Method for creating internal holes in chemically strengthened glass sheet articles

Abstract

The present invention relates to a method for creating an internal hole (1) in a glass sheet article (10) having a thickness T, wherein the internal portion (2) is separated from the glass sheet article along a separation line (3). The method includes, in the following order, at least a fibrous step in which fibrous defects are created within the volume of a glass sheet article in the form of submicron hollow channels adjacently aligned along a separation line, the defects are created by laser pulses of an ultrashort pulse laser, the material of the glass sheet article is transparent to the laser pulses, the laser pulses generate plasma within the volume of the glass sheet article, the plasma causes fibrous defects, the incident point of the laser pulses in the glass sheet article is displaced across its surface along the separation line to introduce adjacently aligned fibrous defects along the separation line, followed by a step of chemical strengthening the glass sheet article, and then a step of separating the inner portion from the glass sheet article at adjacently aligned fibrous defects along the separation line by irradiating the inner portion with an ablation laser to remove at least one segment (4), the at least one segment having two endpoints located on the separation line, substantially having a thickness T, and having a width W (W ≥ 150 μm) of 150 μm or more.

Description

[Technical Field]

[0001] The present invention relates to a laser-based method for creating internal holes in a chemically strengthened glass sheet article. [Background technology]

[0002] In fields such as cover glass for electronic devices, glazing for building materials, and glazing for vehicles, high strength is often required for safety reasons and to comply with safety regulations that apply to such glazing. Therefore, glazing is often chemically strengthened to obtain a glazing or cover with high stress resistance. In chemical strengthening, alkali metal ions with an atomic diameter larger than the original atoms are introduced to the surface of the glass substrate. Thus, a compressive stress layer is formed on the surface of the glass substrate, thereby improving the strength of the glass substrate.

[0003] The conventional method, in which many glass items are first cut to their final shape and then chemically strengthened, is prone to significant scratches and damage if not handled with sufficient care. To avoid these drawbacks, several methods have been developed, such as strengthening larger pieces of glass before cutting the glass product to its final shape.

[0004] For example, European Patent No. 3345877B describes a method combining fiberization and chemical strengthening, in which the chemical strengthening treatment is applied to a large-sized glass material beforehand, and the large-sized glass material is subsequently cut by fiberization to produce a chemically strengthened glass article. International Publication No. 2019 / 154782 proposes a method for producing a coated glass article, comprising the steps of fiberization to separate the glass article from a glass substrate, then chemical strengthening of the glass substrate, and then coating.

[0005] In practice, fiberization techniques are often used to produce glass articles from larger glass panels. The outline of the glass article produced from the glass panel is formed by fiberization separation lines. In addition, fiberization fracture lines are further created around the outline of the glass article to facilitate the removal of the glass article from the glass panel. Several separation techniques are used. A typical technique is to initiate a crack at a controlled location using a mechanical device (diamond tool, cutting wheel, etc.) so that the crack propagates along the fiberization separation line. It is known that additional voids are created near the fiberization separation line to provide controlled crack propagation along the fiberization separation line. The initial crack initiation at the appropriate location induces the separation of the glass article from the initial glass panel. Although this technique allows for obtaining the glass article without affecting its quality, this mechanical separation involves the fracture of the initial glass panel from which the glass article originates and cannot be used to create internal voids.

[0006] Another technique involves bending the substrate to create stress in the sheet glass substrate. The material is stretched in one half of its volume, thereby creating tensile stress in that half, while the other half is compressed, thereby creating compressive stress. However, bending the glass substrate is not suitable for removing small inner portions, in particular.

[0007] In fact, even if the glass has enough internal stress to initiate self-separation after the formation of a defect line, the geometry of the cut shape can prevent the internal glass piece from being released. This is true for most closed or internal shapes, such as simple holes or slots. The inner portion of the hole remains in place due to the compressive forces present in the glass sheet. While cracks can propagate between the puncture defects, there is no room for the internal piece to fall out of the mother sheet.

[0008] Mechanical separation techniques can nevertheless be used to remove the interior of the glass by applying some pressure to it. However, when using such mechanical separation techniques, the edges of the inner portion and the inner bore rub against each other, resulting in low-quality edges that are unsuitable for applications requiring extremely sharp edges.

[0009] Other techniques have also been designed in the art to remove the inner portion of a glass article to create such an internal cavity, and are typically based on thermal compression. For example, U.S. Patent Application Publication No. 2018134606 discloses a method for separating a portion from a sheet glass element having a thickness of at least 2 millimeters. The method comprises making fibrous damage along a separation line and heating and / or cooling the glass sheet element to cause expansion and / or contraction to pull the portion away from the main part along the separation line.

[0010] However, it has been found that separation techniques based on thermal compression cannot be used to create small-sized internal pores. In fact, such techniques rely on the expansion of the main part and / or the contraction of the part to be removed, causing these parts to change their size differently from one another. However, in cases where the part to be removed is small, the temperature difference between the glass article and the inner part to be removed is too large to be used effectively, even if it does not destroy the main part.

[0011] Therefore, there is still a need to find a suitable method for creating small internal pores with high-quality edges within chemically strengthened glass articles. [Overview of the project]

[0012] Other aspects and advantages of the embodiments will become apparent from the following detailed description, in conjunction with the accompanying drawings illustrating the principles of the embodiments described.

[0013] The present invention relates to a method for creating an internal hole in a glass sheet article having a thickness T, wherein the internal portion is separated from the glass sheet article along a separation line. The method comprises, in the following order, at least: a) A fiberization step, wherein fibrous defects are created within the volume of a glass sheet article in the form of submicron hollow channels aligned adjacently along a separation line, the defects are created by laser pulses of an ultrashort pulse laser, the material of the glass sheet article is transparent to the laser pulses, the laser pulses generate plasma within the volume of the glass sheet article, the plasma causes fibrous defects, the incident point of the laser pulses in the glass sheet article is displaced across its surface along the separation line, introducing fibrous defects aligned adjacently along the separation line, b) Steps for chemical strengthening of glass sheet articles, e) A step of separating an inner portion from a glass sheet article in adjacent, aligned fibrous defects along a separation line by irradiating the inner portion with an ablation laser to remove at least one segment, wherein at least one segment has two endpoints located along the separation line, has a substantially thick T, and has a width W of 150 μm or more (W ≥ 150 μm). Includes.

