendicular to it on the other side. Of course, in embodiments of glass articles having a rectangular shape, the long side of the glass article is actually longer than the short side. In particular, the length of the long side is the same as the length y of the glass article, while the length of the short side is the same as the width z of the glass article.

[0034] In any case, whether the glass object is rectangular or square, the first axis of symmetry is specifically perpendicular to the second axis of symmetry.

[0035] The folding axis of a glass article can be one of its axes of symmetry. In particular, the folding axis can be the axis of symmetry of the glass article that is parallel to the shorter side of the glass article.

[0036] In the 2PB test, a glass article is placed in a U-shape between two parallel plates. These plates are large enough to cover the entire article. One plate is then moved towards the other at 60 mm / min while remaining parallel, until the designed folding distance is reached, which is 50 times the center thickness. The folding distance is defined as the distance between the two plates. If the foldable article remains intact when the folding distance is reached, it is considered to have passed the test. For ultra-thin glass (UTG), the center thickness of the glass article corresponds to the average thickness of the central region of the glass article. For partially thinned glass (LSG), the center thickness of the glass article corresponds to the average thickness of the folded area in the central region. The pass rate is the number of passed samples divided by the total number of measured samples.

[0037] The glass articles described in this disclosure specifically have a pass rate of at least 65% in the 2PB test, such as at least 70%, at least 75%, at least 80%, at least 85%, or at least 90%. The pass rate in the 2PB test can, for example, be up to 99.9%, up to 99%, up to 98%, up to 97%, up to 96%, or up to 95%. The pass rate in the 2PB test can, for example, be in the range of 65% to 99.9%, 70% to 99%, 75% to 98%, 80% to 97%, 85% to 96%, or 90% to 95%. Specifically, the 2PB test is performed using a sample size of at least 50 pieces, for example, 50 pieces.

[0038] To evaluate the fracture origin of glass in the 2PB test, a polymer film was laminated on both sides of the test glass, the length and width of which were 5 mm larger than the glass. The adhesion between the glass and the polymer film was electrostatic. The film material was PE (polyethylene) to have a low modulus of elasticity. Each side of the glass was laminated with a 50 µm thick monolayer of polymer. Through this operation, cracks and fragments were trapped in the polymer film, and their origin points could be analyzed through the network crack structure. In this analysis, it was found that the glass articles of this disclosure showed more fracture origins originating from the center of the glass than from its edges. When calculated as a periphery to center fracture ratio (P2C), the P2C of the glass of the present invention is particularly less than 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, or at most 15%. The P2C ratio can, for example, be at least 0.1%, at least 0.2%, at least 0.5%, at least 1.0%, at least 2.0%, at least 3.0%, at least 4.0%, or at least 5.0%. The P2C ratio can, for example, range from 0.1% to <50%, 0.2% to 45%, 0.5% to 40%, 1.0% to 35%, 2.0% to 30%, 3.0% to 25%, 4.0% to 20%, or 5.0% to 15.0%. Specifically, the P2C ratio is determined based on a sample size of at least 50 items, for example, 50 items.

[0039] The P2C ratio represents the percentage of rupture sources originating from the peripheral region out of the total number of ruptures. The P2C ratio is calculated using the following formula: .

[0040] In this regard, the term "periphery" refers to the peripheral area of ​​a glass article, which consists of a portion of the glass article that, when measured parallel to the first or second main surface, has a closest distance of at most 5.0 mm to the edge surface. Similarly, the term "center" refers to the central area of ​​a glass article, which consists of a portion of the glass article that, when measured parallel to the first or second main surface, has a closest distance of more than 5.0 mm to the edge surface.

[0041] Specifically, the glass article of this disclosure can pass a sliding test, wherein the folding distance of the sliding test is equal to 50 times the center thickness of the glass article (refer to the center thickness described above). In this test, the foldable glass article is placed in a U-shape between two parallel plates. These two plates are large enough to cover the entire article. Then, one plate moves towards the other plate at a speed of 60 mm / min while remaining parallel until the designed distance is reached. The folding distance is defined as the distance between the two plates. Then, the moving plate begins to move back and forth along the length of the article at a speed of 10 mm / s and a travel distance of 10 mm. A glass article that withstands 10 slides without glass breakage is considered to have passed the test. Figure 5 The setup for the sliding test is illustrated schematically.

[0042] In a sliding test with a folding distance of 50 times the center thickness of the glass article, a plate speed of 10 mm / s, and a plate travel distance of 10 mm, the glass article of this disclosure passed 10 repetitions without breakage. In the sliding test with a folding distance of 50 times the center thickness of the glass article, a plate speed of 10 mm / s, and a plate travel distance of 10 mm, the pass rate of the glass article of this disclosure is particularly greater than 50%, for example, at least 55%, at least 60%, at least 65%, at least 70%, or at least 75%. In the sliding test with a folding distance of 50 times the center thickness of the glass article, a plate speed of 10 mm / s, and a plate travel distance of 10 mm, the pass rate of the glass article of this disclosure can be, for example, 100%, at most 99%, at most 98%, at most 95%, at most 90%, or at most 87%. In a sliding test with a folding distance of 50 times the center thickness of the glass article, a plate speed of 10 mm / s, and a plate travel distance of 10 mm, the pass rate of the glass article described in this disclosure can, for example, be in the range of >50% to 100%, 55% to 99%, 60% to 98%, 65% to 95%, 70% to 90%, or 75% to 87%. Specifically, the sample size is at least 50 pieces, for example, 50 pieces.

[0043] In some embodiments, the glass article of this disclosure has a chamfered edge. When the tangent angle of the first surface is defined as 0° and the tangent angle of the second surface is defined as 180°, specifically, the chamfered structure has an average chamfered surface with a profile such that at any position xi of the average chamfered surface, the tangent angle α of the average chamfered surface is... xi Within the range of >0° to <180°. Specifically, the chamfered structure has a chamfer height H, which is defined from the average chamfered surface closest to the first surface of the glass article and α. xi At a position xi of 45°, the closest point to the second surface is reached, and α... xj=135° is the length of the projection of the line segment at position xj onto a line that makes a 90° angle with both the tangents of the first and second surfaces. The total chamfer height variation TCHV along the length y and / or width z of the glass article is defined as the maximum chamfer height H along at least a portion of the length y and / or width z of the article. 最大值 and minimum chamfer height H 最小值 The difference divided by the average chamfer height H along the length y and / or width z of the article 平均值 The portion therein is at least 25% of the length y and / or width z. Specifically, (t*H) 平均值 The ratio of ) / TCHV can be at least 250µm 2 .

[0044] An average beveled surface is obtained by overlapping optical layers based on the cross-section of the beveled surface profile. To obtain such an image, the glass artifact is observed in transmitted light mode using an optical microscope. A magnification of 200x is used. The focus is on the top plane, so the edges appear very sharp. The glass artifact is positioned so that the top plane is not tilted. Therefore, the top plane is perpendicular to the direction of light. Using automatic white balance, automatic brightness, and automatic contrast, especially with a Nikon Y-TV55 microscope, particularly high-quality images can usually be obtained. Since depth of field determines the depth of overlap, an average beveled surface can be observed in this image. Using the above method, the average beveled structure is based on an overlapping optical layer with a depth of approximately 0.5 mm. For example, the sample has an extension of at least 1 mm in the observation direction to ensure sufficient depth for overlap.

[0045] In some embodiments, the chamfer structure has a chamfer width W, defined as the distance from a specific location on the average chamfer surface to a line forming a 90° angle with both the first and second surface tangents, wherein the distance is measured perpendicular to the corresponding line forming a 90° angle with both the first and second surface tangents, wherein there are no other locations on the average chamfer surface with a greater distance from the corresponding line forming a 90° angle with both the first and second surface tangents, the distance being measured perpendicular to the corresponding line forming a 90° angle with both the first and second surface tangents. In one aspect of this disclosure, the chamfer width W is related to the average chamfer height H. 平均值 The ratio can range from 0.1:1 to 10:1, for example, 1:1 to 10:1, 2:1 to 7.5:1, 3:1 to 6:1, or 3.5:1 to 5:1. The chamfer width W and the average chamfer height H... 平均值 The ratio can be, for example, at least 0.1:1, at least 1:1, at least 2:1, at least 3:1, or at least 3.5:1. The chamfer width W and the average chamfer height H... 平均值The ratio can be, for example, up to 10:1, up to 7.5:1, up to 6:1, or up to 5:1.

