Special protective glass and preparation method thereof

Abstract

The invention relates to the technical field of special glass, and discloses special protective glass and a preparation method thereof.The special protective glass comprises a glass substrate and a self-healing coating coated on the surface of the glass substrate; the glass substrate consists of oxides of the following elements: a silicon source, an aluminum source, a lithium source, a sodium source, a magnesium source, a zirconium source, a phosphorus source, a titanium source, a cerium source and a tin source; the self-healing coating comprises an organosiloxane film forming component, a crosslinking component, a silane anchoring component and nanoparticles; the cross-linking component comprises a boric acid ester bond cross-linking structure and a disulfide bond cross-linking structure; the silane anchoring component comprises at least one molecule with a trialkoxy silicon group at the tail end, and the self-healing coating is combined with a silanol group on the surface of the glass substrate through a silicon-oxygen bond to form an interface covalent binding layer. According to the invention, the glass can be effectively repaired after cracks appear, so that not only is the optical performance ensured, but also the mechanical strength of the glass is enhanced.

Description

Technical Field

[0001] This invention relates to the field of special glass technology, and more specifically, to a special protective glass and its preparation method. Background Technology

[0002] Specialty glass is widely used in modern industry, construction, automobiles, optical equipment and many other fields. It not only requires excellent optical properties, such as high transparency, low optical distortion and uniform refractive index, but also needs to have certain mechanical strength, wear resistance and corrosion resistance to cope with complex environmental conditions.

[0003] However, in practical applications, although special glasses have achieved certain improvements in mechanical strength and abrasion resistance, cracks appearing on the glass surface due to external impacts can lead to a decline in optical performance, structural strength, and service life over time. While existing glass surface strengthening technologies, such as surface hardening treatment and ion exchange strengthening, can improve the scratch resistance and impact resistance of glass to some extent, these technologies have limitations in crack repair. Once cracks appear on the glass surface, traditional glass repair techniques often cannot effectively restore its optical properties and surface smoothness, thus affecting the overall performance of the glass. Summary of the Invention

[0004] The purpose of this invention is to provide a special protective glass and its preparation method, which aims to improve the service life and durability of the special protective glass and enable effective repair after cracks appear in the glass.

[0005] The present invention provides a special protective glass, comprising a glass substrate and a self-healing coating applied to the surface of the glass substrate; The glass substrate is composed of the following oxides in parts by weight: 55.0-68.0 parts SiO2, 12.0-20.0 parts Al2O3, 2.5-6.0 parts Li2O, 6.0-13.0 parts Na2O, 0.5-4.5 parts MgO, 0.5-3.0 parts ZrO2, 0.10-1.00 parts P2O5, 0.00-2.00 parts TiO2, 0.05-0.60 parts CeO2, and 0.05-0.40 parts SnO2; The self-healing coating comprises organosiloxane film-forming components, cross-linking components, silane anchoring components, and nanoparticles; The cross-linking components include borate ester cross-linking structures and disulfide cross-linking structures; The silane anchoring component contains at least one molecule with a terminal trimekoxysilane group, and the self-healing coating forms an interfacial covalent bonding layer by bonding with the silanol group on the surface of the glass substrate through silicon-oxygen bonds. The dry film thickness of the self-healing coating is 1.5-8.0 μm, and the D50 of the nanoparticles is 5-20 nm.

[0006] Furthermore, the organosiloxane film-forming component in the self-healing coating is at least one of terminal hydroxyl polydimethylsiloxane and organosilsesquioxane; The crosslinking component includes a borate ester crosslinking agent and a disulfide bond crosslinking agent. The borate ester crosslinking agent is a difunctional phenylboronic acid ester or a difunctional alkylboronic acid ester, and the disulfide bond crosslinking agent is a dihydroxy disulfide or a diamino disulfide. The nanoparticles are nano-ZrO2 particles or nano-SiO2 particles.

[0007] Furthermore, based on the total dry film mass of the self-healing coating, the self-healing coating contains 55-78 wt% organosiloxane film-forming component, 8-25 wt% crosslinking component, 3-12 wt% silane anchoring component, and 1-10 wt% nanoparticles.

[0008] Furthermore, the mass ratio of terminal hydroxyl polydimethylsiloxane to organosilicon silsesquioxane in the organosiloxane film-forming component is 3-15:1; the mass ratio of borate ester crosslinking agent to disulfide bond crosslinking agent in the crosslinking component is 1-4:1; the silane anchoring component includes bis(triethoxysilyl)ethane and 3-glycidyl etheroxypropyltrimethoxysilane, with a mass ratio of bis(triethoxysilyl)ethane to 3-glycidyl etheroxypropyltrimethoxysilane of 0.5-3:1; the surface of the nanoparticles is silanized by one or more molecules of bis(triethoxysilyl)ethane and 3-glycidyl etheroxypropyltrimethoxysilane, with the amount of silanization modification being 0.5-5 wt% of the nanoparticle mass.

