Display screen glass with antibacterial surface and preparation method thereof

Abstract

The invention relates to the technical field of display screen glass, in particular to display screen glass with an antibacterial surface and a preparation method of the display screen glass. The preparation method comprises the following steps: S1, cleaning and drying a glass substrate; s2, activating the to-be-formed film surface of the glass substrate to improve the surface hydroxyl density; s3, forming a contact sterilization layer on the surface to be subjected to film forming: hydrolyzing and condensing the silane compound containing the quaternary ammonium salt group on the surface to be subjected to film forming, and covalently bonding the silane compound with the surface hydroxyl to form a siloxane network layer; s4, depositing and forming a transparent inorganic protection layer on the outer side of the contact sterilization layer; and S5, forming an anti-fingerprint layer on the outer side of the transparent inorganic protective layer. By constructing the contact sterilization layer, the siloxane network layer, the transparent inorganic protection layer and the anti-fingerprint layer, high light transmittance and low haze of the display screen are guaranteed, and unification of non-release contact sterilization, durability and user experience is achieved.

Description

Technical Field

[0001] This application relates to the field of display glass technology, and in particular to a surface-antibacterial display glass and its preparation method. Background Technology

[0002] Common antibacterial methods for existing display screen cover glass include: antibacterial by metal ions or nanoparticles such as silver / copper, photocatalytic antibacterial, and surface organic antibacterial coatings.

[0003] However, in the actual application of antibacterial technology in display glass, there are multiple contradictions: the effectiveness of antibacterial technology versus glass transmittance / haze, the antibacterial layer versus its lifespan (high-frequency touch wiping causes the coating to peel off or fail), and the difficulty in balancing antibacterial function with the requirements for fingerprint resistance / feel. Summary of the Invention

[0004] This application provides a surface-antibacterial display glass and a method for preparing the same, in order to solve the above-mentioned problems.

[0005] In a first aspect, this application provides a display screen glass with antibacterial surface, comprising a glass substrate and a composite functional film layer disposed on the outer surface of the glass substrate, wherein the composite functional film layer comprises, from the inside to the outside:

[0006] The contact sterilization layer is a siloxane network layer formed by the hydrolysis and condensation of a silane compound containing quaternary ammonium salt groups on the surface of a glass substrate and its covalent bonding with hydroxyl groups on the surface of the glass substrate.

[0007] A transparent inorganic protective layer covers the outside of the contact bactericidal layer to improve wear resistance and abrasion resistance.

[0008] An anti-fingerprint layer is disposed on the outside of the transparent inorganic protective layer to reduce surface energy and thus reduce the adhesion of fingerprints and oil stains.

[0009] The above technical solution constructs a contact bactericidal layer formed by covalent bonding on the surface of the glass substrate, which stably anchors quaternary ammonium salt groups in the siloxane network, preventing ion migration and yellowing. Then, by covering the outside with a dense and optically transparent inorganic protective layer, a physical barrier is provided without blocking the contact between bacteria and cations, significantly improving scratch resistance, sweat resistance, and wipe life. Finally, an ultra-thin oleophobic top layer is introduced, which uses the low surface energy properties of fluorine to inhibit the adsorption of fingerprints and oil stains and improve the sliding feel. The three work together to ensure high light transmittance and low haze, and achieve a balance between non-release contact bactericidal properties, durability, and user experience.

[0010] Optionally, the thickness of the contact sterilization layer is 2nm to 50nm;

[0011] The quaternary ammonium salt groups in the contact sterilization layer are provided by a quaternary ammonium salt silane precursor with a trialkoxysilyl group, wherein the alkoxy group of the quaternary ammonium salt silane precursor is methoxy and / or ethoxy.

[0012] By limiting the thickness of the contact sterilization layer to the range of 2nm to 50nm, the above technical solution ensures that a sufficient density of quaternary ammonium salt groups are exposed on the surface to achieve efficient contact sterilization, while avoiding cracking caused by excessive thickness leading to increased light interference and scattering or stress accumulation within the film. Simultaneously, a trimethoxy / triethoxysilane-based quaternary ammonium salt precursor is used. Its alkoxy groups can undergo controlled hydrolysis under weakly acidic conditions to generate silanol groups, which then condense with hydroxyl groups on the glass surface to form Si–O–Si covalent bonds, and further crosslink into a three-dimensional siloxane network, thereby enhancing the film density and interfacial bonding strength. The methoxy group has a faster hydrolysis rate and higher reactivity, while the ethoxy group is milder and has better film uniformity. The combination of these two allows for flexible control of reaction kinetics within the process window, supporting the feasibility of multiple film formation pathways, including solution and gas-phase methods.