[0046] In some embodiments, the thickness t is related to the average chamfer height H. 平均值 The ratio can range from 1.2:1 to 10:1, for example, 1.3:1 to 7.5:1, 1.5:1 to 5:1, 1.75:1 to 4:1, or 2.0:1 to 3.25:1. The thickness t is related to the average chamfer height H. 平均值 The ratio can be, for example, at least 1.2:1, at least 1.3:1, at least 1.5:1, at least 1.75:1, or at least 2.0:1. The thickness t and the average chamfer height H... 平均值 The ratio can be, for example, up to 10:1, up to 7.5:1, up to 5:1, up to 4:1, or up to 3.25:1.

[0047] The glass articles can be of any size. For example, they can be rolled ultrathin long strips of glass (glass rolls) or individual smaller glass sections cut from glass rolls, or individual glass plates, or individual smaller glass articles (such as fingerprint sensors (FPS) or display cover glass), etc. Optionally, the glass articles of this disclosure are sheet-like or sheet-like articles, particularly rectangular or square articles having a length y and a width z. Preferably, both the length y and the width z are much larger than the thickness z of the article. For example, the length y and / or the width z can be at least 1 mm, at least 2 mm, at least 5 mm, at least 10 mm, at least 15 mm, at least 20 mm, at least 25 mm, at least 30 mm, at least 40 mm, or at least 50 mm. For example, the length y and / or width z can be up to 500 mm, up to 400 mm, up to 300 mm, up to 200 mm, up to 150 mm, up to 125 mm, up to 100 mm, or up to 70 mm. The ratio of length y to width z can be 1:1 or higher. In some embodiments, the glass article may have a groove, particularly for use with a front-facing camera in smartphone applications.

[0048] In one embodiment of this disclosure, the length y of the article is in the range of 10 mm to 500 mm, and / or the width z is in the range of 5 mm to 400 mm. For example, the length y and / or width z are in the range of 10 mm to 400 mm, 15 mm to 300 mm, 20 mm to 200 mm, 25 mm to 150 mm, 30 mm to 125 mm, 40 mm to 100 mm, or 50 mm to 70 mm. The length y and / or width z can be, for example, at least 5 mm, at least 10 mm, at least 15 mm, at least 20 mm, at least 25 mm, at least 30 mm, at least 40 mm, or at least 50 mm. The length y and / or width z can be, for example, at most 500 mm, at most 400 mm, at most 300 mm, at most 200 mm, at most 150 mm, at most 125 mm, at most 100 mm, or at most 70 mm.

[0049] Optionally, the article has exactly one edge connecting its first and second surfaces. Depending on the shape of the article, the edge may have different sides. For example, for a plate or sheet-like article with a rectangular or square shape, the edge has four sides, where two opposite sides represent the length y of the article and the remaining two opposite sides represent the width z of the article. The position of two adjacent sides connecting the edge is often referred to as a corner.

[0050] Compressive stress (CS) (also known as “pressure stress” or “surface stress”) is the stress caused by the displacement effect on the glass network that runs through the glass surface after ion exchange, but without deformation of the glass.

[0051] "Penetration depth" or "depth of ion exchange layer" or "ion exchange depth" ("layer depth" or "ion exchange layer depth", DoL) is the thickness of the glass surface layer where ion exchange occurs and compressive stress is generated. The compressive stress CS and penetration depth DoL can be optically measured (specifically, via a waveguide mechanism) using a commercially available stress meter FSM6000 (e.g., "Luceo Co., Ltd.", Tokyo, Japan).

[0052] When a stress center (CS) is generated on one or both sides of a single glass pane, according to Newton's third law, tensile stress must be generated in the central region of the glass to balance the stress; this tensile stress is called central tension (CT). CT can be calculated based on the measured CS and DoL values.

[0053] Ion exchange refers to the hardening or chemical tempering of glass through an ion exchange process (also known as chemical tempering), a process well-known to those skilled in the art of glass manufacturing and processing. Tempering can be achieved by immersing the glass layer in a salt bath containing monovalent ions to exchange with alkali ions within the glass. The radii of the monovalent ions in the salt bath are larger than those of the alkali ions within the glass. After ion exchange, the larger ions are forced into the glass network, thus creating compressive stress on the glass. Ion exchange significantly enhances the strength and flexibility of the glass. Furthermore, the CS produced by chemical tempering improves the bending properties of the tempered glass layer and increases its scratch resistance. Typical salts used for chemical tempering are potassium-containing salts. + Molten salt or salt mixture. An optional salt bath for chemical tempering is one containing Na. + and / or containing K + Molten salts or mixtures of salts are used. Optional salts include NaNO3, KNO3, NaCl, KCl, Na2SO4, K2SO4, Na2CO3, K2CO3, and K2Si2O5. Additives, such as NaOH, KOH, and other sodium or potassium salts, are also used to better control the ion exchange rate used for chemical tempering. Ion exchange, for example, can be carried out in KNO3 at temperatures ranging from 300°C to 480°C, particularly 340°C to 450°C, or 390°C to 450°C, for durations ranging from, for example, 30 seconds to 48 hours, particularly about 20 minutes. Chemical tempering is not limited to a single step. It can include multiple steps in a salt bath with different concentrations of alkali metal ions to achieve better tempering properties. Therefore, chemically tempered glass layers can be tempered in one step or in several steps, such as two steps. Two-step chemical tempering is particularly suitable for Li2O-containing glasses because lithium can exchange with both sodium and potassium ions.

[0054] In one embodiment of this disclosure, the average chamfered surface profile is such that for any position xi of the average chamfered surface, there is exactly an average chamfered surface tangent angle α. xi For example, an average chamfered surface can be described by a continuous function. In another embodiment of this disclosure, more than one angle α xi This can be attributed to more than one location xi of the average chamfered surface, for example, two of its locations. Specifically, the average chamfer structure may include a peak or angle at location xi connecting locations xh and xj, where the tangent angle α of the average chamfered surface at location xh is... xh The angle α between the average chamfered surface and the average chamfered surface tangent at position xj on the average chamfered surface. xjThe difference is at least 1°, at least 2°, at least 5°, or at least 10°, for example, 15° to 80°, 20° to 70°, or 30° to 60°. For example, the tangent angle α of the average chamfered surface at position xh on the average chamfered surface. xh It can be 30°, while the average tangent angle α of the chamfered surface at position xj on the average chamfered surface is... xj It can be 90°. In this case, the angle at position xi, which connects positions xh and xj, changes rapidly. In fact, any angle in the range of 30° to 90° can be attributed to the average tangent angle α of the chamfered surface at position xi. i Wherein position xi connects α xh The position xh at 30° and α xj The position xj is 90°.

[0055] In one embodiment of this disclosure, the average chamfered surface profile is such that the tangent angle α of the average chamfered surface at any position xi on the average chamfered surface is... xi The tangent angle α of the average chamfered surface at any other location xj on the average chamfered surface is different. xj In other words, the average chamfered surface profile can be represented as a strictly monotonic function. However, in another embodiment of this disclosure, the average chamfered surface profile makes the tangent angle α of the average chamfered surface at position xi of the average chamfered surface... xi The angle α between the average chamfered surface and the average chamfered surface at another position xj on the average chamfered surface. xj The same. In one embodiment of this disclosure, the average chamfered surface profile such that for at least 90%, at least 95%, at least 99%, or at least 99.9% of the positions xi of the average chamfered surface, the tangent angle α of the average chamfered surface is... xi The range is >0° to <45°, >135° to <180°, or 89° to 91°. In one embodiment of this disclosure, the average chamfered surface profile such that for at least 5% to 20% of the positions xi of the average chamfered surface, the tangent angle α of the average chamfered surface is... xi The range is 89° to 91°.