[0009] On the other hand, the present invention provides a method for preparing special protective glass, comprising the following steps: S1: Weigh the silicon source, aluminum source, lithium source, sodium source, magnesium source, zirconium source, phosphorus source, titanium source, cerium source and tin source raw materials according to the glass substrate formula, and mix them to obtain the compound material; S2: The batch is melted and clarified in an electric melting furnace at 1550-1680℃. During the clarification stage, dry oxygen is introduced into the glass melt and the furnace dew point is maintained at no higher than −40℃ to obtain clarified glass melt. S3: The clarified glass liquid is subjected to overflow and downward drawing or casting to obtain a glass substrate blank, and the glass substrate blank is subjected to annealing treatment to obtain an annealed glass substrate. S4: The annealed glass substrate is placed in potassium nitrate molten salt for ion exchange strengthening treatment to obtain a strengthened glass substrate; S5: Plasma activation treatment is performed on the surface of the tempered glass substrate to form a surface silanol enrichment layer; S6: Coat the surface silanol-enriched layer with a primer containing silane anchoring components and cure to obtain an interface primer layer; S7: Coat the self-healing coating precursor onto the interface undercoat and cure it to obtain the special protective glass.

[0010] Furthermore, in step S2, the melting time is 2.5-6.0 h, and the clarification stage adopts gas bubbling clarification. The bubbling gas is a mixture of dry oxygen and dry nitrogen, with an oxygen volume fraction of 10-60% and a bubbling flow rate of 0.2-2.0 L / min.

[0011] Furthermore, in step S4, the molten salt for ion exchange strengthening treatment is potassium nitrate molten salt, the ion exchange strengthening treatment temperature is 380-450℃, the ion exchange strengthening treatment time is 2-16h, and after ion exchange strengthening treatment, the strengthened glass substrate is desalted, cleaned, and dried.

[0012] Furthermore, in step S5, the plasma activation treatment uses oxygen plasma or argon-oxygen mixed plasma, with a radio frequency power of 50-250W and a treatment time of 30-300s. Furthermore, in step S6, the primer liquid contains a bifunctional silane molecule, which is at least one of bis(triethoxysilyl)ethane and 3-glycidoxypropyltrimethoxysilane. The primer liquid has a curing temperature of 80-140℃ and a curing time of 10-60 min.

[0013] Furthermore, in step S7, the self-healing coating precursor includes an organosiloxane film-forming component, a crosslinking component, a silane anchoring component, and nanoparticles. In step S7, the film formation method is dip coating, and the dip coating speed is 20-180 mm / min; The curing methods in step S7 include UV curing and thermal curing. The UV irradiation energy is 0.3-2.5 J / cm², the thermal curing temperature is 80-140℃, and the thermal curing time is 10-90 min.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention achieves integrated protection and repair through the synergistic effect of a high-strength substrate, a covalent interface, and a reversible network coating. Firstly, the glass substrate uses SiO2-Al2O3 as the framework, Li2O / Na2O as the exchangeable alkali metal source, and introduces a combination system of MgO, ZrO2, P2O5, TiO2, CeO2, and SnO2. This allows the glass network to achieve higher structural density and surface damage resistance while maintaining visible light transparency. The ion exchange strengthening step uses potassium nitrate molten salt to drive Na... + / Li + With K+ Gradient displacement establishes a compressive stress layer on the surface, which blunts the stress at the crack tip caused by external forces, thereby reducing the crack propagation rate and improving impact and crack resistance. Secondly, plasma activation induces the formation of a silanol-rich layer on the glass surface. After hydrolysis and condensation, the silane anchoring component in the primer forms Si-O-Si covalent bonds with the silanol groups, constructing a stable interfacial covalent bonding layer. This transforms the traditional physical adhesion between the self-healing coating and the glass substrate into a chemical bond, reducing the risk of interfacial delamination under humid heat, friction, and thermal cycling conditions. Furthermore, the self-healing coating provides a high-transmittance, low-stress, and flexible film-forming matrix using organosiloxane film-forming components. The crosslinking components simultaneously introduce two types of reversible crosslinking structures: borate ester bonds and disulfide bonds. When cracks or scratches occur on the glass surface, the network segments at the cracks undergo local breakage and interface exposure. This region achieves reconnection of cross-sectional segments and interface reconstruction through reversible exchange of borate ester bonds and reversible rearrangement of disulfide bonds, thereby restoring the refractive index and structural continuity at the cracks and reducing scattering and hazy appearance caused by cracks. At the same time, nano-ZrO2 or nano-SiO2, as inorganic reinforcing phases, improves the surface hardness and wear resistance of the coating. Moreover, after silanization modification, the nanoparticles form a more stable interfacial compatibility structure with the organosiloxane phase, which not only inhibits optical scattering caused by agglomeration but also reduces local plastic damage to the coating under stress. Thus, a synergistic protective path of scratch resistance and post-damage repair is achieved. In addition, the introduction of dry oxygen and control of the furnace dew point to be no higher than -40°C during the melting and refining stage, combined with bubbling refining, can reduce the probability of introducing volatile gases and hydroxyl-related defects in the glass melt and promote the discharge of bubbles, thereby reducing internal scattering centers from the source and making the transparency and optical uniformity of the substrate more stable. Detailed Implementation

