Reinforced via glass and method of making and using same

Abstract

The application discloses a preparation method of reinforced through-hole glass products, comprising the following steps: pre-strengthening a through-hole glass substrate to obtain a pre-strengthened through-hole glass substrate, strengthening the pre-strengthened through-hole glass substrate to obtain a strengthened through-hole glass substrate, and cooling and oil-bathing the strengthened through-hole glass substrate to obtain the reinforced through-hole glass, wherein the oil-bathing comprises using one or more of silicon oil, synthetic heat-conducting oil and perfluoropolyether oil for treatment, and the temperature of the oil-bathing is 340-350 DEG C. The preparation method of the application repairs micro-cracks and pit defects on the surface of the through-hole glass and near the hole area, prevents the through-hole glass from being deformed, warped, damaged and blocked during the strengthening process, and prevents the through-hole glass from being burst / damaged, the strength and stability of the through-hole glass are greatly improved, the super-thin and flexible through-hole glass is reinforced, and the application can be widely applied to related electronic products.

Description

TECHNICAL FIELD

[0001] The present application relates to glass processing technology, in particular to a kind of reinforced through-hole glass and its preparation method and application. BACKGROUND

[0002] Glass is a typical brittle material, there are a large number of microcracks on its surface and inside, under the action of external force and environmental medium, it is easy to crack propagation, so that the glass is destroyed. At present, chemical tempering can effectively improve the surface stress of glass and its bending strength, which is one of the effective glass strengthening methods. With the continuous progress of science and technology, the light and thin trend of mobile phones, displays and other related products makes the shortcomings of glass gradually appear, especially the ultra-thin, flexible glass with through-hole structure, which is filled with through-holes inside, and there are microcracks, pits or burr defects on the surface and around the hole area, which is easy to cause burst / breakage. The conventional chemical tempering method cannot meet the performance requirements of the ultra-thin, through-hole glass product, resulting in the use performance of related application products cannot meet the standard. SUMMARY

[0003] Therefore, it is necessary to provide a preparation method capable of reducing the breakage and warping of through-hole glass during the strengthening process, improving the stress of through-hole glass, and the application of reinforced through-hole glass.

[0004] In a first aspect, the present application provides a preparation method of reinforced through-hole glass, comprising the following steps:

[0005] pre-tempering the through-hole glass substrate to obtain a pre-tempered through-hole glass substrate;

[0006] tempering the pre-tempered through-hole glass substrate to obtain a tempered through-hole glass substrate;

[0007] cooling and oil-bathing the tempered through-hole glass substrate to obtain the reinforced through-hole glass;

[0008] The oil-bathing includes treating with one or more of silicone oil, synthetic heat-conducting oil and perfluoropolyether oil, and the temperature of the oil-bathing is 340-350℃.

[0009] In some embodiments, the pre-tempering is treated with a pre-tempering treatment agent, and the tempering is treated with a tempering treatment agent, and the composition of the pre-tempering treatment agent and the tempering treatment agent each independently includes one or more of lithium salt, potassium salt and sodium salt.

[0010] In some embodiments, the pre-tempering treatment agent and the tempering treatment agent further satisfy at least one of the following (1)-(7):

[0011] (1) the lithium salt is selected from one or more of lithium nitrate, lithium sulfate, lithium chloride, lithium hydroxide and lithium carbonate;

[0012] (2) the potassium salt is selected from one or more of potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, and potassium phosphate;

[0013] (3) the sodium salt is selected from one or more of sodium fluoride, sodium nitrate, sodium chloride, sodium sulfate, and sodium carbonate;

[0014] (4) the composition of the pre-strengthening treatment agent comprises a lithium salt and a sodium salt;

[0015] (5) the mass percentage of the lithium salt in the composition of the pre-strengthening treatment agent is 1-5 wt%, and the mass percentage of the sodium salt is 60-95 wt%;

[0016] (6) the composition of the strengthening treatment agent comprises a potassium salt and a sodium salt;

[0017] (7) the composition of the strengthening treatment agent comprises 90 wt%-95 wt% of the potassium salt and 5 wt%-10 wt% of the sodium salt.

[0018] In some embodiments, the composition of the pre-strengthening agent comprises, by mass percentage:

[0019] 60%-70% of sodium nitrate,

[0020] 1%-5% of lithium nitrate, and

[0021] 5%-15% of sodium fluoride;

[0022] and / or, the composition of the strengthening agent comprises, by mass percentage:

[0023] 90%-95% of potassium nitrate, and

[0024] 5%-10% of sodium nitrate.