[0013] Optionally, the thickness of the transparent inorganic protective layer is 5 nm to 60 nm;

[0014] The transparent inorganic protective layer comprises one or more of nano-silicon-based oxides (SiOx), silicon oxide carbides (SiOxCy), and nano-alumina (Al2O3);

[0015] The transparent inorganic protective layer has a nanoscale surface microstructure or nanopores.

[0016] Through the above technical solutions, by controlling the thickness of the transparent inorganic protective layer within the range of 5nm to 60nm, it can provide effective mechanical protection while avoiding the decrease in visible light interference color difference and transmittance caused by increased thickness. Materials such as SiOx, SiOxCy, or Al2O3 are selected because they have high hardness, excellent chemical inertness, and good optical transparency, and can form a dense and continuous film under low-temperature deposition conditions. Furthermore, by adjusting the PECVD power, sputtering bias voltage, or ALD cycle parameters, nanoscale (5–30nm) surface micro-protrusions or through-pores are introduced into the protective layer. On the one hand, this maintains its "penetration" to the bactericidal function of the underlying layer, allowing bacteria to still directly contact the quaternary ammonium salt groups through the gaps or channels in the microstructure. On the other hand, it improves the surface hydrophobicity and antifouling ability, synergistically enhancing the overall durability performance.

[0017] Optionally, the thickness of the anti-fingerprint layer is 0.5nm to 10nm;

[0018] The anti-fingerprint layer is one of a fluorinated silane self-assembled layer, a fluorinated organosilicon coating, or an oleophobic DLC layer.

[0019] By strictly limiting the thickness of the anti-fingerprint layer to 0.5nm–10nm, surface energy can be controlled at the molecular level. This satisfies the oleophobic requirements of a water contact angle ≥105° and an oil contact angle ≥60°, while minimizing optical path difference and interface reflection, ensuring a transmittance of ≥92% and a haze of ≤0.3% for the entire film system. Using fluorinated silanes (such as heptadecafluorodecyltriethoxysilane, FAS-17) vapor deposition or solution self-assembly, a monolayer (approximately 1–2nm thick) can be oriented on the surface of the inorganic protective layer, with vertically aligned fluorocarbon chains forming a low-energy surface. If a fluorinated organosilicon coating or an ultrathin DLC layer (3–8nm thick) is selected, the crosslinking density and thermal stability are enhanced through the synergistic effect of C–F bonds and Si–O–Si or C–C networks. Combined with post-baking treatment, the adhesion can reach grade 0 in the cross-linking test, significantly extending the anti-fingerprint lifespan.

[0020] Secondly, this application provides a method for preparing a display screen glass with an antibacterial surface, the method comprising:

[0021] S1. Clean and dry the glass substrate;

[0022] S2. The surface of the glass substrate to be film-forming is activated to increase the surface hydroxyl density;

[0023] S3. Forming a contact sterilization layer on the surface of the film to be formed: hydrolyzing and condensing a silane compound containing quaternary ammonium salt groups on the surface of the film to be formed and covalently bonding it with the surface hydroxyl groups to form a siloxane network layer;

[0024] S4. A transparent inorganic protective layer is deposited on the outer side of the contact sterilization layer;

[0025] S5. An anti-fingerprint layer is formed on the outside of the transparent inorganic protective layer.

[0026] Through the above technical solution, a five-step progressive process is set up to ensure that each functional layer is constructed sequentially, controllably, and stably: S1 cleaning removes organic residues and particulate contaminants, providing a clean interface for subsequent film formation; S2 activation treatment generates high-density hydroxyl groups in situ on the glass surface, providing sufficient reaction sites for silane grafting; S3 through a four-stage reaction of hydrolysis-condensation-grafting-curing, quaternary ammonium silanes achieves covalent anchoring and network cross-linking at the atomic scale; S4 uses low-temperature deposition technology to construct an inorganic protective layer on the organic sterilization layer, avoiding thermal damage and ensuring interfacial compatibility; S5 completes the outermost oleophobic modification through molecular self-assembly or vapor deposition, ultimately forming a structurally complete and functionally coupled multilayer composite system; this process is suitable for roll-to-roll coating lines and flat glass mass production lines, and is fully compatible with the post-processing of already bonded touch modules.

[0027] Optionally, the activation treatment in step S2 includes one or more of oxygen plasma treatment, UV-O3 treatment, or chemical hydroxylation treatment.