[0015] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to specific embodiments. Example 1

[0016] (1) Preparation of batch materials By weight of oxides: SiO2 65.0, Al2O3 16.0, Li2O 4.0, Na2O 9.0, MgO 2.0, ZrO2 2.0, P2O5 0.50, TiO2 1.0, CeO2 0.30, SnO2 0.20.

[0017] Raw materials selected: quartz sand (SiO2 source), alumina powder (Al2O3 source), lithium carbonate (Li2O source), sodium carbonate (Na2O source), magnesium carbonate (MgO source), zirconium oxide powder (ZrO2 source), ammonium dihydrogen phosphate (P2O5 source), titanium dioxide powder (TiO2 source), cerium dioxide powder (CeO2 source), and tin dioxide powder (SnO2 source).

[0018] Weigh the raw materials and place them in a sealed mixing tank. Mix them in a drum mixer at 30 rpm for 25 minutes to obtain the batch.

[0019] (2) Melting and Clarification The batch material is placed in a platinum crucible or a high-alumina crucible and fed into an electric melting furnace; the temperature is raised to 1620℃ and held for 4.0 hours to complete melting and clarification.

[0020] During the clarification stage, a dry mixed gas is bubbled into the bottom of the molten glass. The mixed gas is O2 / N2, with an O2 volume fraction of 30% and a flow rate of 1.0 L / min. The furnace dew point is controlled at −45℃ (through a closed-loop control between the dry gas source and the dew point meter).

[0021] (3) Molding and annealing A glass substrate blank with a thickness of 2.0 mm was formed by using an overflow pull-down method.

[0022] Annealing process: Hold at 560℃ for 2.5h, then reduce to 350℃ at a rate of 1.0℃ / min and cool to room temperature in the furnace to obtain annealed glass substrate. Before annealing, the edges of the glass substrate blank are mechanically chamfered with a chamfer width of 0.3mm.

[0023] (4) Ion exchange enhancement The annealed glass substrate was immersed in potassium nitrate molten salt and kept at 420℃ for 8.0h.

[0024] After ion exchange, the substrate is removed, rinsed with deionized water for 8 minutes, and dried with hot air at 60°C for 20 minutes to obtain a reinforced glass substrate.

[0025] (5) Surface cleaning and plasma activation The tempered glass substrate is subjected to the following steps in sequence: ultrasonic cleaning with neutral cleaning agent for 10 minutes → rinsing with deionized water → rinsing with anhydrous ethanol → drying at 80℃ for 15 minutes.

[0026] The cleaned tempered glass substrate was placed in a plasma treatment chamber and evacuated to 50 Pa. O2 gas (80 sccm) was introduced and treated with 150 W radio frequency power for 120 s to obtain a silanol-based enriched layer on the surface.

[0027] (6) Preparation, application and curing of primer Primer formulation (parts by weight): 94.0 parts anhydrous ethanol, 6.0 parts deionized water, 0.60 parts bis(triethoxysilyl)ethane, 0.30 parts 3-glycidyl etheroxypropyltrimethoxysilane, and 0.10 parts glacial acetic acid.

[0028] Preparation sequence: First, mix ethanol and water, add glacial acetic acid to adjust the pH to 4.5; then add bis(triethoxysilyl)ethane and 3-glycidoxypropyltrimethoxysilane in sequence, stir magnetically at 25°C for 30 min, and let stand for 60 min to age to obtain the primer.

[0029] Coating: Immerse the tempered glass substrate in the primer liquid at a lifting speed of 60 mm / min; level at room temperature for 10 min; cure at 120℃ for 30 min to obtain the interface primer layer.

[0030] (7) Silanization modification of nanoparticles Nano ZrO2 (D50=10nm) was selected.

[0031] 10.0 g of nano ZrO2 was added to 90.0 g of ethanol and ultrasonically dispersed for 30 min; 0.20 g of 3-glycidoxypropyltrimethoxysilane (2.0 wt% of the nanoparticle mass) was added and stirred at 25 °C for 2.0 h; after centrifugation, the nano ZrO2 was washed once with ethanol and then redispersed with ethanol to obtain a silanized nano ZrO2 dispersion.