[0025] In some embodiments, the preparation method further satisfies at least one of the following (1)-(4):

[0026] (1) the temperature of the pre-strengthening is 330°C-360°C;

[0027] (2) the temperature of the strengthening is 380°C-390°C;

[0028] (3) the cooling is performed by means of salt dripping cooling;

[0029] (4) the temperature after the cooling is 340°C-370°C.

[0030] In some embodiments, the strengthened through-hole glass has a thickness of 0.03 mm-0.2 mm; and / or the strengthened through-hole glass comprises through-holes with an inner diameter of 5 μm-80 μm.

[0031] In some embodiments, the oil bath step is followed by one or more of annealing and cleaning.

[0032] In some embodiments, the annealing procedure comprises: heating to 400-420℃, slow cooling to 250-300℃ after 5-10min, fast cooling to 90-100℃; cooling rate: slow cooling 40-60℃ / H, fast cooling 80-100℃ / H.

[0033] In a second aspect, the present application further provides a strengthened through-hole glass, which is prepared by the above-mentioned method for preparing a strengthened through-hole glass.

[0034] In a third aspect, the present application further provides a strengthened through-hole glass product, which comprises a strengthened through-hole glass and a strengthening layer laminated on at least one surface of the strengthened through-hole glass; the strengthened through-hole glass is the strengthened through-hole glass prepared by the above-mentioned method for preparing a strengthened through-hole glass, or is the above-mentioned strengthened through-hole glass.

[0035] In some embodiments, the strengthening layer laminated on the surface of the strengthened through-hole glass is at least one layer.

[0036] In a fourth aspect, the present application further provides an electronic product comprising the above-mentioned strengthened through-hole glass product.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] The existing through-hole glass surface and the surrounding hole area have micro-cracks, pits or burr defects, which are easy to cause burst / damage, especially in the steeling process, the hole area is prone to burst and warping, and in the conventional steeling process, the condensation and pulling deformation of the salt in and around the hole during cooling causes product deformation, damage and hole area blockage, thereby seriously affecting the performance and use of the through-hole glass. The present application pre-steeled the through-hole glass substrate to achieve preliminary steeling and repair the micro-cracks and pit defects on the surface and around the hole of the through-hole glass to prevent burst / damage caused by stress, improve the strength of the substrate, further improve the steeling effect and stability of the through-hole glass substrate, remove the liquid salt after steeling by oil bath to prevent the hole area from being deformed, warped, damaged and blocked due to the crystallization of solidified liquid salt, and finally make the surface stress depth and surface stress of the strengthened through-hole glass high, thereby realizing the strengthening of the ultra-thin and flexible through-hole glass. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 The figure is a schematic diagram of the preparation process of the strengthened through-hole glass and the strengthened through-hole glass product of the present application. DETAILED DESCRIPTION

[0040] For the purpose of promoting an understanding of the application, the preferred embodiments of the application will be described below in greater detail. It should be noted, however, that the application can be practiced in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.

[0041] It should be noted that the experimental methods in the following examples of the present application, which are not specified with specific conditions, are generally carried out according to the conventional conditions, or according to the conditions suggested by the manufacturers. The various common chemical reagents used in the examples are commercially available products.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0043] Glass is a typical brittle material, with low tensile strength, and a large number of micro-cracks exist on the surface and inside the glass, which can easily expand under the action of external force and environmental medium, thereby causing the glass to be damaged. For example, during the glass tempering process, the existence of micro-cracks can cause local stress concentration during heating and cooling, resulting in uneven stress distribution inside the glass, affecting the overall strength and stability of the glass. In particular, through-hole glass, due to the existence of a large number of dense through-holes inside the glass, is prone to hole area burst or warping, etc. Therefore, the present application provides a method for preparing strengthened through-hole glass.

[0044] In a first aspect, the present application provides a method for preparing strengthened through-hole glass, comprising the following steps:

[0045] pre-tempering the through-hole glass substrate to obtain a pre-tempered through-hole glass substrate;

[0046] tempering the pre-tempered through-hole glass product to obtain a tempered through-hole glass substrate;

[0047] cooling and oil-bathing the tempered through-hole glass product to obtain strengthened through-hole glass;

[0048] The oil-bathing includes using one or more of silicone oil, synthetic heat-conducting oil and perfluoropolyether oil for treatment, and the temperature of the oil-bathing is 340-350℃.