[0014] In another embodiment, the present invention relates to a corresponding method for manufacturing a glass sheet article having a thickness T and containing internal holes from a larger glass substrate. The method is as follows: a1) A fiberization step to produce at least one glass sheet article along a separation line, wherein the separation line is for dividing a glass substrate into at least one glass sheet article. a2) A step of fiberization for separating an inner part from a glass sheet article along a separation line defining the separated inner part, wherein fibrous defects are created within the volume of the glass substrate in the form of sub-micron hollow channels aligned adjacent to each other along the separation line, the defects are created by laser pulses of an ultra-short pulse laser, the material of the glass substrate is transparent to the laser pulses, the laser pulses create a plasma within the volume of the glass substrate, the plasma causes fibrous defects, and the point of incidence of the laser pulses on the glass substrate is displaced along its surface along the separation line to introduce fibrous defects aligned adjacent to each other along the separation line. b) A step of chemically strengthening the glass substrate. e) e1) A separation step for separating the glass sheet article from the glass substrate. e2) A step of separating the inner part from the glass sheet article at the fibrous defects aligned adjacent to each other along the separation line by irradiating the inner part with an ablation laser to remove at least one segment, wherein the at least one segment has two end points located on the separation line, has a substantially thickness T, and has a width W (W≧150μm) of 150μm or more. Including.

[0015] In both embodiments, the method preferably further includes a splitting step d) performed along the separation line where the fibers are interconnected, and such a splitting step is performed immediately before the separation step e). Preferably, the coating step c) of the glass sheet article or the glass sheet substrate is performed after the chemical strengthening step b) and before the splitting step d) if it exists.

[0016] The inner hole made in the glass sheet article is preferably 300 mm 2 or less (S≦300 mm 2 ), preferably 150 mm 2 or less (S≦150 mm 2 ), preferably 120 mm 2 or less (S≦120 mm 2)、 more preferably 80 mm 2 or less (S ≦ 80 mm 2 ) and has a surface area. The inner hole is typically 3 mm 2 or more (S ≧ 3 mm 2 ), preferably 5 mm 2 or more (S ≧ 5 mm 2 ) and has a surface area.

[0017] In the separation step e1), the ablation laser removes at least one segment that is preferably 200 μm or more (W ≧ 200 μm), preferably 250 μm or more (W ≧ 250 μm) within the inner portion. In one embodiment, there are at least two segments within the inner portion. In a preferred embodiment, at least one segment extends along at least 50%, preferably at least 75%, more preferably 100% of the outer circumference of the inner portion.

[0018] The present invention further relates to a glass sheet article obtained by the method of the present invention. The glass sheet article preferably has a thickness of at least 0.1 mm, preferably at least 0.3 mm, more preferably at least 0.5 mm, and preferably less than 20 mm, preferably less than 10 mm, more preferably less than 2 mm, more preferably less than 1.5 mm, more preferably less than 1 mm. Preferably, the glass sheet article has a soda-lime silicate glass composition, an aluminosilicate glass composition or an alkali aluminosilicate glass composition. The glass sheet article typically has a CTE of 70 × 10 -7 / °C to 100 × 10 -7 / °C, preferably 80 × 10 -7 / °C to 95 × 10 -7 / °C.

Brief Description of the Drawings

[0019] [Figure 1a] Figure 1a shows a top view of a glass sheet article including an inner hole according to an embodiment of the present invention. [Figure 1b]Figure 1b shows the same glass sheet article, with the inner portion, separation line, and ablation segment removed to create the internal void.

[0020] [Figure 2] This shows a top view of a glass substrate including a glass sheet article with internal holes, according to another embodiment of the present invention.

[0021] [Figures 3a-3e] The present invention illustrates several embodiments of the inner portion to be removed, each comprising different ablation segments. Figure 3a shows a top view of an inner portion having a rectangular shape, comprising an ablation segment extending along 100% of the outer circumference of the inner portion. Figure 3b shows a top view of an inner portion having an ellipse shape, comprising an ablation segment along the longest diameter of the inner portion. Figure 3c shows a top view of an inner portion having a circular shape, comprising two vertical ablation segments. Figure 3d shows a top view of an inner portion having a circular shape, comprising a crescent-shaped ablation segment extending along 50% of the outer circumference of the inner portion. Figure 3e shows a top view of an inner portion having a circular shape, comprising an ablation segment extending along 100% of the outer circumference of the inner portion.

[0022] [Figure 4] This is a schematic diagram of a method according to a first aspect of the present invention.

[0023] [Figure 5] This is a schematic diagram of a method according to a second aspect of the present invention. [Modes for carrying out the invention]

[0024] The object of the present invention is to provide a chemically strengthened glass sheet article containing high-quality internal pores. Currently available manufacturing techniques do not provide the required quality and / or are not suitable for creating small internal pores. Surprisingly, the manufacturing method of the present invention has been found to overcome the shortcomings of the prior art.

[0025] An object of the present invention is to enable efficient and high-quality separation of the inner portion from a chemically strengthened glass sheet article while minimizing the risk of harmful cracking in the remaining main portion of the glass article. A further object is to provide a simple, effective, and rapid method for manufacturing a chemically strengthened glass article optionally containing internal pores. By high quality, it is understood herein that the edges of the internal pores are sharp and at least partially strengthened, and that there should be no coating material when a coating step is added to the manufacturing process of the present invention.

[0026] In the same steps of fiberization, chemical strengthening, and potentially coating, such glass sheet articles are produced from much larger glass substrates. The manufacturing method of the present invention is not only time and cost-effective, but it has also been found to maintain the rigidity of the large glass sheet despite the presence of numerous internal pores within the glass sheet article, thereby greatly facilitating handling and transportation.

[0027] As shown in Figures 1a and 1b, the present invention relates in a first embodiment to a method for creating an internal hole (1) in a glass sheet article (10) having a thickness T, wherein the internal portion (2) is separated from the glass sheet article along a separation line (3). The separation line (3) divides the glass sheet article into the internal portion to be separated and the remaining main portion of the glass sheet article.