[0032] (8) Preparation of self-healing coating precursor (corresponding to S7, supplement solid content / solvent / filtration) Based on total dry film mass (wt%): Organosiloxane film-forming component 70.0 (of which terminal hydroxyl polydimethylsiloxane: organosilsesquioxane = 8:1, mass ratio); Crosslinking component 15.0 (of which difunctional phenylboronic acid ester: dihydroxy disulfide = 2:1, mass ratio); Silane anchoring component 8.0 (of which bis(triethoxysilyl)ethane: 3-glycidoxypropyltrimethoxysilane = 2:1, by mass). Nanoparticles 7.0 (for step (7) silanized nano ZrO2).

[0033] The above components were added to ethanol to prepare a precursor solution with a solid content of 12.0 wt%; stirred at 25°C for 60 min; filtered once through a 0.45 μm filter membrane for later use.

[0034] (9) Dip coating and curing (corresponding to S7, supplement UV band / distance / environment) The precursor solution was dipped into the interface base coating at a lifting speed of 80 mm / min and leveled at room temperature (25℃) for 15 min.

[0035] UV curing: A 254nm UV lamp was used, with the sample 80mm away from the lamp tube, and the cumulative irradiation energy was 1.2J / cm². Thermosetting: Hold at 110℃ for 45 minutes.

[0036] Dry film thickness measurement: The thickness was measured using a step meter (steps were prepared by the masking method), and the dry film thickness was 3.5 μm. Example 2

[0037] (1) Preparation of batch materials By weight of oxides: SiO2 58.0, Al2O3 19.0, Li2O 5.5, Na2O 10.0, MgO 2.5, ZrO 2.5, P2O 5 0.60, TiO 2 1.2, CeO 2 0.40, SnO 2 0.30.

[0038] Mixing conditions: drum mixing at 35 rpm for 30 min.

[0039] (2) Melting and clarifying Insulation at 1600℃ for 3.5h; bubbling gas O2 / N2, O2 volume fraction 50%, flow rate 0.6L / min; dew point −42℃.

[0040] (3) Casting and annealing Casting thickness 3.0mm; Annealing: 575℃ for 2.0h, then cooled in the furnace at 0.8℃ / min to 320℃.

[0041] (4) Ion exchange Potassium nitrate molten salt was applied at 400℃ for 12.0 h; desalting and washing were performed for 10 min; and drying was carried out at 70℃ for 15 min.

[0042] (5) Plasma activation The cleaning process is the same as in Example 1.

[0043] Plasma: Ar / O2 volume ratio 3:1, total flow rate 120 sccm; chamber pressure 60 Pa; radio frequency power 200 W; processing time 90 s.

[0044] (6) Primer By weight, the following ingredients were used: 92.0 parts ethanol, 8.0 parts water, 0.45 parts bis(triethoxysilyl)ethane, 0.45 parts 3-glycidyl etheroxypropyltrimethoxysilane, and 0.12 parts glacial acetic acid; pH was adjusted to 4.3; the mixture was stirred for 40 min and aged for 90 min.

[0045] Dip coating and pull-out at 80 mm / min; cure at 130℃ for 25 min.

[0046] (7) Silanization of nanoparticles 10.0 g of nano-SiO2 (D50=15 nm); 90.0 g of ethanol; 0.30 g (3.0 wt%) of bis(triethoxysilyl)ethane; stirred at 25 °C for 2.0 h; washed once with ethanol and then redispersed.

[0047] (8) Self-healing coating precursor Dry film formulation (wt%): Film-forming component 66.0 (hydroxyl-terminated polydimethylsiloxane: organosilicon silsesquioxane = 10:1), crosslinking component 20.0 (difunctional alkyl borate ester: dihydroxy disulfide = 3:1), silane anchoring component 6.0 (bis(triethoxysilyl)ethane: 3-glycidyl etheroxypropyltrimethoxysilane = 1:1), nanoparticles 8.0.

[0048] Ethanol was prepared to a solid content of 10.0 wt%; stirred for 70 min; and filtered through a 0.45 μm filter.

[0049] (9) Dip coating and curing Lifting speed 120mm / min; leveling 20min.

[0050] UV curing: 254nm, distance 90mm, energy 0.8J / cm²; Heat curing: 120℃ for 60 minutes.

[0051] Dry film thickness: 5.5 μm, measured by the masking step method. Example 3

[0052] (1) Preparation of batch materials By weight of oxides: SiO2 66.0, Al2O3 12.5, Li2O 2.8, Na2O 12.0, MgO 3.0, ZrO2 1.8, P2O5 0.30, TiO2 0.7, CeO2 0.60, SnO2 0.30.

[0053] Mixing: 25 rpm, 20 min.

[0054] (2) Melting and clarifying Insulation at 1650℃ for 5.0h; bubbling gas O2 / N2, O2 volume fraction 20%, flow rate 1.5L / min; dew point −41℃.