[0049] In some embodiments, the synthetic heat-conducting oil can be selected from hydrogenated terphenyl heat-conducting oil

[0050] The present application can slow down the defects such as micro-cracks in the through-hole glass by pre-strengthening treatment, which is beneficial to improve the strength and stability of the through-hole glass, thereby improving the rigidification effect of the through-hole glass; further, the glass after strengthening is cooled and oil-bathed, and the oil-bathing is high-temperature oil-bathing, which can prevent the hole area of the through-hole glass from being blocked and deformed due to the existence of dense through holes, the residual solidification crystallization in the strengthening step, and the like, thereby reducing the occurrence of serious problems such as micro-cracks, pits, deformation and breakage, and further improving the flatness and strength of the through-hole glass.

[0051] In some embodiments, the pre-strengthening is treated by a pre-strengthening agent, the strengthening is treated by a strengthening agent, and the composition of the pre-strengthening agent and the strengthening agent each independently includes one or more of lithium salt, potassium salt and sodium salt.

[0052] The present application uses one or more inorganic salts including lithium salt, potassium salt and sodium salt as the pre-strengthening agent and the strengthening agent, which can enable the salt ions in the molten salt to perform deep, slow and uniform ion exchange reaction with the through-hole glass, and achieve slow flattening of defects such as micro-cracks.

[0053] In some embodiments, the lithium salt in the composition of the pre-strengthening agent and the strengthening agent is selected from one or more of lithium nitrate, lithium sulfate, lithium chloride, lithium hydroxide and lithium carbonate; further, the use of lithium nitrate can better assist the entire ion exchange process and slow and uniform exchange depth.

[0054] In some embodiments, the potassium salt in the composition of the pre-strengthening agent and the strengthening agent is selected from one or more of potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate and potassium phosphate; further, the use of potassium nitrate can better perform more sufficient and deep exchange reaction.

[0055] In some embodiments, the sodium salt in the composition of the pre-strengthening agent and the strengthening agent is selected from one or more of sodium fluoride, sodium nitrate, sodium chloride, sodium sulfate and sodium carbonate; further, the use of sodium fluoride can slowly react with silicon dioxide in the through-hole glass to achieve slow flattening of defects such as micro-cracks, and the use of sodium nitrate can assist the entire exchange process and slow and uniform exchange depth.

[0056] In some embodiments, the composition of the pre-strengthening agent includes lithium salt and sodium salt.

[0057] In some embodiments, the pre-strengthening treatment agent has a composition including 1 wt% to 5 wt% lithium salt and 60 wt% to 95 wt% sodium salt; wherein the lithium salt content includes but is not limited to 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof; and wherein the sodium salt content includes but is not limited to 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92, 95 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof.

[0058] In some embodiments, the pre-strengthening treatment agent has a composition including 1 wt% to 5 wt% lithium nitrate, 60 wt% to 70 wt% sodium nitrate, and 5 wt% to 15 wt% sodium fluoride; wherein the lithium nitrate content includes but is not limited to 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof; wherein the sodium nitrate content includes but is not limited to 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof; and wherein the sodium fluoride content includes but is not limited to 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof.

[0059] With the pre-strengthening treatment agent described above, the sodium nitrate within the range of the ratio is used to ion exchange with lithium ions of the through-hole glass, the lithium nitrate within the range of the ratio is used as an auxiliary agent to make the entire exchange process and exchange depth slow and uniform, and the sodium fluoride within the range of the ratio is used to make the substrate silicon dioxide slowly react, so as to achieve slow smoothing of defects such as micro-cracks.

[0060] In some embodiments, the strengthening treatment agent has a composition including a potassium salt and a sodium salt.

[0061] In some embodiments, the strengthening treatment agent has a composition including 90 wt% to 95 wt% potassium salt and 5 wt% to 10 wt% sodium salt; wherein the potassium salt content includes but is not limited to 90, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof; and wherein the sodium salt content includes but is not limited to 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 wt% or any value within the range formed by any two of the foregoing, and any value within the range thereof.

[0062] In some embodiments, the steeling agent includes 90-95wt% potassium nitrate and 5-10wt% sodium nitrate; potassium nitrate in this proportion range can exchange sodium ions and lithium ions in the through-hole glass more fully and deeply, and sodium nitrate in this proportion range can slow down and evenly the whole exchange process and exchange depth.