[0056] The chamfered structure has a chamfer height H, which is defined as the position xi (α) closest to the first surface of the glass article from the average chamfered surface. xi = 45°) to the position xj (α) closest to the second surface of the glass product on the average chamfered surface. xj The projection of a line segment (=135°) onto a line that forms a 90° angle with both the tangents of the first and second surfaces.

[0057] The chamfer height is preferably determined using an optical microscope, specifically based on a microscope image with the observation direction facing the edge of the glass artifact. Based on such a microscope image, particularly in transmitted light mode, the chamfer height H can be visually determined as the height H of the chamfered structure. The magnification can be, for example, 200x. The focus is on the top plane. The glass artifact is positioned such that the top plane is not tilted. Therefore, the top plane is perpendicular to the direction of light. Typically, images of particularly high quality are obtained using a Nikon Y-TV55 microscope, particularly with automatic white balance, automatic brightness, and automatic contrast.

[0058] It is worth noting that the chamfer height H can vary at different locations around the perimeter of the glass article. For example, at location p1, H(p1) = H1, and at location p2, H(p2) = H2, where p1 ≠ p2 and H1 ≠ H2. The local chamfer height LH is defined herein as the average local chamfer height along a portion of the length y and / or width z of the article, where the length of said portion is 300µm to 600µm (e.g., 350µm or 500µm). The local chamfer height LH can be determined by optical microscopy, particularly based on microscopic images with a viewing direction facing the edge of the glass article. For example, in such images, the boundary of the chamfer can be fitted to a box with a length of 300 to 600µm, such as 350µm or 500µm, and the height of the box can be recorded as the local chamfer height LH. The height of the box is chosen such that the top and bottom lines best fit the boundary of the chamfer along the length of the box. Therefore, the local chamfer height LH represents the average value over the length of the box. Measuring the local chamfer height LH as an average value along a portion from 300 to 600 µm, for example, along a portion of 350 µm or 500 µm, has proven particularly advantageous for characterizing local chamfer heights. If this portion is reduced, the risk of noise in the data increases. If the portion is increased, the risk of the associated chamfer height variation being averaged increases. The local chamfer height LH can, for example, be measured as an average value along a portion of at least 300 µm or at least 350 µm. The local chamfer height LH can, for example, be measured as an average value along a portion of at most 600 µm or at most 500 µm.

[0059] The total chamfer height variation (TCHV) of the chamfer height H along the length y and / or width z of the glass article is defined as the maximum chamfer height H along at least a portion of the article's length y and / or width z. max With minimum chamfer height H min The difference divided by the average chamfer height H along the portion of the article's length y and / or width z avg The portion is at least 25% of the length y and / or width z.

[0060] TCHV = (H) max -H min ) / H avg (Formula 1) Optionally, the portion is at least 50% of the length y and / or the width z, at least 75% of the length y and / or the width z, at least 90% of the length y and / or the width z, at least 99% of the length y and / or the width z, or 100% of the length y and / or the width z. In one embodiment of this disclosure, the portion is at least 25%, at least 50%, at least 75%, at least 90%, at least 99%, or 100% of the length y and the width z.

[0061] In one embodiment of this disclosure, the TCHV is at most 0.75, at most 0.70, at most 0.65, at most 0.60, at most 0.55, at most 0.50, at most 0.45, at most 0.40, at most 0.35, at most 0.30, at most 0.25, or at most 0.20. The TCHV may, for example, be greater than 0.05, greater than 0.10, or greater than 0.15.

[0062] As described above, the local chamfer height LH is defined herein as the average local chamfer height along a portion of the length y and / or width z of the article, wherein the length of said portion is 300µm to 600µm, for example 350µm or 500µm. Optionally, H is determined based on the corresponding local chamfer height LH at different locations along the perimeter of the glass article. max H min and H avg Specifically, the local chamfer height LH can be measured every 10mm around the entire circumference of the glass product. max It can be defined as the highest LH, H min It can be defined as the lowest LH, H avg It can be defined as the average of all local chamfer heights LH determined around the perimeter of the glass article. Conversely, H can be determined from this. max H min and H avg Calculate TCHV (based on Equation 1).

[0063] When determining the local chamfer height LH, the corners of two adjacent sides connecting the edges can be excluded. For example, for a glass article with a length y of 60 mm and a width z of 60 mm, if actual corners of the article are excluded, determining the local chamfer height every 10 mm can produce a total of 20 different LH values, allowing measurements to be taken at length positions of y = 10 mm, 20 mm, 30 mm, 40 mm, and 50 mm, and width positions of z = 10 mm, 20 mm, 30 mm, 40 mm, and 50 mm (excluding y and z = 0 mm and y and z = 60 mm). A resolution of 10 mm has proven sufficient to characterize variations in the chamfer height of a glass article. However, if higher resolution is required, the local chamfer height LH can certainly be determined at more locations around the circumference of the glass article, such as every 5 mm, every 2 mm, every 1 mm, or every 0.5 mm.

[0064] As described above, for a glass article with a length y of 60 mm and a width z of 60 mm, if the actual corners of the article are excluded, a total of 20 different LH values ​​are generated by determining the local chamfer height every 10 mm around the entire circumference of the glass article. In this case, TCHV is determined as the maximum chamfer height H along 100% of the article's length y and width z. max With minimum chamfer height H min The difference divided by the average chamfer height H along 100% of the product's length y and width z avg The reason is that the local chamfer height LH is determined around the entire perimeter of the glass article, and therefore along 100% of the article's length y and width z. Typically, it is necessary to determine the local chamfer height LH around the entire perimeter of the glass article (and therefore along 100% of the article's length y and width z).

[0065] However, in embodiments of this disclosure, the TCHV along a specific portion of the length and / or width of the glass article may be particularly relevant. For example, in some cases, a specific portion of the length and / or width of the glass article requires particularly high edge impact resistance because these portions are exposed to particularly large forces, for example, during handling and / or use. Therefore, it is not necessary to determine the TCHV of the chamfer height H in the length y and / or width z direction of the glass article along 100% of the article's length y and width z. A portion along at least 25% of the length y and / or width z may be sufficient to determine the TCHV.

[0066] In some embodiments, the ratio (t*H) avg / TCHV is at least 250µm 2 At least 500µm 2 At least 750µm 2 At least 1000µm 2At least 1250µm 2 At least 1500µm 2 At least 1750µm 2 At least 2000µm 2 At least 2250µm 2 At least 2500µm 2 For example, at least 2750µm 2 At least 3000µm 2 At least 3500µm 2 At least 4000µm 2 At least 4500µm 2 At least 5000µm 2 At least 6000µm 2 At least 7000µm 2 or at least 8000µm 2 The corresponding ratio is a good indicator of edge impact resistance. Ratio (t*H) avg The higher the ratio (t*H) / TCHV, the better the edge impact resistance. avg The ratio R / TCHV is also referred to as "ratio R" or simply "R" in this paper. Ratio R can be below 20000µm. 2 Below 15000µm 2 or below 10000µm 2 .

[0067] The glass articles disclosed herein are not limited to certain glass compositions. However, some glass compositions are particularly advantageous. In one embodiment, the glass may be a silicate glass, such as aluminosilicate glass, lithium aluminosilicate glass, or borosilicate glass. The glass may also be soda-lime glass. The glass may contain alkali metal oxides, such as Na₂O, particularly in an amount sufficient to allow for chemical tempering.

[0068] The glass may comprise the following components in weight percentages: 45.0 to 75.0 wt% SiO2, 0 to 8.5 wt% B2O3, 2.5 to 25.0 wt% Al2O3, 0 to 10.0 wt% Li2O, 5.0 to 20.0 wt% Na2O, 0 to 10.0 wt% K2O, 0 to 15.0 wt% MgO, 0 to 10.0 wt% CaO, 0 to 5.0 wt% BaO, 0 to 5.5 wt% ZnO, 0 to 5.0 wt% TiO2, 0 to 5.0 wt% ZrO2, and 0 to 20.0 wt% P2O5. Optionally, the glass may comprise the following components in weight percentages: 45.0 to 75.0 wt% SiO2, 0 to 5.0 wt% B2O3, 2.5 to 25.0 wt% Al2O3, 0 to 10.0 wt% Li2O, 5.0 to 20.0 wt% Na2O, 0 to 10.0 wt% K2O, 0 to 15.0 wt% MgO, 0 to 10.0 wt% CaO, 0 to 5.0 wt% BaO, 0 to 5.0 wt% ZnO, 0 to 2.5 wt% TiO2, 0 to 5.0 wt% ZrO2, and 0 to 20.0 wt% P2O5. In some embodiments, the glass is composed of the components mentioned in the foregoing list, with a total content of at least 95.0 wt%, at least 97.0 wt%, or at least 99.0 wt%.