[0055] (3) Overflow pull-down and annealing The thickness of the pull forming is 1.1 mm; annealing: hold at 545℃ for 3.0 h, and then cool in the furnace at 1.2℃ / min down to 300℃.

[0056] (4) Ion exchange Potassium nitrate molten salt at 440℃ for 6.0 h; washing for 6 min; drying at 60℃ for 25 min.

[0057] (5) Plasma activation O2 flow rate 60 sccm; cavity pressure 45 Pa; RF power 80 W; processing time 180 s.

[0058] (6) Primer By weight, the mixture consisted of 95.0 parts ethanol, 5.0 parts water, 0.30 parts bis(triethoxysilyl)ethane, 0.60 parts 3-glycidyl etheroxypropyltrimethoxysilane, and 0.10 parts glacial acetic acid; pH=4.6; stirring for 35 min and aging for 60 min.

[0059] Dip coating and pull-out at 50 mm / min; cure at 100℃ for 40 min.

[0060] (7) Silanization of nanoparticles 10.0 g of nano ZrO2 (D50=8 nm); 90.0 g of ethanol; 0.10 g (1.0 wt%) of 3-glycidyl etheroxypropyltrimethoxysilane was added; the mixture was stirred at 25 °C for 2.5 h; and then redispersed after washing once with ethanol.

[0061] (8) Self-healing coating precursor Dry film formulation (wt%): film-forming component 74.0 (hydroxyl-terminated polydimethylsiloxane: organosilicon silsesquioxane = 6:1), crosslinking component 12.0 (difunctional phenylboronic acid ester: diamine disulfide = 1:1), silane anchoring component 6.0 (bis(triethoxysilyl)ethane: 3-glycidyl etheroxypropyltrimethoxysilane = 0.8:1), nanoparticles 8.0.

[0062] Ethanol was prepared to a solid content of 14.0 wt%; stirred for 60 min; and filtered through a 0.45 μm filter.

[0063] (9) Dip coating and curing Lifting speed 60mm / min; leveling 12min.

[0064] UV curing: 254nm, distance 70mm, energy 1.8J / cm²; Heat curing: 90℃ for 80 minutes.

[0065] Dry film thickness: 2.0 μm as measured by the step method.

[0066] Comparative Example 1 The difference between this comparative example and Example 1 is that: (1) In the primer step, the primer of Example 1 contains bis(triethoxysilyl)ethane and 3-glycidyl etheroxypropyltrimethoxysilane; the primer of this comparative example is changed to consist only of 94.0 parts of anhydrous ethanol, 6.0 parts of deionized water and 0.10 parts of glacial acetic acid. When preparing the primer, the pH is adjusted to 4.5 and the primer is allowed to stand for 60 min for aging. Then, the primer is applied at the same dip-coating speed of 60 mm / min as in Example 1 and cured at 120°C for 30 min. However, the primer does not introduce trialkoxysilyl molecules.

[0067] (2) In the self-healing coating precursor formulation, the silane anchoring component of Example 1 was 8.0 wt%; in this comparative example, the silane anchoring component was adjusted to 0 wt%, and the organosiloxane film-forming component was adjusted from 70.0 wt% to 78.0 wt%, the crosslinking component was kept at 15.0 wt%, the nanoparticles were kept at 7.0 wt%, and the remaining preparation and film-forming curing conditions were the same as in Example 1.

[0068] Comparative Example 2 The difference between this comparative example and Example 1 is that: (1) In the crosslinking composition of the self-healing coating, the crosslinking component of Example 1 is composed of difunctional phenylboronic acid ester and dihydroxy disulfide in a mass ratio of 2:1; in this comparative example, the boronic acid ester crosslinking agent is omitted, and the boronic acid ester crosslinking agent is 0 wt%, and the crosslinking component is composed entirely of dihydroxy disulfide at 15.0 wt%; in order to keep the total dry film formulation at 100 wt%, the organosiloxane film-forming component is adjusted from 70.0 wt% to 70.0 wt%, the silane anchoring component is kept at 8.0 wt%, and the nanoparticles are kept at 7.0 wt%.

[0069] (2) Except for the changes in the composition of the crosslinking components mentioned above, the other steps (S1-S7, primer formulation, plasma activation conditions, dip-coating speed, UV curing and thermal curing regime, dry film thickness control method) are the same as in Example 1.

[0070] Comparative Example 3 The difference between this comparative example and Example 1 is that: (1) In the nanoparticle processing step, Example 1 performed silanization modification on nano ZrO2 (using 3-glycidyl etheroxypropyltrimethoxysilane as a modifier, with a modification amount of 2.0 wt% of the nanoparticle mass); this comparative example omits the nanoparticle silanization modification step, does not perform any silanization reaction and washing redispersion treatment, and directly uses unmodified nano ZrO2 (D50=10nm) to add to the self-healing coating precursor.