[0063] In some embodiments, the pre-steeling agent includes, by mass percentage:

[0064] sodium nitrate 60%-70%,

[0065] lithium nitrate 1%-5%,

[0066] sodium fluoride 5%-15%, and

[0067] water 20%-30%.

[0068] In some embodiments, the steeling agent includes, by mass percentage:

[0069] potassium nitrate 90%-95%, and

[0070] sodium nitrate 5%-10%.

[0071] In some embodiments, the through-hole glass can be preheated before pre-steeling, and the through-hole glass is preheated from room temperature to 300-350°C and kept for 20-60min.

[0072] In some embodiments, the pre-steeling temperature in the preparation method is 330-360°C, including but not limited to 330, 335, 340, 345, 350, 355, 360°C or a temperature range formed by any two of the foregoing and any value within the range.

[0073] In some embodiments, the pre-steeling time in the preparation method is 30-120min, including but not limited to 30, 40, 50, 60, 70, 80, 90, 100, 110, 120min or a time range formed by any two of the foregoing and any value within the range.

[0074] In some embodiments, the pre-steeling through-hole glass can be preheated before steeling, and the pre-steeling through-hole glass is preheated to 340-390°C.

[0075] In some embodiments, the steeling temperature in the preparation method is 380-390°C, including but not limited to 380, 382, 384, 385, 386, 388, 390°C or a temperature range formed by any two of the foregoing and any value within the range.

[0076] In some embodiments, the pre-strengthening time in the preparation method is 10-40 min, including but not limited to 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40 min or a temperature range formed by any two of the foregoing and any value within the range thereof.

[0077] In some embodiments, the temperature after cooling in the preparation method is 340-370℃, including but not limited to 340, 345, 350, 355, 360, 365, 370℃ or a temperature range formed by any two of the foregoing and any value within the range thereof.

[0078] In some embodiments, the cooling in the preparation method is carried out by salt dripping cooling.

[0079] The salt dripping cooling is carried out by dripping salt in the preheating furnace after the substrate is strengthened, and then the temperature is lowered to the post-processing process, wherein the preheating furnace is preheated to 370-390℃, and the strengthened glass substrate is sent to the preheating furnace, and then the temperature is slowly lowered to 340-370℃, and the liquid salt automatically drips during the process, and the surface residue is preliminarily reduced.

[0080] Because there are many crystals remaining on the through-hole glass after pre-strengthening, strengthening and cooling processes, and due to the existence of dense through-holes in the glass, the salt crystals will be accumulated in a large area in the hole area after the liquid salt is cooled to the freezing point. In order to prevent the residual molten liquid salt crystals in the hole area from causing the deformation and damage of the ultra-thin glass due to pulling, and to prevent the hole area from being blocked, the strengthened through-hole glass substrate after cooling is subjected to oil bath desalting treatment to remove the residual liquid salt in the hole and around the hole, so as to avoid the deformation and fragmentation of the ultra-thin substrate due to pulling, and to further improve the flatness and strength of the substrate. The temperature of the oil bath is 340-350℃, including but not limited to 340, 342, 344, 345, 346, 348, 350℃ or a temperature range formed by any two of the foregoing and any value within the range thereof. The temperature of the oil bath is 10-30 min, including but not limited to 10, 12, 15, 18, 20, 22, 25, 28, 30 min or a time range formed by any two of the foregoing and any value within the range thereof.

[0081] In some embodiments, the thickness of the through-hole glass is 0.03-0.2 mm, including but not limited to 0.03, 0.05, 0.06, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2 mm or a thickness range formed by any two of the foregoing and any value within the range thereof.

[0082] In some embodiments, the reinforced via glass comprises a via inner diameter of 5-80 μm, including but not limited to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80 μm or a via inner diameter range formed by any two of the foregoing and any value within the range thereof.

[0083] In some embodiments, the oil bath step is further followed by one or more of an annealing and a cleaning step.

[0084] In some embodiments, the oil bath treatment is further followed by an annealing procedure.

[0085] In some embodiments, the annealing procedure comprises: heating to 400-420 °C, cooling to 250-300 °C at a cooling rate of 40-60 °C / H, and cooling to 90-100 °C at a cooling rate of 80-100 °C / H.

[0086] In some embodiments, the cleaning comprises but is not limited to ultrasonic cleaning.

[0087] In some embodiments, the ultrasonic cleaning procedure comprises: ultrasonic cleaning at 50-90 °C for 20-30 min.