[0028] Creating an internal cavity in a glass sheet article involves separating an inner portion along a separation line in the form of a closed loop. The internal cavity can be of any shape. If the shape of the internal cavity includes a straight line, such lines are preferably connected by a curved angle to form a closed loop. Preferably, the internal cavity is elliptical, more preferably circular. A glass sheet article may contain one or more internal cavities of the same or different shapes and of the same or different sizes.

[0029] This invention is particularly useful for creating small-sized internal holes in glass sheet articles. These small sizes typically refer to 300 mm. 2 Less than 150 mm, preferably 150 mm2 Less than 120 mm, preferably 120 mm 2 Less than, more preferably 80 mm 2 It is understood to have a surface area of ​​less than 3 mm. Typically, the method of the present invention has a surface area of ​​at least 3 mm 2 Preferably at least 5 mm 2 It is used to create a circular internal hole with a surface area.

[0030] As shown in Figure 4, in the first embodiment, the method of the present invention first comprises a fiberization step (step a), followed by a chemical strengthening step (step b), which may optionally be followed by a coating step (step c) and preferably a cleavage step (step d) and finally a separation step (step e).

[0031] Correspondingly, the method of the present invention includes fiberization as a first step. The glass sheet article is fiberized by laser pulses, i.e., micro-perforated along at least one defined separation line. Such separation lines form closed loops and define the inner contour of the inner portion to be removed. Subsequently, a chemical strengthening step is performed on the glass sheet article. The method may optionally then include a coating step. The cleavage step is preferably performed along the separation line of the inner contour, so that the fibers are interconnected so that the inner contour is separated from the main portion without being detached from the main portion.

[0032] The method of the present invention finally includes a separation step, in which the inner portion (2) is separated from the glass article (10) by irradiating the inner portion with an ablation laser to remove at least one segment (4) of such inner portion. The ablation of the segments of the inner portion must be large enough to make the inner portion smaller, thereby freeing the inner portion. This particular ablation step allows the edges of the pores created within the glass sheet article portion to maintain the extremely high edge quality obtained through the fiberization step. Furthermore, the edges benefit from the chemical strengthening step performed earlier.

[0033] Fiber formation step (a) Laser fiberization is a technique for cutting glass articles from glass sheets. Irreversible damage in the form of fibers is induced in the glass substrate by high-energy laser pulses, and a series of aligned such damages makes it possible to separate the glass. Fibers are made by ultrashort laser pulses that cause self-focusing within the glass due to the Kerr effect until the energy density becomes high enough that plasma ignites at several points. A plasma explosion occurs, during which the glass is irreversibly damaged around this plasma generation site. From there, further radiation is emitted, undergoing self-focusing and ending in another plasma explosion. This effect is repeated several times depending on the intensity.

[0034] Therefore, the first step a) of the method for creating internal holes in a glass sheet article is a fibrous step, in which fibrous defects are created within the volume of the glass sheet article in the form of submicron hollow channels aligned adjacently along a separation line, the defects are created by laser pulses of an ultrashort pulse laser, the material of the glass sheet article is transparent to the laser pulses, the laser pulses generate plasma within the volume of the glass sheet article, the plasma causes fibrous defects, the incident point of the laser pulse in the glass sheet article is displaced across its surface along a separation line, introducing fibrous defects aligned adjacently along the separation line.

[0035] Details of the fiberization step of the present invention are described in detail in sections

[0037] to

[0074] under step S130 with reference to Figures 3 to 7 in European Patent No. 3345877B granted to AGC Inc. on March 23, 2022, which is incorporated herein by reference and summarized herein below.

[0036] A laser is shone onto the glass material to form an in-plane void region on the first main surface of the glass material. Two or more rows of internal voids are formed extending from the in-plane void region toward the second main surface. The "in-plane void region" refers to two or more surface voids formed in a predetermined arrangement. Furthermore, the "row of internal voids" refers to a linear region having one or more voids formed on the inside of the glass material extending from the first main surface toward the second main surface.

[0037] Each surface void corresponds to the laser irradiation position on the first main surface and has a diameter of, for example, 1 to 5 μm. The diameter of the surface voids varies with the laser irradiation conditions, the type of glass material, etc. The distance P between the centers of adjacent surface voids can be determined based on the composition and thickness of the glass material, the laser processing conditions, etc. For example, the distance P between the centers of adjacent surface voids may be in the range of 2 to 10 μm. The distance P between the centers of surface voids does not need to be equal at all locations and may vary depending on the location. That is, the surface voids may be arranged at irregular intervals. The shape, size, and pitch of the internal voids are not particularly specified. When viewed from the Y direction, the voids may have shapes such as circles, ellipses, rectangles, triangles, etc. Furthermore, the maximum dimension of the voids when viewed from the Y direction (typically corresponding to the length of the voids along the direction of extension of the internal void rows) may be in the range of, for example, 0.1 to 1000 μm. Each of the internal void rows has a corresponding surface void.

[0038] As can be understood from the above, the in-plane void region is not actually formed as a continuous "line," but represents a virtual linear region formed by connecting each surface void. Similarly, the internal void row is not actually formed as a continuous "line," but represents a virtual linear region formed by connecting each void.

[0039] The in-plane void region and internal void rows described above can be formed by irradiating a first principal surface of the glass material with a laser. More specifically, first, the laser is directed to a first position on the first principal surface of the glass material to form a first internal void row containing surface voids from the first principal surface to the second principal surface. Next, the position from which the laser is directed to the glass material is changed so that the laser is directed to a second position on the first principal surface of the glass material to form a second internal void row containing second surface voids from the first principal surface to the second principal surface. The in-plane void region and the corresponding internal void rows can be formed by repeating this operation.

[0040] If an internal void row with voids sufficiently close to the second principal surface is not formed by a single laser pass, i.e., if the void closest to the second principal surface is sufficiently far from the second principal surface (for example, the void closest to the second principal surface is at a distance of less than half the thickness of the glass material from the first principal surface), the laser may be applied to substantially the same position more than once. Note that "substantially the same (laser application) position" indicates not only that the two positions coincide perfectly, but also that the two positions may be slightly misaligned (e.g., a deviation of up to 3 μm). For example, to form the first in-plane void region and the corresponding internal void row, the laser may be applied more than once along a first direction parallel to the first principal surface of the glass material (first pass), and then the laser may be applied in substantially the same direction and at substantially the same position as the first pass (second pass), thereby forming a "deeper" internal void row corresponding to the first in-plane void region.