[0071] (2) The self-healing coating dry film formulation is the same as that in Example 1: 70.0 wt% organosiloxane film-forming component, 15.0 wt% crosslinking component, 8.0 wt% silane anchoring component, and 7.0 wt% nanoparticles. The remaining preparation and film-forming curing conditions are the same as those in Example 1.

[0072] Comparative Example 4 The difference between this comparative example and Example 1 is that: (1) In the surface activation step, in Example 1, O2 plasma activation (cavity pressure 50Pa, O2 80sccm, RF power 150W, treatment 120s) was performed on the reinforced glass substrate in step S5 to form a surface silanol enrichment layer; in this comparative example, the plasma activation treatment in step S5 was omitted, and the reinforced glass substrate was directly entered into the primer coating step S6 after only undergoing the same cleaning and drying process as in Example 1.

[0073] (2) Except for the elimination of plasma activation, the primer formulation, self-healing coating precursor formulation, dip coating and curing regime are the same as in Example 1.

[0074] Experimental tests were conducted on Examples 1-3 and Comparative Examples 1-4, and Examples 1-3 and Comparative Examples 1-4 were numbered as groups 1-7 respectively.

[0075] The detection method is as follows: 1) Transmittance and haze: Samples of the characteristic protective glass prepared in Examples 1-3 and Comparative Examples 1-4 were prepared with a sample size of 50mm×50mm×2.0mm.

[0076] Transmittance: Measured average transmittance (Tavg) at 400-700 nm.

[0077] Haze: Haze H was measured, with n=3 for each group, and the average value was taken. The test results are shown in Table 1.

[0078] 2) Evaluation of artificial injury and self-healing Scratch preparation: Scratch tester, load 5N, scratch speed 5mm / s, length 10mm, single scratch.

[0079] Scratch depth: The maximum scratch depth d is measured using a profilometer.

[0080] Self-healing conditions: 25℃, 50% relative humidity, kept in the dark; measurements were taken at 2h, 6h, 24h, and 48h.

[0081] Recovery rate: R(t) = (d0−dt) / d0×100%.

[0082] 3) Adhesion Hundred-grid method: Records levels 0-5.

[0083] Pull-out method: Record the pull-out strength σ (MPa).

[0084] Aging conditions: 85℃, 85%RH for 168 h; and 25℃ deionized water for 168 h.

[0085] 4) Wear-resistant Taber wear: CS-10F grinding wheel, single wheel load 500g, 500 rpm. Record the haze before and after wear, and calculate ΔH=H.after -H before .

[0086] Table 1 Transmittance and Haze Group Undamaged Tavg (%) Undamaged H (%) Damage 0h Tavg (%) Damage 0h H (%) 24h healing time (Tavg) (%) Healing 24h H (%) Healing time 48 hours Tavg (%) Healing 48h H (%) 1 92.3 0.18 88.9 1.52 92 0.21 92.2 0.19 2 91.9 0.24 88.4 1.7 91.5 0.3 91.8 0.26 3 92.5 0.16 89.3 1.45 92.2 0.18 92.4 0.17 4 92.4 0.19 88.7 1.6 90.2 0.95 90.5 0.9 5 92.2 0.19 88.8 1.55 91 0.55 91.3 0.48 6 90.5 0.85 86.9 2.2 88.8 1.1 89.2 1 7 92.3 0.2 88.6 1.65 90.9 0.7 91.2 0.65 Table 2. Scratch depth variation over time and recovery rate Group d0(0h) d2h d6h d24h d48h R24h R48h 1 2.6 1.8 1.1 0.55 0.3 78.80% 88.50% 2 2.5 1.95 1.35 0.75 0.48 70.00% 80.80% 3 2.7 1.65 0.95 0.45 0.25 83.30% 90.70% 4 2.55 2.2 2.05 1.8 1.75 29.40% 31.40% 5 2.6 2.05 1.6 1.25 1.1 51.90% 57.70% 6 2.65 2.25 1.95 1.6 1.55 39.60% 41.50% 7 2.58 2.05 1.7 1.2 1.15 53.50% 55.40% Note: d is in μm.

[0087] Table 3. Repeatable healing data after 3 cycles Group 1st R24h 2nd R24h 3rd R24h 1 78.80% 76.50% 74.20% 2 70.00% 67.10% 64.00% 3 83.30% 81.00% 79.20% 5 51.90% 44.60% 38.20% Note: Day 24 was measured after standing at 25℃ and 50%RH for 24 hours.