[0088] In some embodiments, the cleaning step can be performed after the oil bath treatment, or after the annealing procedure.

[0089] In the method for preparing the reinforced via glass, to prevent the via glass from being bent or otherwise adversely affected due to temperature difference, the via glass is subjected to pre-steel annealing from pre-heating, or to steel annealing from pre-heating, or to cooling from pre-heating, or to oil bath isothermal from pre-heating, and the temperature difference is not greater than 20 °C, or vice versa. To ensure this condition, the equipment should be started to pre-heat or cool down in advance.

[0090] In a second aspect, the present application further provides a reinforced via glass prepared by the method for preparing the reinforced via glass as described above.

[0091] In a third aspect, the present application further provides a reinforced via glass product, which comprises a reinforced via glass and a reinforcing layer laminated on at least one surface of the reinforced via glass; the reinforced via glass is prepared by the method for preparing the reinforced via glass as described above, or is the reinforced via glass as described above.

[0092] In some embodiments, the reinforcing layer laminated on the surface of the reinforced via glass is at least one layer.

[0093] In some embodiments, the thickness of the reinforcing layer is 3-10 μm.

[0094] In some embodiments, the strengthening layer is prepared by magnetron sputtering and / or evaporation, etc.

[0095] The present application sets a strengthening layer on the strengthened through-hole glass, which not only improves the strength (such as mechanical strength, hardness, impact resistance, etc.) of the strengthened through-hole glass, but also further repairs the surface micro-cracks and defects such as pits, thereby improving the stability of the strengthened through-hole glass product.

[0096] In some embodiments, the material of the strengthening layer is selected from one or more of organic silicon coating, inorganic nanoparticles and other polymer coatings; further, the strengthening layer is prepared by one or more materials selected from silicon oxide, silicon carbide, zirconium oxide and aluminum oxide, etc.

[0097] In some embodiments, the raw materials for preparing the strengthening layer include, by mass percentage:

[0098] 60%-70% of silicon oxide,

[0099] 25%-35% of zirconium oxide, and

[0100] 5%-15% of aluminum oxide.

[0101] The present application prepares an etching solution to remove the strengthening layer on the surface of the through-hole of the strengthened through-hole glass, and the composition of the etching solution includes, by mass percentage:

[0102] 50%-60% of sulfuric acid,

[0103] 5%-10% of potassium hydrogen fluoride,

[0104] 1%-5% of ammonium fluoride,

[0105] 10%-20% of oxalic acid, and

[0106] 20%-30% of water.

[0107] In some embodiments, the etching solution can be removed by alkaline solution cleaning.

[0108] In a fourth aspect, the present application further provides an electronic product comprising the strengthened through-hole glass product.

[0109] In some embodiments, the electronic product contains a mini LED structure and / or device of the strengthened through-hole glass product.

[0110] In the following specific embodiments, the experimental parameters not specified are preferred to refer to the guidance given in this application document, and can also refer to the experimental manual in the art or other experimental methods known in the art, or refer to the recommended experimental conditions of the manufacturer.

[0111] The raw materials and reagents involved in the following specific examples can be obtained commercially or prepared by those skilled in the art according to known means.

[0112] Preparation of strengthened through-hole glass

[0113] The present application prepares a strengthened through-hole glass, comprising the following steps:

[0114] A through-hole glass substrate with a thickness of 0.07 mm and an inner hole diameter of 50 μm is cleaned, inserted into a basket, and then placed in a preheating furnace and preheated to 320℃ for 20 min.

[0115] The preheated through-hole glass substrate is placed in a pre-strengthening furnace and pre-strengthened using a pre-strengthening agent, with a pre-strengthening temperature of 330℃ and a pre-strengthening time of 30 min, to obtain a pre-strengthened through-hole glass; the composition of the pre-strengthening agent is:

[0116] Sodium nitrate 70%,

[0117] Lithium nitrate 2%,

[0118] Sodium fluoride 8%, and

[0119] Water 20%.

[0120] The preheating furnace is preheated to 350℃, the pre-strengthened through-hole glass is transferred from the pre-strengthening furnace to the preheated preheating furnace, and the pre-strengthened through-hole glass is further preheated to 370℃.

[0121] The preheated pre-strengthened through-hole glass is transferred to a strengthening furnace and strengthened using a strengthening agent, with a strengthening temperature of 380℃ and a strengthening time of 10 min, to obtain a strengthened through-hole glass; the composition of the strengthening agent is:

[0122] Potassium nitrate 95%, and

[0123] Sodium nitrate 5%.