[0041] The distance from the center of the void closest to the second main surface among the voids constituting the internal void row to the second main surface is preferably in the range of 0 to 10 μm, but such a distance may vary with the thickness of the glass material.

[0042] In particular, densely packed micron hollow channels, i.e., hollow channels with a diameter of less than 5 microns, are manufactured. The fibrous damage created by the laser pulse preferably has a length of at least 200 microns, more preferably at least 500 microns. For this purpose, suitable pulse energy and pulse duration are selected. The shortest length of the identified fibrous damage is advantageous because they facilitate the separation of parts.

[0043] Particularly advantageous for generating long, fibrous damage is the operation of an ultrashort pulse laser in so-called burst mode. In this mode of operation, the laser pulse is not emitted as a single pulse, but as a series of continuously emitted pulses that form pulse packets, so-called bursts. Accordingly, one embodiment of the present invention considers the operation of an ultrashort pulse laser in the form of emission of laser pulses in the form of bursts or pulse packets in a temporal continuity, each of which preferably generates one of each of the fibrous damages. Such pulse packets generally have slightly higher energy than a single pulse in conventional single-shot operation. However, the pulses in a burst contain significantly lower energy than a single pulse. Furthermore, the pulse energy of the pulses typically decreases within the burst.

[0044] A preferred laser source according to the present invention is a neodymium-doped yttrium aluminum garnet laser having a wavelength of 1064 nanometers. The laser source operates at a repetition rate of 10 kHz to 1 MHz, preferably 30 kHz to 300 kHz, and most preferably 35 kHz to 200 kHz. The scanning speed can preferably be selected, depending on the repetition rate, such that the spacing between adjacent fibrous damages is in the range of 2 microns to 10 microns.

[0045] In this case, a suitable pulse duration for the laser pulse is less than 100 picoseconds, preferably less than 100 picoseconds. The pulse duration may also be less than 30 picoseconds. Most preferably, the laser source operates at a typical power output in the range of 30 to 500 watts. According to one advantageous embodiment of the present invention, to achieve fibrous damage, a pulse energy exceeding 200 microjoules and a total burst energy exceeding 400 microjoules are applied in bursts.

[0046] When an ultrashort pulse laser operates in burst mode, the repetition rate is the rate at which repeated burst emissions occur. The pulse duration is essentially independent of whether the laser operates in single-pulse mode or burst mode. Pulses within a burst typically have a pulse length similar to that of pulses in single-pulse mode.

[0047] Except for a very small amount, the material is not removed from the separation seam during micro-perforation used for the present invention. When fibrous damage is introduced, both parts to be separated are still substantially connected to each other. Once micro-perforation is achieved, a predetermined fracture line exists in the material along the separation line, and along the separation line, the material is still not separated, but can be easily separated when suitable stress is induced in the material. In particular, a cleavage step is suitable for this purpose.

[0048] Due to the highly precise separation process in step a), extremely high edge quality is achieved at the cut edges. Since the quality of the glass edge is very important for the bending strength of the glass element, high edge quality also leads to increased bending strength of the main part of the glass article. In fact, glass that is as smooth as possible, with as few, preferably none, chips, notches and other irregularities as possible, contributes to reducing the risk of glass breakage. In particular, the edges are characterized by chipping of less than 10 microns, more preferably less than 5 microns, and a roughness with an Rz value of less than 30 microns, preferably 20 microns, and more preferably 10 microns.

[0049] Steps in chemical strengthening - Step (b) The method for creating pores in a glass article of the present invention further comprises a chemical strengthening step b) immediately after the fiberization step a) and before the separation step e), and before the coating step c) and / or cleavage step d), if present.

[0050] Details of the preferred chemical strengthening steps of the present invention are provided in sections

[0075] to

[0089] under step S120 of European Patent No. 3345877B, granted to AGC Inc. on March 23, 2022, which are incorporated herein by reference.

[0051] The conditions for the chemical strengthening treatment are not particularly limited. Chemical strengthening can be performed, for example, by immersing a glass sheet article in a molten salt at 380°C to 500°C for 1 minute to 72 hours, wherein at least one separation line defines the contour line of at least one glass article.

[0052] Nitrates can be used as molten salts. For example, when replacing lithium ions in a glass sheet article with larger alkali metal ions, a molten salt containing at least one of sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate can be used. Furthermore, when replacing sodium ions in a glass sheet article with larger alkali metal ions, a molten salt containing at least one of potassium nitrate, rubidium nitrate, and cesium nitrate can be used. Furthermore, when replacing potassium in a glass sheet article with larger alkali metal ions, a molten salt containing at least one of rubidium nitrate and cesium nitrate can be used. In addition, one or more types of salts, such as potassium carbonate, can be further added to the molten salt. In this case, a low-density layer having a thickness of 10 nm to 1 μm can be formed on the surface of the glass sheet article.

[0053] A compressive stress layer can be formed on both the surface and the edges of the internal pores of a glass sheet article by chemical strengthening treatment, wherein at least one separation line defines the contour of the inner portion. The thickness of the compressive stress layer corresponds to the penetration depth of the alkali metal ions for substitution. For example, when sodium ions are substituted for potassium ions using potassium nitrate, the thickness of the compressive stress layer may be 8 μm to 27 μm for soda-lime glass, and 10 μm to 100 μm for aluminosilicate glass. In the case of aluminosilicate glass, the penetration depth of the alkali metal ions is preferably 10 μm or more, more preferably 20 μm or more.

[0054] Therefore, because the glass sheet articles are chemically strengthened, it is easier to ensure the production of glass sheet articles with a flawless appearance and strength compared to conventional manufacturing methods. Consequently, the production yield can be increased. More specifically, the glass articles with internal bores have similarly chemically strengthened edges after separation of the inner portion through the separation line. Thus, sufficient strength is obtained for the glass articles. Consequently, the quality of chemical strengthening is improved at the internal bore edges, and the level of loss and, more specifically, the edge effect is reduced.

[0055] Optional but preferred coating step c) In a preferred embodiment of the present invention, the process includes an additional step c) coating after the chemical strengthening step b) and before the separation step e), and before step d) if present.