[0069] As used herein, the terms "free of X" and "free of component X" preferably mean that the glass substantially does not contain said component X, that is, this component exists in the glass at most as an impurity or contaminant, but is not added to the glass composition as a single component. This means that component X is not added in the necessary amount. The unnecessary amount according to this disclosure is less than 100 ppm (m / m), less than 50 ppm, or less than 10 ppm. Therefore, "X" can refer to any component, such as lead cations or arsenic cations. Optionally, the glass described herein is substantially free of any components not mentioned in this disclosure.

[0070] In one embodiment, the glass may comprise the following components in weight percentages: 45.0 to 72.0 wt% SiO2, 0 to 4.7 wt% B2O3, 4.0 to 24.0 wt% Al2O3, 0 to 6.0 wt% Li2O, 8.0 to 18.0 wt% Na2O, 0 to 8.0 wt% K2O, 0 to 10.0 wt% MgO, 0 to 3.0 wt% CaO, 0 to 2.0 wt% BaO, 0 to 3.0 wt% ZnO, 0 to 1.0 wt% TiO2, 0 to 4.6 wt% ZrO2, and 0 to 15.0 wt% P2O5.

[0071] In one embodiment, the glass may comprise the following components by weight percentage: 51.0 to 65.0 wt% SiO2, 0 to 4.7 wt% B2O3, 11.0 to 24.0 wt% Al2O3, 0 to 6.0 wt% Li2O, 8.0 to 18.0 wt% Na2O, 0 to 8.0 wt% K2O, 0 to 5.5 wt% MgO, 0 to 1.0 wt% CaO, 0 to 1.0 wt% BaO, 0 to 3.0 wt% ZnO, 0 to 1.0 wt% TiO2, 0 to 4.6 wt% ZrO2, and 0 to 10.0 wt% P2O5.

[0072] In one embodiment, the glass may comprise the following components by weight percentage: 45.0 to 72.0 wt% SiO2, 0 to 4.7 wt% B2O3, 4.0 to 24.0 wt% Al2O3, 0 to 3.0 wt% Li2O, 8.0 to 18.0 wt% Na2O, 0 to 8.0 wt% K2O, 0 to 5.5 wt% MgO, 0 to 1.0 wt% CaO, 0 to 2.0 wt% BaO, 0 to 3.0 wt% ZnO, 0 to 1.0 wt% TiO2, 0 to 3.0 wt% ZrO2, and 0 to 15.0 wt% P2O5.

[0073] The lower limit of the amount of SiO2 can be, for example, at least 45% by weight, at least 51% by weight, or at least 55% by weight. The upper limit of the amount of SiO2 can be, for example, at most 75% by weight, at most 72% by weight, or at most 65% by weight.

[0074] The lower limit of the amount of B2O3 may be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of B2O3 may be, for example, at most 5% by weight, at most 2% by weight, or at most 1% by weight. The glass may, for example, be free of B2O3.

[0075] The lower limit of the amount of Al2O3 can be, for example, at least 2.5% by weight, at least 4% by weight, or at least 11% by weight. The upper limit of the amount of Al2O3 can be, for example, at most 25% by weight, at most 24% by weight, or at most 20% by weight.

[0076] The lower limit of the amount of Li2O can be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of Li2O can be, for example, at most 10% by weight, at most 6% by weight, or at most 3% by weight. The glass may, for example, be free of Li2O.

[0077] The lower limit of the amount of Na2O can be, for example, at least 5% by weight, at least 8% by weight, or at least 10% by weight. The upper limit of the amount of Na2O can be, for example, at most 20% by weight, at most 18% by weight, or at most 16% by weight.

[0078] The lower limit of the amount of K2O may be, for example, at least 0.5% by weight, at least 1% by weight, or at least 2% by weight for some variants. The upper limit of the amount of K2O may be, for example, at most 10% by weight, at most 8% by weight, at most 5% by weight, at most 3% by weight, or at most 2% by weight or at most 1.5% by weight for some variants. The glass may, for example, be K2O-free.

[0079] The lower limit of the amount of MgO can be, for example, at least 0.5% by weight, at least 1% by weight, or at least 2% by weight. The upper limit of the amount of MgO can be, for example, at most 15% by weight, at most 10% by weight, or at most 5.5% by weight. The glass may, for example, be free of MgO.

[0080] The lower limit of the amount of CaO can be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of CaO can be, for example, at most 10% by weight, at most 3% by weight, or at most 1% by weight. The glass may, for example, be free of CaO.

[0081] The lower limit of the amount of P2O5 can be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of P2O5 can be, for example, at most 20% by weight, at most 15% by weight, or at most 10% by weight. The glass may, for example, be free of P2O5.

[0082] The lower limit of the amount of BaO can be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of BaO can be, for example, at most 5% by weight, at most 2% by weight, or at most 1% by weight. The glass may, for example, be free of BaO.

[0083] The lower limit of the amount of ZnO can be, for example, at least 0.1% by weight, at least 0.2% by weight, or at least 0.5% by weight. The upper limit of the amount of ZnO can be, for example, at most 5% by weight, at most 3% by weight, or at most 1% by weight. The glass may, for example, be free of ZnO.

[0084] The lower limit of the amount of ZrO2 can be, for example, at least 0.2 wt%, at least 0.5 wt%, or at least 1 wt%. The upper limit of the amount of ZrO2 can be, for example, at most 5 wt%, at most 4.6 wt%, or at most 3 wt%. The glass may, for example, be free of ZrO2.

[0085] The lower limit of the amount of TiO2 can be, for example, at least 0.1 wt%, at least 0.2 wt%, or at least 0.5 wt%. The upper limit of the amount of TiO2 can be, for example, at most 2.5 wt%, at most 1.5 wt%, or at most 1 wt%. The glass may, for example, be free of TiO2.

[0086] Optionally, the glass comprises the following components in the amounts shown below (by weight %):

[0087] Optionally, the glass comprises the following components in the amounts shown below (by weight %):

[0088] This disclosure also relates to a method for producing chemically tempered glass articles, and particularly to the chemically tempered glass articles of this disclosure. The method specifically includes the following steps in the order shown: A (separate) glass article is provided, comprising: a first main surface and a second main surface, and at least one edge surface connecting the first main surface and the second main surface. Chemical tempering of glass products, and subsequent... Both the central and peripheral regions of the glass product are brought into contact with the etching solution, with the etching rate in the peripheral region being higher than that in the central region. The central region consists of a portion of glass material whose closest distance to the edge surface, measured parallel to the first or second main surface, is greater than 5.0 mm. The peripheral area is composed of a portion of glass material, measured parallel to the first or second main surface, with a minimum distance of 5.0 mm from the edge surface.

[0089] To ensure that both the central and peripheral regions of the glass article are in contact with the etching solution, the contact step (etching step) of this disclosure is performed on a single glass article. Specifically, "single glass article" refers to a glass article that is not composed of any kind of layered composite material. The entire surface of the glass article should be able to contact the etching solution. Specifically, this includes both the first and second main surfaces of the glass article as a whole.

[0090] The contact step (etching step) performed on a single piece of glass distinguishes this disclosure from prior art disclosures involving the etching of layers of glass. Typically, such etching of layers is intended to create a chamfered structure at the edges of the glass. However, this chamfered structure is quite different from the advantageous peripheral regions of this disclosure. While the glass articles of this disclosure may also include chamfered structures, they additionally or optionally have the advantageous peripheral regions described herein.