[0124] The preheating furnace is preheated to 370℃, the strengthened through-hole glass is transferred from the strengthening furnace to the preheated preheating furnace, and the strengthened through-hole glass is cooled to 360℃ using salt dripping precooling.

[0125] The cooled strengthened through-hole glass is immersed in high-temperature modified synthetic silicon oil UOLEN-150H at 340℃ for oil bath treatment for 10 min.

[0126] The oil-bathed strengthened through-hole glass is transferred to a preheating furnace for annealing treatment, and the annealing program is:

[0127] Firstly, the temperature is raised to 400℃ and kept for 10 min, then slowly annealed and cooled to 280℃ at a cooling rate of 40℃ / H, and then rapidly cooled to 90℃ at a cooling rate of 80℃ / H.

[0128] The annealed and tempered through-hole glass is placed in a water solution containing 30wt% of commercially available super-strong cleaning agent JX-643 to remove oil stains through ultrasonic cleaning, the ultrasonic temperature is 80℃, and the ultrasonic time is 20 min, thereby obtaining the strengthened through-hole glass.

[0129] Example 2, preparation of strengthened through-hole glass

[0130] The present application prepares a strengthened through-hole glass, comprising the following steps:

[0131] The through-hole glass substrate with a thickness of 0.07mm and an inner hole diameter of 50μm is cleaned, inserted into a basket, and then placed in a preheating furnace and preheated to 350℃ and kept for 20 min.

[0132] The preheated through-hole glass substrate is placed in a pre-tempering furnace and pre-tempered using a pre-tempering agent, the pre-tempering temperature is 360℃, and the pre-tempering time is 30 min, thereby obtaining a pre-tempered through-hole glass; the composition of the pre-tempering agent is:

[0133] 70% of sodium nitrate,

[0134] 2% of lithium nitrate,

[0135] 8% of sodium fluoride, and

[0136] 20% of water.

[0137] The preheating furnace is preheated to 370℃ in advance, the pre-tempered through-hole glass is transferred from the pre-tempering furnace to the preheated preheating furnace, and the pre-tempered through-hole glass is further preheated to 380℃.

[0138] The preheated pre-tempered through-hole glass is transferred to a tempering furnace and tempered using a tempering agent, the tempering temperature is 390℃, and the tempering time is 15 min, thereby obtaining a tempered through-hole glass; the composition of the tempering agent is:

[0139] 95% of potassium nitrate, and

[0140] 5% of sodium nitrate.

[0141] The preheating furnace is preheated to 380℃ in advance, the tempered through-hole glass is transferred from the tempering furnace to the preheated preheating furnace, and the tempered through-hole glass is cooled to 360℃ using salt dripping precooling.

[0142] The above cooled tempered through-hole glass is immersed into an oil bath of high-temperature modified synthetic silicon oil UOLEN-150H at 340 ℃ for 10 min.

[0143] The above tempered through-hole glass after oil bath treatment is transferred into a preheating furnace for annealing treatment, and the annealing program is as follows:

[0144] firstly heated to 400 ℃ and kept for 10 min, then slowly annealed and cooled to 280 ℃ at a cooling rate of 40 ℃ / H, and then quickly cooled to 90 ℃ at a cooling rate of 80 ℃ / H.

[0145] The above annealed tempered through-hole glass is placed in deionized water for ultrasonic cleaning to remove oil stains, and the ultrasonic temperature is 60 ℃ and the ultrasonic time is 10 min, to obtain a strengthened through-hole glass.

[0146] Example 3, preparation of a strengthened through-hole glass

[0147] The difference between this example and Example 1 is that the composition of the pre-tempering treatment agent is different, and the composition of the pre-tempering treatment agent in this example is specifically as follows:

[0148] The composition of the pre-tempering treatment agent is:

[0149] sodium nitrate 55%,

[0150] lithium nitrate 8%,

[0151] sodium fluoride 17%, and

[0152] water 20%.

[0153] The remaining steps are consistent with Example 1.

[0154] Example 4, preparation of a strengthened through-hole glass

[0155] The difference between this example and Example 1 is that the composition of the pre-tempering treatment agent is different, and the composition of the pre-tempering treatment agent in this example is specifically as follows:

[0156] The composition of the pre-tempering treatment agent is:

[0157] potassium nitrate 70%,

[0158] lithium nitrate 1%,

[0159] sodium nitrate 9%, and

[0160] water 20%.