[0056] In fact, in one preferred embodiment of the present invention, the glass sheet article is coated before the inner portion is separated from the glass sheet article through at least one separation line. In fact, it has been found that when such a coating step is performed before the separation of the inner portion from the rest of the glass sheet article, if the inner pores are made before the coating step, it is possible to coat the rest of the glass sheet up to the separation line while avoiding the coating dripping along the edges of the inner pores. The method of the present invention is extremely efficient and can provide not only extremely sharp and smooth edges and partially reinforced edges, but also extremely smooth coated surfaces in a simple and fast manufacturing process.

[0057] According to one embodiment of the present invention, a glass sheet article is coated with at least one transparent, conductive thin layer. The transparent, conductive thin layer according to the present invention may be, for example, a layer based on SnO2:F, SnO2:Sb or ITO (indium tin oxide), ZnO:Al or similarly ZnO:Ga.

[0058] According to another advantageous embodiment of the present invention, a glass sheet article is coated with at least one anti-reflective layer. The anti-reflective layer according to the present invention may be, for example, a layer based on porous silica having a low refractive index, or it may consist of a stack of alternating layers of dielectric material having low and high refractive indices, and ending with a layer having a low refractive index. A textured glass sheet article may also be used to avoid reflection. Etching or coating techniques may also be used.

[0059] According to another embodiment, a glass sheet article is coated with at least one anti-fingerprint layer or treated to reduce or prevent fingerprints. Such a layer or treatment may be combined with a thin, transparent, conductive layer laminated on the opposite side. Such a layer may be combined with an anti-reflective layer laminated on the same side, with the anti-fingerprint layer being on the outside of the stack and therefore covering the anti-reflective layer.

[0060] According to another embodiment, the glass sheet article is a digital or silkscreen printed article, or an etched article.

[0061] According to another embodiment, the glass sheet article is coated with a pigment / enamel, an antimicrobial glass coating, etc. According to the present invention, the term “coated” can refer to a pigment or surface treatment that can modify the properties of the glass surface (mechanical, chemical, photoenergetic, biological, electrical, aesthetic properties, etc.) by adding or removing or modifying the physicochemical properties of the coating itself and the surface material (at temperatures below its Tg that are “visible through glass”).

[0062] According to another embodiment, the glass sheet article is coated with a coating selected from the following non-exclusive list of coatings: low-e coating, solar control coating, diamond coating, self-cleaning coating (TiO2, etc.), ion implantation coating, lacquer coating (Lacobel type), silver or dielectric coating, conductive ink, infrared-transmitting ink, translucent ink, fluorescent or upconversion material, "mesh" lamination (silver nanowire, carbon nanotube), surface (nano) laser structure, safety film, double-sided adhesive, sol-gel coating (with all their functions, i.e., color change, enzyme integration, etc.), solar type coating and thin film, acid attack, polishing, surface engraving, etc.

[0063] Depending on the desired application and / or properties, the coating may be applied to one and / or both surfaces of the glass sheet article. Several combinations of coatings may also be laminated to one and / or the other surface of the glass sheet article, such as a silkscreen print and the coating itself.

[0064] According to one preferred embodiment of the present invention, a glass sheet article is provided with an anti-glare, anti-reflective and anti-fingerprint coating on surface 1 (a term well known to those skilled in the art) and a multi-color silkscreen printed safety film on surface 2.

[0065] Optional but preferred cleavage step (d) In a preferred embodiment, the method of the present invention further includes a cleavage step d). Cleavage occurs when adjacent and aligned fibrous damage is introduced along a separation line. The incident point of laser radiation, preferably a carbon dioxide laser, is displaced across the surface of the glass article along the separation line so that local tensile stress is induced in the glass along the separation line to cause crack formation between adjacent fibrous damage. This cleavage method step may also be facilitated by heating followed by local cooling to increase the tensile stress generated in the material. The cleavage step is used for provisional separation. This makes it possible to initiate the formation of cracks connecting the fibrous damage along the separation line so as to cause a break along at least a portion of the separation line without pulling that portion away from the main part. Both the fibrous structure itself and the additional cracks induced by the cleavage step are provisional damage to the material extending along the separation line.

[0066] Ablation step e) The final required step of the method of the present invention is the separation of an inner portion (2) from a glass sheet article (10) at adjacent, aligned fibrous defects along a separation line (3), as shown in Figure 1b. Separation is achieved by irradiating with an ablation laser to remove at least one segment (4) within the inner portion (2). The segment has two endpoints located on the separation line (3). It has substantially the same thickness T as the glass sheet article and a width of ≥150 μm or more, so that the inner portion is separated from the main portion at adjacent, aligned fibrous defects along the separation line.

[0067] The glass sheet article extends along a plane P defined by the longitudinal axis X and the vertical axis Y. The thickness is measured perpendicular to plane P. The width is measured along plane P. In a preferred embodiment, the segment (4) has a width of 200 μm or more (W≧200 μm), preferably 250 μm or more (W≧250 μm). It is conceivable that the segment does not have the same width along its length, such as being crescent-shaped. In this example, the minimum width of the ablation segment is required to be 150 μm or more. Typically, the segment has a width of 500 μm or less (W≦500 μm), preferably 450 μm or less (W≦450 μm), more preferably 400 μm or less (W≦400 μm). It is found that the separation step takes longer as the segment width increases.

[0068] The objective of the ablation step in the process of the present invention is to reduce the volume of the inner portion in order to counteract the compressive forces between the rest of the glass sheet article and the inner portion. In fact, even if the glass has sufficient internal stress to initiate self-separation after the formation of a defect line, the geometry of the cut shape may prevent the inner portion from being released. This is true for most closed or internal shapes, such as simple holes or slots. The inner portion of the hole remains in place due to the compressive forces present in the glass sheet. While cracks may propagate between the puncture defects, there is no room for fragments to fall out of the glass sheet article.

[0069] Depending on the shape of the inner portion to be removed, several embodiments for the segment to be removed may be considered to further increase the speed and ease of removal of the inner portion. For example, two or more segments across the inner portion may be considered. In another embodiment, the segment to be removed extends along at least 50%, preferably at least 75%, and more preferably at least 100% of the outer circumference of the inner portion.