[0091] To achieve the chamfered structure, etching is necessary on the layered composite material. For example, even if the chamfered structure is introduced only on a single glass article, the glass article must be provided as a partially layered composite material to achieve the chamfered structure through etching. In this case, the glass article is typically laminated between two thick dummy glasses to achieve the chamfered structure through etching.

[0092] In contrast, in order to obtain the glass articles of this disclosure having the advantageous peripheral regions as described herein, an etching step is performed on individual glass articles that do not belong to any kind of partially layered composite material.

[0093] In this disclosure, it has been found that correspondingly modified etching and / or edge treatment steps can be beneficial to edge strength. It has been found that it is advantageous if the etching rate around the edge is higher than the etching rate at the center of the glass. In particular, the thinning of the etch is adjusted by fine-tuning the etching rate, by adjusting, for example, the etching medium, temperature, and etching duration. The etching duration can, for example, range from 5 seconds to 120 minutes, such as 30 seconds to 60 minutes, 1.0 to 30 minutes, 2.0 to 15 minutes, or 5.0 to 10 minutes. The etching duration can, for example, be at least 5 seconds, at least 30 seconds, at least 1.0 minute, at least 2.0 minutes, or at least 5.0 minutes. The etching duration can, for example, be at most 120 minutes, at most 60 minutes, at most 30 minutes, at most 15 minutes, or at most 10 minutes.

[0094] In some embodiments, the etching rate of the peripheral region is at least 10%, at least 20%, at least 25%, at least 50%, at least 75%, at least 100%, at least 150%, at least 200%, at least 250%, at least 300%, or at least 400% higher than the etching rate of the central region of the glass article. In some embodiments, the etching rate of the peripheral region is at most 1000%, at most 950%, at most 900%, at most 850%, at most 800%, at most 750%, at most 700%, at most 650%, at most 600%, at most 550%, or at most 500% higher than the etching rate of the central region of the glass article. In some embodiments, the etching rate of the peripheral region is 10% to 1000%, 20% to 950%, 25% to 900%, 50% to 850%, 75% to 800%, 100% to 750%, 150% to 700%, 200% to 650%, 250% to 600%, 300% to 550%, or 400% to 500% higher than the etching rate of the central region of the glass article.

[0095] In some embodiments, the step of contacting both the central and peripheral regions of the glass article with the etching solution reduces the average thickness of the central region of the glass article by 0.5 to 4 μm, and / or reduces the average thickness of the peripheral region of the glass article by 1.5 to 14 μm. Specifically, if the etching rate of the peripheral region is higher than the etching rate of the central region of the glass article, the step of contacting both the central and peripheral regions of the glass article with the etching solution results in a smaller reduction in the average thickness of the central region compared to the reduction in the average thickness of the peripheral region. For example, if the average thickness of the central region is reduced by 4 μm, the reduction in the average thickness of the peripheral region is greater than 4 μm.

[0096] Optionally, the glass can be rotated in the etching solution. Optionally, it rotates about a central axis of rotation; ideally, the glass is placed vertically, and the folding axis (for a single folded cover glass) is perpendicular to the axis of rotation. By adjusting / matching the etching solution and process temperature (= etching rate or etching speed) and the rotation speed and / or direction, the etching rate of the peripheral region of the glass can be controlled in particular. By doing so, thinning of the peripheral region is achieved, and the width of the thinned region can also be fine-tuned. As an alternative or supplement to rotating the glass in the etching solution, stirring the etching solution is also an option to make the etching solution flow around the edge of the glass. Here, the direction of rotation can also be alternated; however, due to the inertia of the etching solution, the reverse rotation time is usually longer.

[0097] In particular, the method may include one or more measures selected from the group consisting of: Rotate the glass artifact in the etching solution. The etching solution causes foaming, with stronger foaming occurring at the periphery of the glass artifact compared to the central area. The etching solution is stirred so that the etching rate in the peripheral region is higher than that in the central region of the workpiece. The etching solution is directed to the peripheral area of ​​the glass article, specifically through at least one nozzle present in an etching tank containing the etching solution, and Combinations of two or more of them.

[0098] The glass product can rotate clockwise or counterclockwise, or alternate between clockwise and counterclockwise, around the axis of rotation.

[0099] The ratio of the duration of clockwise rotation to the duration of counterclockwise rotation can, for example, be in the range of 1:3 to 3:1, such as 1:2 to 2:1, and particularly approximately 1:1. The ratio of the duration of clockwise rotation to the duration of counterclockwise rotation can, for example, be at least 1:3, at least 1:2, or at least 1:1. The ratio of the duration of clockwise rotation to the duration of counterclockwise rotation can, for example, be at most 3:1, at most 2:1, or at most 1:1.

[0100] The rotational speed of the glass article can be, for example, in the range of 0.1 to 10.0 revolutions per minute (rpm), such as 0.2 to 5.0 rpm, or 0.5 to 2.0 rpm. The rotational speed of the glass article can be, for example, at least 0.1 rpm, at least 0.2 rpm, or at least 0.5 rpm. The rotational speed of the glass article can be, for example, at most 10.0 rpm, at most 5.0 rpm, or at most 2.0 rpm.

[0101] Furthermore, regarding the optional rotation of the glass in the etching solution, further fine-tuning of the process can be achieved by changing the balance between one rotation direction and the opposite rotation direction to introduce symmetrical or asymmetrical chamfers (here, opposing edges show opposite chamfer directions). Additionally, for partially thinned glass (LSG), i.e., glass with a thinned region and a thicker unfolded region around its fold axis, the thinned edge can have additional benefits to its flexural strength and can also mitigate the wrinkling effect around the thinned section due to non-uniform expansion during chemical tempering. In the latter case, such an LSG is preferably rotated about its longitudinal axis (perpendicular to the fold axis). Figure 6 The corresponding embodiments are illustrated schematically.

[0102] Furthermore, rotation around a central axis perpendicular to the folding axis of the glass product is advantageous not only for LSG but also for glass products in general, because the most critical sections of the peripheral region of the glass product are those that bend during application. Therefore, enhanced etching of these segments in the peripheral region is advantageous compared to the segments of the peripheral region that do not bend during application. Enhanced etching is performed on the segments of the peripheral region parallel to the longitudinal axis by rotation around the longitudinal axis. These segments parallel to the longitudinal axis can also be referred to as the long sides of the glass product. These long sides typically bend during application. In contrast, the short sides typically do not bend during application.

[0103] In some embodiments, the rotation step includes rotating the glass article about a rotation axis, wherein the rotation axis is perpendicular to the folding axis of the glass article. Specifically, the rotation axis may be parallel to the long side of the glass article and the folding axis may be parallel to the short side of the glass article, or the rotation axis may be parallel to the short side of the glass article and the folding axis may be parallel to the long side of the glass article.

[0104] In some embodiments, the axis of rotation is one of the axes of symmetry of the glass article. In particular, the axis of rotation is an axis of symmetry of the glass article that is parallel to the long side of the glass article.

[0105] In some embodiments, the etching solution is stirred such that it moves about a stirring shaft parallel to the long side of the glass article.

[0106] In some embodiments, an etching solution stream is directed onto a peripheral area of ​​the glass article. The etching solution stream can be a new etching solution stream, an existing etching solution stream, or a combination of both. The etching solution stream can be directed onto the peripheral area of ​​the glass article, particularly through at least one nozzle. For example, a new etching solution can be applied from one or more etching tanks containing etching solutions and directed onto the peripheral area of ​​the glass article through at least one nozzle. An existing etching solution stream can be directed onto the peripheral area of ​​the glass article, for example, by forming an etching solution circulation, particularly through at least one pump.

[0107] In some embodiments, the method includes taking measures during etching, such as masking areas not to be etched or immersing the glass article in an etch solution in a bent state. Immersion in a bent state means that the glass article is folded, and then only the folded area is immersed in the etching solution. The additional thinning of the folded area reduces the CS / DoL of the thinned folded area, resulting in a more balanced strength and scalability compared to the unfolded area. Another advantage is the lower thickness of the thinned area, which is beneficial for folding.

[0108] In some embodiments, the etching solution comprises HF and / or NH4HF2, and additional inorganic and / or organic acids. The inorganic acids are particularly selected from the group consisting of HCl, HNO3, H2SO4, and mixtures of two or more thereof.