[0161] The remaining steps are consistent with Example 1.

[0162] Comparative Example 1

[0163] The difference between the example 1 and the present comparative example is that the strengthened through-hole glass of the present comparative example is not pre-strengthened, and the ultrasonic cleaning step is not used in the preparation process, and the conventional tempering process using potassium nitrate solution is used in the tempering process, and the conventional tempering process is as follows:

[0164] The conventional tempering process does not have pre-strengthening, oil bath treatment after tempering and secondary ultrasonic cleaning process, and the process route of the conventional tempering is: preheating-tempering-salt dripping-cooling-water washing.

[0165] The through-hole glass substrate is preheated to 390℃, and then tempered at 390℃ for 15min, the tempering molten liquid is potassium nitrate, and salt dripping is performed for 5min after tempering, and then cooled to 80℃, and the water washing is completed to obtain the conventional tempered through-hole glass.

[0166] Comparative Example 2

[0167] The difference between the example 1 and the present comparative example is that the strengthened through-hole glass of the present comparative example is not pre-strengthened, and the ultrasonic cleaning step is not used in the preparation process, and the conventional tempering process using potassium nitrate solution is used in the tempering process, and the conventional tempering process is as follows:

[0168] Comparative Example 3

[0169] The difference between the example 1 and the present comparative example is that the strengthened through-hole glass of the present comparative example is not pre-strengthened, and the ultrasonic cleaning step is not used in the preparation process, and the conventional tempering process using potassium nitrate solution is used in the tempering process, and the conventional tempering process is as follows:

[0170] Comparative Example 4

[0171] The difference between the example 1 and the present comparative example is that the strengthened through-hole glass of the present comparative example is not pre-strengthened, and the ultrasonic cleaning step is not used in the preparation process, and the conventional tempering process using potassium nitrate solution is used in the tempering process, and the conventional tempering process is as follows:

[0172] Test Example 1, Performance Test of Strengthened Through-Hole Glass

[0173] The above-prepared ultra-thin flexible strengthened through-hole glass and the through-hole glass substrate before strengthening of examples 1-4 and comparative examples 1-4 are tested for performance, and the test method is as follows:

[0174] Fragmentation rate: the number of fragments after tempering is visually counted to calculate the fragmentation rate.

[0175] Warpage: the warpage amount is measured after tempering using a plug gauge.

[0176] Surface stress depth: the result is obtained by using a surface stress tester after tempering.

[0177] Surface stress: the result is obtained by using a surface stress tester after tempering.

[0178] According to the above test method, the results are shown in Table 1:

[0179] Table 1: Performance test results of strengthened through-hole glass

[0180]

[0181] From the test results of Table 1, it can be seen that the surface stress depth of the strengthened through-hole glass prepared by the preparation method of the present application can reach 11 μm-15 μm, the surface stress is 450 MPa-700 MPa, and the strengthening of the ultra-thin, flexible through-hole glass with a thickness of 0.03 mm-2 mm is achieved. The through-hole glasses prepared by Comparative Examples 1-4 have a high breakage rate and many warps, and the surface stress and depth of the strengthened through-hole glass are also relatively low.

[0182] Example 5, Preparation of a strengthened through-hole glass product

[0183] The strengthened through-hole glass prepared in Example 2 was plated with a strengthening layer to obtain a strengthened through-hole glass product, and the specific steps are as follows:

[0184] A film coating machine was used to coat both sides of the strengthened through-hole glass with a commercially available photosensitive dry film, and a mask was set on the hole area by mark calibration exposure development, the mask above the hole was circular with a diameter of 60 um, covering the hole area.

[0185] The above film-coated strengthened through-hole glass was plated with a strengthening layer by magnetron sputtering and / or evaporation, and the thickness of the strengthening layer was 5 μm, and the strengthening layer had the following mass percentage composition:

[0186] Silicon oxide 60%,

[0187] Zirconium oxide 35%, and

[0188] Aluminum oxide 5%.

[0189] Both sides of the above strengthened through-hole glass plated with a strengthening layer were again coated with a commercially available photosensitive dry film, and exposed and developed to set a mask on the non-hole area, and then soaked in an etching liquid to expose the hole area, and the etching liquid had the following mass percentage composition:

[0190] Sulfuric acid 60%,

[0191] Potassium hydrogen fluoride 8%,

[0192] Ammonium fluoride 2%,

[0193] Oxalic acid 10%, and

[0194] Water 20%.