[0070] Figure 3 shows a different embodiment of the glass sheet article of the present invention, in which the inner portion differs in shape and the shape and size of the ablation segments. All figures should be considered for illustrative purposes only. In particular, Figures 1b and 3 are very schematic in order to show the separation line, inner portion and segments.

[0071] Figure 3a shows a glass sheet article having an inner portion having a curved, angled rectangle and an ablation segment extending along 100% of the outer circumference of the inner portion. Figure 3b shows a glass sheet article having an inner portion having an ellipse and a single ablation segment along the longest diameter of the inner portion. Figures 3cde show three different embodiments of a glass sheet article having an inner portion having a circle. Figure 3c shows an embodiment having two ablation segments extending along two diameters of the circular inner portion. In this example, the two segments are perpendicular to each other, but any angle between the segments can be assumed herein. Figure 3d shows an embodiment having a single ablation segment extending along 50% of the outer circumference of the circular inner portion, and the ablation segment has a crescent shape. In this example, the ablation segment does not have the same width along its length. Figure 3e shows an embodiment having a single ablation segment extending along the entire outer circumference of the circular inner portion.

[0072] Laser glass ablation is a process in which a laser is used to remove material from a glass surface. The laser heats the glass to a high temperature, causing it to evaporate and simultaneously removing a small amount of material. Ablation is achieved with a laser beam strong enough to cause rapid melting, which leads to the evaporation of the glass. The ablation process is carried out layer by layer until a thickness T is removed. Typically, ablation laser systems have wavelengths in the range of 193 nm to 1070 nm, pulse durations of less than 1 μs, ideally less than 100 ns. The average power output of the laser system is generally several hundred watts. The laser can operate with repetition frequencies exceeding 100 Hz and laser spot diameters of less than 100 μm on the glass surface. The scanning speed of the laser system is typically greater than 50 mm / s.

[0073] Manufacturing of glass sheet articles from glass substrates Glass sheet articles can be manufactured by any method known in the art. However, it is preferable that glass sheet articles are manufactured from a glass substrate by similar manufacturing methods using fiberization / chemical strengthening / separation, and that a large number of glass sheet articles can typically be manufactured from a large glass substrate.

[0074] Accordingly, in a second embodiment, the present invention relates to a method for producing at least one glass sheet article (10) having a thickness T and containing an internal pore (1) from a glass substrate (20). As shown in Figure 5, such a production method first comprises a fiberization step (step a)), followed by a chemical strengthening step (step b), then optionally a coating step (step c)) and preferably a cleavage step (step d)), and finally a separation step (step e)). The descriptions of the different steps described above with reference to the glass sheet article are applied to the glass substrate with necessary modifications as provided herein.

[0075] In fact, it has been found that if internal pores are created in a glass sheet article before the glass substrate undergoes chemical strengthening, this reduces the rigidity of the glass substrate and significantly increases the risk of breakage during all subsequent processing steps, such as chemical strengthening coating, handling, and transportation. Therefore, a second embodiment of the present invention avoids these drawbacks and provides an efficient method for manufacturing high-quality glass sheet articles containing internal pores.

[0076] The fiberization process of step a) is the same step described above in relation to the method for creating an inner pore in a glass sheet article. This step includes a fiberization substep a1) for producing at least one glass sheet article along an intended separation line that divides the glass substrate into at least one glass sheet article to be separated and the rest of the substrate. This step also includes a fiberization substep a2) for separating the inner portion (2) from the glass sheet article along an intended separation line (3) that defines the inner portion to be separated. For process efficiency, it is preferable that the separation line for dividing the glass sheet article from the glass substrate and the separation line for separating the inner portion are carried out simultaneously. However, substeps a1) and a2) may be carried out separately in any order.

[0077] As described above, step b) of the chemical strengthening is performed on the surface of the glass substrate. By subjecting a glass substrate having separation lines that divide it into at least one glass sheet article to be separated and separation lines that define the inner portion to be separated, a compressive stress layer can be formed on both sides of the glass sheet article and on the edges of the glass sheet article and the edges of the inner holes.

[0078] A third, optional but preferred coating step c) may be performed on the surface of the glass substrate. When the glass sheet article / hole is made before the coating step, it has been found that when such a coating step is performed before the separation of the inner portion from the rest of the glass sheet article and before the separation of different glass sheet articles from the glass substrate, it is possible to coat the glass sheet article up to the separation line around its edges and around the edges of the hole, while avoiding the coating dripping along the edges of the glass sheet article / hole. Thus, the method of the present invention can provide extremely smooth coated surfaces, as well as extremely sharp and smooth edges and partially reinforced edges, in an extremely efficient, simple and fast manufacturing process.

[0079] A fourth, optional but preferred step is a cleavage step d), which includes a cleavage step d1) of the separation line (3) forming the glass sheet article (10) and a cleavage step d2) of the separation line (3) forming an inner hole (1) in the glass sheet article (10). For process efficiency, it is preferable that the separation line for separating the glass sheet article (10) from the glass substrate (20) and the separation line for separating the intended inner portion are performed simultaneously. However, substeps d1) and d2) may be performed separately in any order. With respect to the cleavage step d), the same technique described above applies herein.

[0080] The final step of the method of the second embodiment of the present invention is a separation step e), which includes a separation step e1) for separating a glass sheet article (10) from a glass substrate (20). Any separation technique may be used. Separation step e) further includes a step e2) for separating the inner portion (2) from the glass sheet article (10) at adjacent and aligned fibrous defects (3) along a separation line by irradiating with an ablation laser to remove at least one segment within the inner portion, wherein at least one segment has two endpoints located on the separation line, has a substantially thick T, and has a width W (W ≥ 150 μm) of 150 μm or more. Depending on the separation technique used to separate the glass sheet article from the glass substrate, steps e1) and e2) may be performed simultaneously or sequentially in any order.

[0081] Separation of a glass sheet article from a glass substrate is preferably achieved by a fiberization process of release lines created around the outer shape of the glass sheet article. The fiberization step of release line a3) may be performed separately, or during the fiberization step a1) for the production of at least one glass sheet article along a separation line that divides the glass substrate into at least one glass sheet article to be separated, and / or during the step a2) for the separation of the inner portion from the glass sheet article along a separation line (3) that defines the inner portion to be separated. In practice, the fiberization steps a1), a2) and / or a3) may be performed simultaneously or sequentially in any order. In a preferred embodiment, the fiberization steps a1) and a2) are performed simultaneously in a single step, followed by the fiberization step a3), and then the chemical strengthening step. Alternatively, the fiberization step of release line a3) may be performed immediately before or after the step e1) for the separation of the inner portion from the glass article.