[0109] More specifically, the etchant solution optionally comprises or consists of a mixture of the following substances: HF and / or NH4HF2, and inorganic acids (e.g., HCl, HNO3, H2SO4 or a mixture of two or more thereof) and / or organic acids (e.g., acetic acid).

[0110] The total amount of HF and NH4HF2 can, for example, range from 0.1 wt% to 10.0 wt%, such as 0.5 to 5.0 wt%, or 1.0 to 2.0 wt%. The total amount of HF and NH4HF2 can, for example, be at least 0.1 wt%, at least 0.5 wt%, or at least 1.0 wt%. The total amount of HF and NH4HF2 can, for example, be at most 10.0 wt%, at most 5.0 wt%, or at most 2.0 wt%.

[0111] The weight ratio of the total amount of inorganic acid to the total amount of HF and NH4HF2 can be, for example, in the range of 0.1:1 to 10:1, such as 0.2:1 to 5:1, or 0.5:1 to 2:1. The weight ratio of the total amount of inorganic acid to the total amount of HF and NH4HF2 can be, for example, at least 0.1:1, at least 0.2:1, or at least 0.5:1. The weight ratio of the total amount of inorganic acid to the total amount of HF and NH4HF2 can be, for example, at most 10:1, at most 5:1, or at most 2:1.

[0112] For example, the weight ratio of the total amount of organic acids to the total amount of HF and NH4HF2 can be, for example, in the range of 0.1:1 to 10:1, such as 0.2:1 to 5:1, or 0.5:1 to 2:1. The weight ratio of the total amount of organic acids to the total amount of HF and NH4HF2 can be, for example, at least 0.1:1, at least 0.2:1, or at least 0.5:1. The weight ratio of the total amount of organic acids to the total amount of HF and NH4HF2 can be, for example, at most 10:1, at most 5:1, or at most 2:1.

[0113] The etchant solution may, for example, comprise 3% by weight of NH4HF2 and 3% by weight of HNO3, or consist thereof; or the etchant solution may comprise 2% by weight of NH4HF2, 2% by weight of HNO3 and 5% by weight of acetic acid, or consist thereof; or the etchant solution may comprise 1% by weight of HF and 1% by weight of HNO3, or consist thereof. The etchant solution may comprise one or more surfactants, such as alkylphenol ethoxylate, or ammonium dodecyl sulfate, or a mixture of alkylphenol ethoxylate and ammonium dodecyl sulfate.

[0114] The temperature of the etching solution can be, for example, in the range of 1°C to 50°C, 1°C to 40°C, such as 5°C to 30°C, or 15°C to 25°C. The temperature of the etching solution can be, for example, at least 1°C, at least 5°C, or at least 15°C. The temperature of the etching solution can be, for example, at most 50°C, at most 40°C, at most 30°C, or at most 25°C.

[0115] In some embodiments, the method further includes a step of contacting both the central and peripheral regions of the glass article with an etching solution prior to chemical tempering. In the etching step prior to chemical tempering, the etching rate of the peripheral region may be higher than that of the central region of the article.

[0116] The newly developed method of this invention can follow a UTG processing step in its initial step, which includes: - Stack multiple UTG boards with glue. - Cut the "unit" blocks using a disc cutter (cut to size). - Perform edge grinding and / or polishing (optional). - Perform edge etching (immerse the sized blocks in the etching solution). - Divide the block into individual units. - Perform chemical tempering of the unit. - Cleaning / Cleaning.

[0117] In particular, prior to the chemical tempering step, the method of this disclosure may include steps in the following order: Provides layered composite materials comprising multiple glass products. Optionally, the layered composite material can be cut to the required size. Optionally, edge grinding and / or polishing may be performed. The layered composite material is immersed in the etching solution. Layered composite materials are separated into individual glass products.

[0118] Layered composite materials may include, for example, 2 to 30 glass articles, such as 3 to 20 glass articles or 5 to 15 glass articles. The number of glass articles in a layered composite material may be, for example, at least 2, at least 3, or at least 5. The number of glass articles in a layered composite material may be, for example, at most 30, at most 20, or at most 15.

[0119] In some embodiments, the method of this disclosure includes, in particular, the following steps in the order shown: Provides layered composite materials comprising multiple glass products. Optionally, the layered composite material can be cut to the required size. Optionally, edge grinding and / or polishing may be performed. The layered composite material is immersed in the etching solution. Layering of layered composite materials to provide individual glass articles. Optionally, both the central and peripheral regions of a single glass article are brought into contact with the etching solution, wherein the etching rate of the peripheral region is higher than that of the central region of the article. The central region consists of a portion of glass artifacts, measured parallel to the first or second main surface, whose closest distance to the edge surface is greater than 5.0 mm. The outer region consists of a portion of glasswork, measured parallel to the first or second main surface, with a minimum distance of 5.0 mm from the edge surface. Chemical tempering of individual glass items, and subsequently Both the central and peripheral regions of a single glass article are brought into contact with the etching solution, wherein the etching rate of the peripheral region is higher than that of the central region. The central region consists of a portion of glass artifacts, measured parallel to the first or second main surface, whose closest distance to the edge surface is greater than 5.0 mm. The outer region consists of a portion of glasswork that is at most 5.0 mm from the edge surface, as measured parallel to the first or second main surface.

[0120] This disclosure also relates to the uses of the glass articles of this disclosure, particularly in consumer electronics, such as: Foldable handheld devices, including smartphones, tablets, or wearable devices. Laptop Monitor, or Monitor screen.

[0121] In particular, the present invention relates to the use of the glass articles of the present invention in foldable smartphones and laptops. Attached Figure Description

[0122] Figure 1 Three embodiments of the method of this disclosure are illustrated schematically, respectively. Figure 1 A, Figure 1 B and Figure 1 C. Etching solution throughout Figure 1 The middle part is represented by a dashed line.

[0123] Figure 1 A schematic illustration shows an embodiment of rotating a glass article 11 in an etching solution. The rotational motion is indicated by two black arrows. The rotation axis 12 is shown as a dashed line.

[0124] Figure 1 B schematically illustrates an embodiment in which the etching solution flow is directed onto the peripheral area of ​​the glass article 11. This is indicated by a black arrow originating from the location of the etching tank, where the nozzle 13 is located.

[0125] Figure 1 C schematically illustrates an example of stirring an etching solution. The two black arrows indicate stirring.

[0126] Figure 2 A schematic illustration shows an embodiment of rotating a glass article 21 in an etching solution. The rotational motion is indicated by two black arrows. The rotation axis 22 is shown as a dashed line.

[0127] Figure 2 B schematically shows an enlarged view of the glass article, where the rotation axis 22 is shown as a dashed line and the folding axis 24 is shown as a dotted line. The rotation axis 22 is perpendicular to the folding axis 24 of the glass article.

[0128] Figure 2 C also schematically shows an enlarged view of the glass product. Figure 2C indicates that the glass article has two parallel long sides 25 and two parallel short sides 26, wherein the long sides 25 are perpendicular to the short sides 26. The length of the long side 25 is greater than the length of the short side 26.

[0129] Figure 2 B and Figure 2 C schematically shows that the rotation axis 22 is parallel to the long side 25 of the glass article, and the folding axis 24 is parallel to the short side 26 of the glass article.

[0130] Figure 3 The schematic illustration shows a glass article of the present disclosure having a central region 31 and a peripheral region 32. As indicated by the peripheral region 32 being a darker color than the central region 31, the average thickness of the peripheral region 32 is less than the average thickness of the central region 31.

[0131] Figure 4 An image of the glass article of this disclosure is shown. The average thickness of the peripheral region is less than the average thickness of the central region. The image was taken with the glass flat under a uniform light source. The principle is the same as Newton's rings. It shows the interference fringes formed by light being reflected by the upper and lower surfaces of the glass. These lines can be considered as thickness contour lines. Denserly distributed lines indicate more abrupt changes in thickness.