[0088] Table 4 Adhesion and Environmental Durability Group Initial 100 squares Initial σ (MPa) After damp heat, Bai Ge σ (MPa) after humid heat Hundred-grid after soaking σ (MPa) after immersion in water 1 0 6.8 1 6 1 5.9 4 2 2.3 4 0.8 4 0.6 7 1 4 3 2.2 3 2 Table 5 Haze Increment After Taber Wear Group H (%) before wear H (%) after wear ΔH (%) 1 0.18 0.46 0.28 2 0.24 0.49 0.25 3 0.16 0.56 0.4 4 0.85 1.95 1.1 As can be seen from the table: Initial optical performance and undamaged stability As shown in Table 1, Examples 1-3 maintained a high average visible light transmittance and a low haze level under undamaged conditions. The initial transmittance and haze of the comparative samples were generally inferior to those of the Example groups. Furthermore, under conditions without introduced scratches, the transmittance of the Example samples fluctuated less during the observation period, indicating that the coatings possess good optical stability under normal lighting and environmental exposure conditions. In contrast, the transmittance decay and haze increase of the comparative samples were more significant, suggesting that the evolution of internal scattering centers in the coating was more pronounced over time, or that interfacial micro-defects were more likely to accumulate.

[0089] Transmittance recovery and haze reduction after scratches Table 1 shows that after introducing standard scratches, the transmittance of all samples decreased and the haze increased, but Examples 1-3 showed a more significant recovery trend in the subsequent recovery phase. The comparative samples showed a significantly smaller increase in transmittance and a higher residual haze value within the same observation period. These results indicate that the contribution of the example systems to light scattering was more effectively weakened after the introduction of damage, and the influence of defects on optical flux was more easily partially resolved over time.

[0090] Scratch depth evolution and morphology restoration Table 2 provides further support for the aforementioned optical variation trend. In Examples 1-3, the scratch depth continued to decrease over time after being scratched. In contrast, the depth reduction of the comparative samples was smaller, and some samples tended to plateau in the later stages, indicating that the residual scratches were difficult to converge further.

[0091] Based on the data correlation, there is a consistent direction of change between the reduction in scratch depth and the decrease in haze: the samples with a more significant decrease in scratch depth in the example group usually have a greater decrease in haze, indicating that the reduction in morphological defects and the decrease in light scattering intensity have a synergistic relationship.

[0092] Recovery retention after repeated injury cycles Table 3 reflects the recovery and retention capabilities of the system after multiple scratch cycles. Examples 1-3 showed only a slight decrease in recovery rate during the first to third cycles. This result indicates that the systems in these examples can maintain relatively stable recovery capabilities after multiple defect introductions, suggesting that the structural units participating in the recovery process did not undergo significant depletion within a small number of cycles.

[0093] The recovery rate of the comparative sample decreased more rapidly with increasing cycle number. This phenomenon indicates that the comparative system is more prone to irreversible defect accumulation, leading to accelerated decay of subsequent recovery capabilities.

[0094] Evaluation of interfacial adhesion stability and durability The adhesion results shown in Table 4 indicate that the examples remained stable after environmental treatment or cyclic treatment; Comparative Example 1 shows that the comparative example system was more prone to interface failure.

[0095] Table 5 further shows that the surface integrity of the system in the example is better maintained under mechanical action, and the increase in optical scattering centers is more suppressed.

[0096] Based on the data in Tables 1-5, Examples 1-3 exhibited more stable transmittance and haze performance in the undamaged state. After standard scratching, the transmittance recovery of the Example group was greater, the haze reduction was more complete, and the scratch depth decreased more significantly over time, showing a more effective defect morphology convergence trend. Under repeated damage cycles, the recovery rate of the Example group decreased less, demonstrating better cycle retention. Data related to interface adhesion and wear resistance also indicate that the Example systems are superior to the comparative system in terms of interface stability and mechanical durability. These results collectively support the conclusion that the interface anchoring system, crosslinking system combination, and nanoparticle surface treatment strategy used in the Examples all significantly contribute to maintaining transparency, post-damage recovery, and durability stability.

[0097] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A special protective glass, characterized in that, Including glass substrates and self-healing coatings applied to the surface of glass substrates; The glass substrate consists of the following oxides in parts by weight. Composition: SiO2 55.0-68.0 parts, Al2O3 12.0-20.0 parts, Li2O 2.5-6.0 parts, Na2O 6.0-13.0 parts, MgO 0.5-4.5 parts, ZrO2 0.5-3.0 parts, P2O5 0.10-1.00 parts, TiO2 0.00-2.00 parts, CeO2 0.05-0.60 parts, SnO2 0.05-0.40 parts; The self-healing coating comprises organosiloxane film-forming components, cross-linking components, silane anchoring components, and nanoparticles; The cross-linking components include borate ester cross-linking structures and disulfide cross-linking structures; The silane anchoring component contains at least one molecule with a terminal trimekoxysilane group, and the self-healing coating forms an interfacial covalent bonding layer by bonding with the silanol group on the surface of the glass substrate through silicon-oxygen bonds. The dry film thickness of the self-healing coating is 1.5-8.0 μm, and the D50 of the nanoparticles is 5-20 nm.