[0082] The proposed method of the second embodiment allows for the production of chemically strengthened, preferably coated, glass sheet articles with internal pores from a simple method, where the chemical strengthening and optional coating processes can be applied continuously and directly to a larger glass substrate. The glass sheet articles are separated from the larger glass according to separation lines determined according to the required size and shape of the glass article. The inner portions are separated according to separation lines determined according to the required size and shape of the internal pores, following an ablation separation step e2). Thus, the strengthening, preferred coating, and separation of the glass article are better controlled. Coating lamination by this method is also much easier than when performed on larger glass panels, when used. Thus, production yield is increased and manufacturing costs are reduced. Edge-to-edge coating and paint lamination can be easily produced by this method. Furthermore, the method of the present invention provides a means for substantially saving the consumption of coating materials and glass substrates.

[0083] Furthermore, the method of the present invention provides means for obtaining a chemically strengthened coated glass article that can be cold-vented. The method according to the present invention is less expensive and more efficient than conventional methods for manufacturing coated chemically strengthened glass. As the name suggests, cold venting is carried out at the natural temperature of the factory. The process begins by placing the glass into a frame that mechanically bends the glass into the desired frame shape. In the frame installation process, the glass is glued directly to the frame or attached with screws. The frame is then ready for installation in a vehicle or building. The thinner the glass, the easier it is to bend from a mechanical standpoint. The shape may, however, have a twisted design. This method enhances the cold venting action because the end faces of the glass article are strengthened by ion exchange.

[0084] Cold vents are recognized for bending glass articles for interior and exterior glazing parts of a vehicle, such as glass consoles, dashboards, trim elements for doors, pillars, windshields, side windows, rear windows, sunroofs, and partition walls. According to the present invention, after strengthening and preferably coating, the potassium level on the surface of the glass article is higher than the potassium level present at the edges and pores of the glass article. The potassium level at the end faces of the glass article increases during chemical strengthening. Thus, the end faces of the glass article are more resistant to external loads / stresses. Consequently, the surfaces of the glass article that can be subjected to tension are better strengthened (especially in cold vents), and compression is limited where compression is not needed to limit the central tension.

[0085] Glass properties In a preferred embodiment, the glass sheet article and the glass substrate are 70 × 10 -7 / ℃~100×10 -7 / ℃(70×10 -7 / ℃≦CET≦100×10 -7 ( / ℃), preferably 80 × 10 -7 / ℃~95×10 -7 / ℃(80×10 -7 / ℃≦CET≦95×10 -7 It has a thermal expansion coefficient CET (in / °C). The thermal expansion coefficient of glass is a parameter that indicates how the dimensions of the corresponding glass element change due to expansion or contraction as a result of temperature changes. The thermal expansion coefficient is linear thermal expansion a = (1 / L)(ΔL / ΔT) refers to the coefficient, where ΔT is the temperature difference and ΔL is the change along a linear dimension relative to the original length L.

[0086] Typically, the thickness of the glass sheet article / glass substrate is at least 0.1 mm (T≧0.1 mm), preferably at least 0.3 mm (T≧0.3 mm), and more preferably at least 0.5 mm (T≧0.5 mm). Typically, the thickness of the glass sheet article / glass substrate is 20.0 mm or less (T≦20.0 mm), preferably 10.0 mm or less (T≦10.0 mm), more preferably 2 mm or less (T≦2.0 mm), more preferably 1.5 mm or less (T≦1.5 mm), and more preferably 1 mm or less (T≦1 mm). The present invention's method for partial laser separation from sheet glass elements is particularly suitable for sheet elements having the aforementioned thicknesses. In practice, it has been found that the thinner the glass sheet article, the faster the process. It has also been found that the thinner the glass article, the smaller the internal pores that can be achieved.

[0087] Glass sheet articles The present invention also relates to glass articles obtained by the method described above. Glass articles can be used in fields such as cover glass for electronic devices, glazing for building materials, and glazing for vehicles, where high strength is often required for safety reasons and compliance with safety regulations required for such glazing is often necessary.

[0088] In particular, the present invention proposes decorative panels for vehicle interiors. Decorative panels according to the present invention are attached to any part of a vehicle interior to provide better aesthetics or to fix or protect certain parts of the vehicle interior. Such decorative panels may be attached to (completely or partially) cover doors, door handle outlines, parts of the dashboard or center console (center console meaning the console between the passenger seats that may extend toward the dashboard), seat backs (including the backs of the headrests), roofs, armrests, etc. Vehicles refer to any type of vehicle, such as (but not limited to) passenger cars, vans, lorries, motorcycles, buses, trams, trains, drones, aircraft, helicopters, etc. [Examples]

[0089] Forty-five glass articles, each containing two internal holes, were manufactured using the following method. A glass substrate made of aluminosilicate glass, measuring 1000 mm in length, 1000 mm in width, and 1.3 mm in thickness, was prepared. The internal holes were 20 mm. 2 It has the following surface area. The glass substrate has the following composition, expressed as a weight percentage of the total composition. TIFF2026509397000002.tif48170

[0090] Fiberization step a) Internal voids within the glass sheet articles and glass sheet articles within the glass substrate were created by a single fiberization step. To form two or more in-plane void regions in the vertical and horizontal directions, a laser was irradiated onto the glass substrate in the direction of the main plane. A Hyper Rapid NX laser, manufactured by Coherent (Germany), capable of emitting short-pulse lasers on the order of picoseconds, was used. The frequency of one burst of the laser was 80 kHz, and the pulse width was 9 picoseconds. Laser irradiation was achieved only once in each in-plane void region (thus a single-pass laser irradiation). In each in-plane void region, the center-to-center distance between the centers of surface voids was set to 5 μm. Separation lines of the glass sheet articles in the glass substrate and separation lines of internal voids in the glass sheet articles were created simultaneously.

[0091] Chemical strengthening step b) Chemical strengthening was performed by immersing the glass substrate in molten salt at 450°C for 2 hours. The results of the chemical strengthening treatment showed no pre-existing fragmentation in the glass substrate.