[0132] Figure 5 The setup for the sliding test is illustrated schematically. A glass article 51 is tested in the sliding test, where the folding distance 56 is equal to 50 times the center thickness of the glass article 51. For ultra-thin glass (UTG), the center thickness of the glass article 51 corresponds to the average thickness of the central region of the glass article 51. For partially thinned glass (LSG), the center thickness of the glass article 51 corresponds to the average thickness of the folded region of the central region. In the sliding test, the foldable glass is placed in a U-shape between two parallel plates 52 and 53. The two plates 52 and 53 are large enough to cover the entire article 51. Then, one plate (here, 53) moves towards the other plate (here, 52) at a speed of 60 mm / min while remaining parallel (arrow 55 indicates the movement) until the designed folding distance 56 reaches 50 times the center thickness. The folding distance 56 is defined as the distance between the two plates 52 and 53. When the folding distance 56 is reached, the moving plate (here, 52) begins to move back and forth along the length of the article at a speed of 10 mm / s and a travel distance of 10 mm, as indicated by double arrow 54. If the foldable product 51 is subjected to 10 slides without the glass breaking, it is considered to have passed the test.

[0133] Figure 6 The glass articles of the present invention are illustrated schematically, respectively embodied as follows: Figure 6 Locally thinned glass (LSG) in A or Figure 6 Ultra-thin glass (UTG) in B. This description is similar to... Figure 3 The description. Therefore, smaller thicknesses are represented by darker colors. With Figure 3 Compared to the embodiments described herein, for Figure 6 A and Figure 6 In the embodiment described in B, the thickness of the outer region is further reduced in the region surrounding the folding axis.

[0134] Figure 6 A illustrates a glass article of this disclosure having a thinned region around its folding axis and a thicker unfolded region. Figure 6 In A, both the central and peripheral regions of the glass article are like this. The central region of the glass article has a thinned region 61b and a thicker region 61a. Similarly, the peripheral region of the glass article has a thinned portion 62b and a thicker portion 62a.

[0135] Figure 6 B illustrates a glass article of this disclosure. Around a folding axis, the peripheral region of the glass article has a thinned region. Figure 6 Compared to the embodiment of A, Figure 6 Embodiment B does not include the thinned region of the central region 71. The central region 71 of the glass article does not have a thinned region. However, the peripheral region of the glass article has a thinned portion 72b and a thicker portion 72a. Detailed Implementation

[0136] The preparation of the example disclosed herein includes the following steps in the order shown: Provide glass products, Stacking glass products to obtain layered composite materials. Cut and CNC grind to target dimensions. Chamfering is achieved by etching the laminates (i.e., layered composite materials). Layering is performed to obtain individual glass items. Pre-etching of individual glass artifacts (Examples 2, 4, and 6 only). Chemical fortification, Post-etching of individual glass artifacts (Examples 1-6 and 10 only).

[0137] All examples were based on chemically tempered aluminosilicate glass. All samples had comparable chamfer structures, including chamfer heights of 10 to 12 μm and chamfer widths of 40 to 60 μm.

[0138] Examples 7 to 9 were not etched. The etching of Examples 1-6 and 10 was performed using a mixture of 1-5 wt% HNO3 and 1-5 wt% HF. The same mixture and apparatus were used for both pre-etching and post-etching. Pre-etching"This refers to the etching step before chemical tempering." Post-etching "" refers to the etching step following chemical tempering. Both pre-etching and post-etching are performed on individual glass articles (rather than on a stack of glass articles), with an increased etching rate in the peripheral areas of the glass article compared to its central area. For Examples 1 to 6, etching is performed around the edges at an increased etching rate. In Example 10, there is no increased etching rate around the edges.

[0139] The sample size is n = 50. Therefore, 50 samples are used for each test. 2PB, P2C, and sliding are destructive tests. Therefore, 50 samples from different groups are used for each of these tests.

[0140] The results are shown in the table below.

[0141] Table 1 Table 2 CS and DoL represent the final CS and DoL values ​​after all etching steps have been applied.

[0142] For the post-etching of Example 10, the term "is*" indicates post-etching; however, the etching rate around the edges is not increased compared to Examples 1 through 6. Therefore, for Example 10, the average thickness of the central region is equal to the average thickness of the peripheral region. In contrast, for Examples 1 through 6, the average thickness of the peripheral region is less than the average thickness of the central region. The average thickness is determined as further noted below.

[0143] As indicated below, the performance shown in the example is tested.

[0144] Average thickness of the central and outer regions The average thickness of the central region and the average thickness of the outer region are determined in the following manner.

[0145] Outer area: Using a micrometer, measure the thickness along a line 2.5 mm from the profile in the direction towards the center. Take a measurement every 1 cm along the profile. Then calculate the average thickness based on the measurements.

[0146] Central region: Using a micrometer, measure the thickness of the area greater than 5 mm from the profile along the supercenter direction. For each 1 cm... 2 A measurement is taken in the area. Then, the average thickness is calculated based on the measurement.

[0147] 2PB test Perform the two-point bending (2PB) test as follows.

[0148] In this test, a glass article is placed in a U-shape between two parallel plates. These plates are large enough to cover the entire article. One plate is then moved towards the other at a speed of 60 mm / min while remaining parallel, until the designed folding distance reaches 50 times the center thickness. This folding distance is defined as the distance between the two plates. If the foldable article remains intact when the folding distance is reached, it is considered to have passed the test. For ultra-thin glass (UTG), the center thickness of the glass article corresponds to the average thickness of the central region of the glass article. For partially thinned glass (LSG), the center thickness of the glass article corresponds to the average thickness of the folded area in the central region. The pass rate is the number of passed samples divided by the total number of measured samples.

[0149] P2C ratio To evaluate the fracture origin of the glass in the 2PB test, a polymer film was laminated onto both sides of the sample glass, with the polymer film being 5 mm larger than the glass in both length and width. The adhesion between the glass and the polymer film was electrostatic. The film material was polyethylene. Each side of the glass was laminated with a 50 μm thick monolayer of polymer. In this process, cracks and debris within the coating were captured, and the origin point could be analyzed through the network crack structure.

[0150] In this analysis, it was found that glass processed by the method of the present invention originates more frequently from the center of the glass than from its edges. When calculating the periphery to center (P2C) breakage ratio, the P2C ratio for Examples 1-6 ranges from 6% to 13%, while the P2C ratio for Examples 7-10 ranges from 47% to 63%. The P2C ratio represents the percentage of breakage originating from the periphery region out of the total number of breakages. The P2C ratio is calculated based on the following formula: .

[0151] In this regard, the term "periphery" refers to the peripheral area of ​​a glass article, which is formed by a portion of the glass article whose closest distance to the edge surface, measured parallel to the first or second main surface, is at most 5.0 mm. Similarly, the term "periphery"... center "" refers to the central area of ​​a glass article, which is composed of a portion of the glass article that is at least 5.0 mm away from the edge surface, as measured parallel to the first or second main surface.

[0152] Sliding test The glass is further tested in a sliding test, where the folding distance is equal to 50 times the center thickness of the glass product (refer to the explanation of the P2C ratio above). In this test, the foldable glass is placed in a U-shape between two parallel plates. The plates are large enough to cover the entire product. One plate then moves towards the other at a speed of 60 mm / min while remaining parallel, until the designed folding distance is reached, which is 50 times the center thickness. The folding distance is defined as the distance between the two plates. When the folding distance is reached, the moving plate begins to move back and forth along the length of the product at a speed of 10 mm / s and a travel distance of 10 mm. If the foldable product withstands 10 slides without the glass breaking, it is considered to have passed the test.

Claims

1. A chemically tempered glass product, comprising: A first main surface and a second main surface, and at least one edge surface connecting the first main surface and the second main surface. The glass article has a central region and a peripheral region, wherein the first and second main surfaces are substantially parallel to each other in the central region. The central region is composed of a portion of glass material, measured parallel to the first or second main surface, whose closest distance to the edge surface is greater than 5.0 mm. The peripheral region is composed of a portion of glass material, measured parallel to the first or second main surface, at a minimum distance of 5.0 mm from the edge surface. The average thickness of the central region is at most 200µm. The ratio of the average thickness of the peripheral region to the average thickness of the central region is in the range of 75% to 99%. The average thickness of the peripheral region is the average thickness measured parallel to the first or second main surface, along a circumferential line 2.5 mm away from the edge surface.