[0195] Finally, a 20 wt% sodium hydroxide degreasing solution was used at a temperature of 45°C to remove the residual photosensitive dry film to obtain a strengthened through-hole glass product containing a strengthening layer.

[0196] Test Example Two, Performance Test of Strengthened Through-Hole Glass Product Containing a Strengthening Layer

[0197] The results obtained from testing the strengthened via glass articles of Example 5 including a strengthening layer according to the test method of Test Example One are shown in Table 2:

[0198] Table 2: Performance test results for strengthened via glass articles

[0199]

[0200] Each technical feature in the above-described embodiments can be combined with any other technical feature, and for the sake of brevity, not all possible combinations are described, however, it should be understood that the scope of the specification includes all possible combinations.

[0201] The above-described embodiments are merely representative of several embodiments of the present application, and the description is relatively specific and detailed, but should not be construed as limiting the scope of the patent. It should be noted that for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the scope of the present application. Therefore, the scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for producing a reinforced via glass, characterized by, The method comprises the following steps: pre-strengthening the through-hole glass substrate to obtain a pre-strengthened through-hole glass substrate; strengthening the pre-strengthened through-hole glass substrate to obtain a strengthened through-hole glass substrate; cooling and oil-bathing the strengthened through-hole glass substrate to obtain a strengthened through-hole glass; the oil-bathing comprises using one or more of silicon oil, synthetic heat-conducting oil and perfluoropolyether oil, and the temperature of the oil-bathing is 340-350°C.

2. The method of claim 1, wherein the glass is strengthened via ion exchange. the pre-strengthening comprises using a pre-strengthening agent, and the strengthening comprises using a strengthening agent, and the pre-strengthening agent and the strengthening agent each independently comprise one or more of lithium salt, potassium salt and sodium salt.

3. The method of claim 2, wherein the glass is strengthened via ion exchange. the pre-strengthening agent and the strengthening agent further satisfy at least one of the following (1)-(7): (1) the lithium salt is selected from one or more of lithium nitrate, lithium sulfate, lithium chloride, lithium hydroxide and lithium carbonate; (2) the potassium salt is selected from one or more of potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate and potassium phosphate; (3) the sodium salt is selected from one or more of sodium fluoride, sodium nitrate, sodium chloride, sodium sulfate and sodium carbonate; (4) the composition of the pre-strengthening agent comprises lithium salt and sodium salt; (5) the mass percentage of lithium salt in the composition of the pre-strengthening agent is 1-5wt%, and the mass percentage of sodium salt is 60-95wt%; (6) the composition of the strengthening agent comprises potassium salt and sodium salt; (7) the composition of the strengthening agent comprises 90-95wt% of potassium salt and 5-10wt% of sodium salt.

4. The method of claim 2 or 3, wherein the glass is strengthened via ion exchange. the composition of the pre-strengthening agent comprises, by mass percentage: 60-70% of sodium nitrate, 1-5% of lithium nitrate, and 5-15% of sodium fluoride; and / or, the composition of the strengthening agent comprises, by mass percentage: 90-95% of potassium nitrate, and 5-10% of sodium nitrate.

5. The method of claim 1, wherein the glass is strengthened via ion exchange. the preparation method further satisfies at least one of the following (1)-(4): (1) the temperature of the pre-strengthening is 330-360°C; (2) the temperature of the strengthening is 380-390°C; (3) the cooling is performed by dropping salt; (4) the temperature after the cooling is 340-370°C.

6. The method of claim 1, wherein the glass is strengthened via ion exchange. the strengthened through-hole glass has a thickness of 0.03-0.2mm; and / or, the inner diameter of the through hole contained in the strengthened through-hole glass is 5-80μm.

7. A reinforced via glass characterized by, the strengthened through-hole glass is prepared by the method for preparing a strengthened through-hole glass according to any one of claims 1-6.

8. A strengthened via glass article, characterized by, the strengthened through-hole glass product comprises strengthened through-hole glass and a strengthening layer laminated on at least one surface of the strengthened through-hole glass; the strengthened through-hole glass is prepared by the method for preparing a strengthened through-hole glass according to any one of claims 1-6, or comprises the strengthened through-hole glass according to claim 7.

9. The strengthened via glass article of claim 8, wherein, the strengthening layer laminated on the surface of the strengthened through-hole glass is at least one layer.

10. An electronic product, characterized by comprising: the strengthened through-hole glass product according to claim 8 or 9.

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