[0092] Coating step c) After cleaning, two layers of silkscreen printing were performed on one side of the glass substrate. The ink was black organic. The curing conditions were 15 minutes at 100°C for pre-curing and 20 minutes at 150°C for final curing. On the other side of the glass substrate, an anti-reflective coating was added in a vacuum chamber by digital sputtering of the anti-reflective functional layer, and a fingerprint-resistant organic material was laminated on top of the anti-reflective functional layer by evaporation.

[0093] Additional steps After chemical strengthening and coating surface treatment, additional release lines for separation step e1) were created using the same laser and conditions as described above. These additional release lines were self-cleaved by the central tension of the chemically strengthened glass.

[0094] Cleaving step d) The separation lines of glass sheet articles on glass substrates and the separation lines of internal holes in glass sheet articles were coupled together by a CO2 laser, a Diamond J5 manufactured by Coherent. The CO2 laser was irradiated from the anti-reflective and anti-fingerprint coated side. The average power output was 25W, and the estimated focal diameter was 5mm.

[0095] Separation step e) The glass sheet article was first separated from the glass substrate by mechanical fracture of the release line created in the above step.

[0096] To separate the internal pores in the glass sheet article, the inner segment was removed by ablation laser. A nanosecond pulsed green laser was used to irradiate a 150 μm thick segment around 100% of the outer circumference of the inner segment, creating space for the internal pores by dropping the inner segment from the glass sheet article. The average laser power was 50 W, and its estimated focal diameter was 30 μm. TIFF2026509397000003.tif38170

Claims

1. A method for creating an internal hole (1) in a glass sheet article (10) having a thickness T, wherein the internal portion (2) is separated from the glass sheet article along a separation line (3), and the method comprises, in the following order, at least: a) A step of fibrosis, wherein fibrous defects are created within the volume of the glass sheet article in the form of submicron hollow channels aligned adjacently along the separation line, the defects are created by laser pulses of an ultrashort pulse laser, the material of the glass sheet article is transparent to the laser pulses, the laser pulses generate plasma within the volume of the glass sheet article, the plasma causes the fibrous defects, the incident point of the laser pulses in the glass sheet article is displaced across its surface along the separation line to introduce the fibrous defects aligned adjacently along the separation line, b) Steps for chemical strengthening the glass sheet article, e) A step of separating the inner portion from the glass sheet article at adjacent, aligned fibrous defects along the separation line by irradiating the inner portion with an ablation laser to remove at least one segment (4), wherein the at least one segment has two endpoints located on the separation line, substantially the thickness T, and a width W of 150 μm or more (W ≥ 150 μm). Methods that include...

2. A method for manufacturing at least one glass sheet article (10) having a thickness T and containing an internal hole (1) from a glass substrate (20), wherein the method is carried out in the following order: a1) A fiberization step for producing the at least one glass sheet article along a separation line, wherein the separation line is for dividing the glass substrate into the at least one glass sheet article. a2) A fibrous step for separating an inner portion (2) from a glass sheet article along a separation line (3) defining the inner portion to be separated, wherein fibrous defects are created within the volume of the glass substrate in the form of submicron hollow channels adjacently aligned along the separation line, the defects are created by laser pulses of an ultrashort pulse laser, the material of the glass substrate is transparent to the laser pulses, the laser pulses generate plasma within the volume of the glass substrate, the plasma causes the fibrous defects, the incident point of the laser pulses on the glass substrate is displaced across its surface along the separation line to introduce the adjacently aligned fibrous defects along the separation line, b) A step of chemical strengthening the glass substrate (20), and e) e1) Separation step for separating the glass sheet article (10) from the glass substrate (20), e2) Separating the inner portion (2) from the glass sheet article at adjacent, aligned fibrous defects along the separation line (3) by irradiating the inner portion with an ablation laser to remove at least one segment, wherein the at least one segment has two endpoints located on the separation line, substantially the thickness T, and a width W of 150 μm or more (W ≥ 150 μm). A method that includes this.

3. The method according to claim 1 or 2, further comprising a cleavage step d) performed along the separation line through which the fibers are interbonded, wherein the cleavage step is performed immediately before the separation step e).

4. The method according to any one of claims 1 to 3, further comprising a coating step c) of the glass sheet article or glass sheet substrate, performed after the chemical strengthening step b) and before the cleavage step d) if present.

5. The aforementioned internal bore is 300 mm ２ (S ≤ 300 mm) ２ ), preferably 150 mm ２ (S ≤ 150 mm) ２ ), preferably 120 mm ２ Below (S ≤ 120 mm) ２ ), a more preferable 80 mm ２ (S ≤ 80 mm) ２ The method according to any one of claims 1 to 4, having the surface area of ​​).

6. The inner hole is 3 mm ２ or more (S ≥ 3 mm ２ ), preferably 5 mm ２ or more (S ≥ 5 mm ２ ), and has a surface area as described in any one of claims 1 to 5

7. The method according to any one of claims 1 to 6, wherein the at least one segment within the inner portion has a width of 200 μm or more (W ≥ 200 μm), preferably 250 μm or more (W ≥ 250 μm).

8. The method according to any one of claims 1 to 7, wherein the inner portion has at least two segments.

9. The method according to any one of claims 1 to 8, wherein the at least one segment extends along at least 50%, preferably at least 75%, and more preferably 100% of the outer circumference of the inner portion.

10. The method according to any one of claims 1 to 9, wherein the glass sheet article has a thickness of at least 0.1 mm, preferably at least 0.3 mm, more preferably at least 0.5 mm, and less than 20 mm, preferably less than 10 mm, more preferably less than 2 mm, more preferably less than 1.5 mm, and more preferably less than 1 mm.

11. A glass sheet article obtained by the method described in any one of claims 1 to 10.

12. The glass sheet article according to claim 11, comprising a soda lime silicate glass composition, an aluminosilicate glass composition, or an alkali aluminosilicate glass composition.

13. The aforementioned glass sheet article is 70 x 10 －７ / ℃~100×10 －７ / ℃, preferably 80 × 10 －７ / ℃~95×10 －７ A glass sheet article according to claim 11 or 12, having a CTE of / °C.

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