2. The special protective glass according to claim 1, characterized in that, The self-healing coating contains at least one of hydroxyl-terminated polydimethylsiloxane and organosilsesquioxane. The crosslinking component includes a borate ester crosslinking agent and a disulfide bond crosslinking agent. The borate ester crosslinking agent is a difunctional phenylboronic acid ester or a difunctional alkylboronic acid ester, and the disulfide bond crosslinking agent is a dihydroxy disulfide or a diamino disulfide. The nanoparticles are nano-ZrO2 particles or nano-SiO2 particles.

3. The special protective glass according to claim 1, characterized in that, Based on the total dry film mass of the self-healing coating, the self-healing coating contains 55-78 wt% organosiloxane film-forming component, 8-25 wt% crosslinking component, 3-12 wt% silane anchoring component, and 1-10 wt% nanoparticles.

4. The special protective glass according to claim 3, characterized in that, The mass ratio of terminal hydroxyl polydimethylsiloxane to organosilicon silsesquioxane in the organosiloxane film-forming component is 3-15:1; the mass ratio of borate ester crosslinking agent to disulfide bond crosslinking agent in the crosslinking component is 1-4:1; the silane anchoring component includes bis(triethoxysilyl)ethane and 3-glycidyl etheroxypropyltrimethoxysilane, with a mass ratio of bis(triethoxysilyl)ethane to 3-glycidyl etheroxypropyltrimethoxysilane of 0.5-3:1; the surface of the nanoparticles is silanized by one or more molecules of bis(triethoxysilyl)ethane and 3-glycidyl etheroxypropyltrimethoxysilane, with the amount of silanization modification being 0.5-5 wt% of the nanoparticle mass.

5. A method for preparing special protective glass as described in any one of claims 1-4, characterized in that, Includes the following steps: S1: Weigh the silicon source, aluminum source, lithium source, sodium source, magnesium source, zirconium source, phosphorus source, titanium source, cerium source and tin source raw materials according to the glass substrate formula, and mix them to obtain the compound material; S2: The batch is melted and clarified in an electric melting furnace at 1550-1680℃. During the clarification stage, dry oxygen is introduced into the glass melt and the furnace dew point is maintained at no higher than −40℃ to obtain clarified glass melt. S3: The clarified glass liquid is subjected to overflow and downward drawing or casting to obtain a glass substrate blank, and the glass substrate blank is subjected to annealing treatment to obtain an annealed glass substrate. S4: The annealed glass substrate is placed in potassium nitrate molten salt for ion exchange strengthening treatment to obtain a strengthened glass substrate; S5: Plasma activation treatment is performed on the surface of the tempered glass substrate to form a surface silanol enrichment layer; S6: Coat the surface silanol-enriched layer with a primer containing silane anchoring components and cure to obtain an interface primer layer; S7: Coat the self-healing coating precursor onto the interface undercoat and cure it to obtain the special protective glass.

6. The method for preparing protective glass according to claim 5, characterized in that, In step S2, the melting time is 2.5-6.0 h. During the clarification stage, gas bubbling clarification is used. The bubbling gas is a mixture of dry oxygen and dry nitrogen. The volume fraction of oxygen in the mixture is 10-60%, and the bubbling flow rate is 0.2-2.0 L / min.

7. The method for preparing protective glass according to claim 5, characterized in that, In step S4, the molten salt for ion exchange strengthening treatment is potassium nitrate molten salt, the ion exchange strengthening treatment temperature is 380-450℃, the ion exchange strengthening treatment time is 2-16h, and after ion exchange strengthening treatment, the strengthened glass substrate is desalted, cleaned and dried.

8. The method for preparing protective glass according to claim 5, characterized in that, In step S5, the plasma activation treatment uses oxygen plasma or argon-oxygen mixed plasma, with a radio frequency power of 50-250W and a treatment time of 30-300s.

9. The method for preparing protective glass according to claim 5, characterized in that, In step S6, the primer contains a bifunctional silane molecule, which is at least one of bis(triethoxysilyl)ethane and 3-glycidoxypropyltrimethoxysilane. The primer curing temperature is 80-140℃ and the curing time is 10-60 min.

10. The method for preparing protective glass according to claim 5, characterized in that, In step S7, the self-healing coating precursor includes an organosiloxane film-forming component, a crosslinking component, a silane anchoring component, and nanoparticles. In step S7, the film formation method is dip coating, and the dip coating speed is 20-180 mm / min; The curing methods in step S7 include UV curing and thermal curing. The UV irradiation energy is 0.3-2.5 J / cm², the thermal curing temperature is 80-140℃, and the thermal curing time is 10-90 min.