2. The chemically tempered glass product according to claim 1, wherein, The average thickness of the peripheral region is 1.0µm to 10.0µm less than the average thickness of the central region, for example, 1.0µm to 7.0µm, 1.0µm to 5.0µm, or 1.0µm to 3.0µm less.

3. The chemically tempered glass article according to any one of the preceding claims, wherein, The central region includes a folded region and a non-folded region, wherein the average thickness of the central region in the folded region is less than the average thickness of the central region in the non-folded region.

4. The chemically tempered glass article according to any one of the preceding claims, wherein, The peripheral region includes a folded region and an unfolded region, wherein the average thickness of the peripheral region in the folded region is less than the average thickness of the peripheral region in the unfolded region.

5. The chemically tempered glass article according to any one of the preceding claims, in, The central region includes a folded region and a non-folded region, wherein the average thickness of the central region in the folded region is less than the average thickness of the central region in the non-folded region. The peripheral region includes a folded region and a non-folded region, wherein the average thickness of the peripheral region in the folded region is less than the average thickness of the peripheral region in the non-folded region. The average thickness of the folded region in the outer region is 1.0µm to 10.0µm smaller than the average thickness of the folded region in the central region.

6. The chemically tempered glass article according to any one of the preceding claims, in, The central region includes a folded region and a non-folded region, wherein the average thickness of the central region in the folded region is less than the average thickness of the central region in the non-folded region. The peripheral region includes a folded region and a non-folded region, wherein the average thickness of the peripheral region in the folded region is less than the average thickness of the peripheral region in the non-folded region, and The ratio of the average thickness of the folded region in the peripheral region (measured parallel to the first or second main surface and at a closest distance of 2.5 mm to the edge surface) to the average thickness of the folded region in the central region is in the range of 75% to 99%.

7. The chemically tempered glass article according to any one of the preceding claims, wherein, The breakage ratio of the glass article to its center is at most 45%.

8. The chemically tempered glass article according to any one of the preceding claims, wherein, The product is foldable.

9. The chemically tempered glass article according to any one of the preceding claims, wherein, The surface compressive stress at the first and / or second main surfaces is in the range of 300 MPa to 1500 MPa.

10. The chemically tempered glass article according to any one of the preceding claims, wherein, The layer depth at the first and / or second main surfaces is in the range of 0.5µm to 40µm.

11. A chemically tempered glass article according to any one of the preceding claims, wherein, In a sliding test with a folding distance of 50 times the center thickness of the glass product, a plate speed of 10 mm / s, and a plate travel distance of 10 mm, the pass rate of the glass product is greater than 50%, wherein the center thickness of the glass product corresponds to the average thickness of the central region of the glass product, or, if the central region includes a folded region and a non-folded region, the center thickness of the glass product corresponds to the average thickness of the folded region of the central region.

12. A chemically tempered glass article according to any one of the preceding claims, wherein, In a two-point bending test where the folding distance is 50 times the center thickness of the glass article, the pass rate of the glass article is at least 65%, wherein the center thickness of the glass article corresponds to the average thickness of the central region of the glass article, or, if the central region includes a folded region and a non-folded region, the center thickness of the glass article corresponds to the average thickness of the folded region of the central region.

13. The chemically tempered glass article according to any one of the preceding claims, wherein, The average thickness of the central region is in the range of 20µm to 80µm.

14. The chemically tempered glass article according to any one of the preceding claims, wherein, The article has a length y and a width z, and the ratio of the length y to the width z of the article is 1:1 or more.

15. The chemically tempered glass article according to any one of the preceding claims, wherein, The product is axially symmetric.

16. The chemically tempered glass article according to any one of the preceding claims, wherein, The glass product includes one or more axes of symmetry.

17. The chemically tempered glass article according to any one of the preceding claims, wherein, The glass contains the following components in amounts (by weight%): 。 18. A method for manufacturing a chemically tempered glass article according to any one of the preceding claims, wherein, The method includes the following steps performed in the order shown: A glass article is provided, comprising a first main surface and a second main surface, and at least one edge surface connecting the first main surface and the second main surface. The glass article is chemically tempered, and subsequently... Both the central and peripheral regions of the glass article are brought into contact with the etching solution, wherein the etching rate of the peripheral region is higher than that of the central region. The central region is comprised of a portion of the glass article that, when measured parallel to the first or second main surface, has a nearest distance greater than 5.0 mm from the edge surface. The peripheral region is composed of a portion of glass material, measured parallel to the first or second main surface, with a minimum distance of 5.0 mm from the edge surface.

19. The method according to claim 18, wherein, The etching rate of the peripheral region of the glass article is at least 10% higher than that of the central region.

20. The method according to any one of claims 18 and 19, wherein the step of contacting the central region and the peripheral region of the glass article with the etching solution reduces the average thickness of the central region of the glass article by 0.5 µm to 4 µm, and / or reduces the average thickness of the peripheral region of the glass article by 1.5 µm to 14 µm.

21. The method according to any one of claims 18 to 20, wherein, The method includes one or more measures selected from a group of the following: The glass article is rotated in the etching solution. The etching solution is used to create bubbles, wherein the bubbling is more intense in the peripheral region of the glass article than in the central region. The etching solution is stirred, thereby causing the etching rate of the peripheral region of the glass article to be higher than that of the central region. The etching solution is directed to the peripheral region of the glass article, specifically through at least one nozzle present in the etching tank containing the etching solution, and Combinations of two or more.

22. The method according to claim 21, wherein, The rotation step includes rotating the glass article about a rotation axis, wherein the rotation axis is perpendicular to the folding axis of the glass article.

23. The method according to any one of claims 21 and 22, wherein, The rotation axis is parallel to the long side of the glass product, and the folding axis is parallel to the short side of the glass product, or wherein the rotation axis is parallel to the short side of the glass product and the folding axis is parallel to the long side of the glass product.

24. The method according to any one of claims 21 to 23, wherein, The axis of rotation is one of the axes of symmetry of the glass article.

25. The method according to any one of claims 21 to 24, wherein, The axis of rotation is the axis of symmetry of the glass article, which is parallel to the long side of the glass article.

26. The method according to any one of claims 21 to 25, wherein, The article rotates around the rotation axis clockwise or counterclockwise, or alternately clockwise and counterclockwise.

27. The method according to claim 26, wherein, The ratio of the duration of the clockwise rotation to the duration of the counterclockwise rotation is in the range of 1:3 to 3:

1.

28. The method according to any one of claims 21 to 27, wherein, The rotational speed is in the range of 0.1 to 10.0 revolutions per minute.

29. The method according to any one of claims 21 to 28, wherein, The etching solution is stirred, thereby causing the stirring shaft to move about a length parallel to the glass article.

30. The method according to any one of claims 18 to 29, wherein, The etching solution contains HF and / or NH4HF2, as well as additional inorganic and / or organic acids.

31. The method according to claim 30, wherein, The inorganic acid is selected from the group consisting of HCl, HNO3, H2SO4, and mixtures of two or more thereof.

32. The method according to any one of claims 18 to 31, wherein, The temperature of the etching solution is in the range of 1°C to 50°C.

33. The method according to any one of claims 18 to 32, wherein, The method further includes the step of contacting both the central region and the peripheral region of the glass article with the etching solution prior to chemical tempering.

34. The method according to claim 33, wherein, In the etching step prior to chemical tempering, the etching rate of the peripheral region of the article is at least 10% higher than that of the central region.

35. The method according to any one of claims 18 to 34, wherein, Prior to the chemical tempering step, the method further includes the following steps performed in the order shown: Provides layered composite materials comprising multiple glass products. Optionally, the layered composite material is cut to the required size. Optionally, edge grinding and / or polishing may be performed. The layered composite material was immersed in an etching solution, and The layered composite material is layered to obtain individual glass articles.

36. The method according to claim 35, wherein, The layered composite material comprises 2 to 30 glass components.

37. Use of the glass article according to any one of claims 1 to 17 in consumer electronics products, for example: Foldable handheld devices, including smartphones, tablets, or wearable devices. Laptop Monitor, or Monitor screen.

Images