[0028] The above technical solutions can efficiently remove surface hydrocarbon contaminants and generate a large number of suspended hydroxyl groups by using oxygen plasma treatment; or by using UV-O3 treatment to achieve uniform surface oxidation and hydroxyl regeneration under conditions without physical contact; or by using chemical hydroxylation treatment, which is suitable for large-scale impregnation processes; all three methods can increase the hydroxyl density on the glass surface, significantly improve the silane grafting coverage and film uniformity, and the activated surface maintains high reactivity within 4 hours, ensuring the stability of the process window.

[0029] Optionally, step S3 specifically includes:

[0030] A silane compound containing quaternary ammonium salt groups was prepared into an aqueous system and pre-hydrolyzed to generate silanol groups;

[0031] The pre-hydrolyzed silane compound undergoes a condensation reaction on the surface of the film to be formed, forming a siloxane network;

[0032] The silanol groups in the siloxane network are covalently grafted onto the surface hydroxyl groups of the surface to be filmed, and then cured to obtain the contact sterilization layer.

[0033] The above technical solution involves pre-hydrolyzing the trialkoxysilane groups to fully convert them into active silanols (Si–OH), avoiding the formation of particulate aggregates due to rapid polymerization caused by excessively high local concentrations during direct coating. Subsequently, the silanol groups undergo dehydration condensation on the glass surface to construct a Si–O–Si network framework, and simultaneously react with the surface Si–OH to form Si–O–Si covalent bridges, achieving firm anchoring. Finally, thermosetting promotes the cross-linking and hydrogen bond rearrangement of the residual silanols, increasing the cross-linking degree of the contact bactericidal layer and significantly improving its stability against ethanol wiping and sweat immersion.

[0034] Optionally, the concentration of the silane compound in the aqueous system is 0.1 wt% to 5 wt%.

[0035] The pre-hydrolysis conditions are as follows: the pH value of the aqueous system is adjusted to 3-6;

[0036] The curing conditions are as follows: curing temperature is 60℃~120℃, and curing time is 5min~60min.

[0037] By controlling the silane concentration at 0.1wt%–5wt%, the film coverage is ensured while preventing agglomeration and precipitation. Acetic acid is used to adjust the pH to 3–6 to create a weakly acidic environment, resulting in a moderate hydrolysis rate and extending the effective use time of the solution to ≥4h. During the curing stage, the temperature is maintained at 60–120℃ for 5–60min, which can drive deep condensation without causing deformation of the glass substrate or decomposition of organic groups. The resulting contact sterilization layer has a controllable thickness and a roughness Ra≤0.3nm (AFM measurement), meeting the stringent optical requirements of display devices.

[0038] Optionally, step S4 involves depositing the transparent inorganic protective layer using one of PECVD, magnetron sputtering, or ALD at a temperature not exceeding 120°C.

[0039] The deposition thickness of the transparent inorganic protective layer in step S4 is controlled to be 5 nm to 60 nm.

[0040] The above technical solutions enable the deposition of dense SiOxCy films with a refractive index of 1.48 and a hardness of 8.2 GPa via PECVD; nanocrystalline Al2O3 films via magnetron sputtering; and atomically flat SiO2 films via ALD. All three methods can be deposited at ≤120℃, avoiding thermal degradation of the underlying organic bactericidal layer, and the thickness is precisely controlled within the range of 5–60 nm, balancing protective performance and optical compatibility.

[0041] Optionally, step S5 involves forming the anti-fingerprint layer using fluorinated silane vapor deposition or solution self-assembly, followed by a post-baking treatment at 80°C to 120°C to enhance stability.

[0042] Using the above technical solution, an oriented, ordered fluorocarbon monolayer is formed on the surface of the inorganic protective layer through FAS-17 vapor deposition, achieving a fluorine atomic surface density of 1.7 × 10⁻⁶. 15 cm⁻² (XPS measurement), the water contact angle reached 112°; or, by immersion in FAS-17 ethanol solution (0.5wt%) and self-assembly using the dip-coating method, followed by baking at 100°C for 10 min, the residual ethanol was volatilized and Si–O–Si crosslinking was enhanced, increasing the oil contact angle from the initial 52° to 68°, and reducing the coefficient of friction by 42% (relative to untreated glass). After 500 chamois wipings, the water contact angle remained ≥105°, confirming the key role of post-baking treatment in the stability of the oleophobic layer structure. Attached Figure Description

[0043] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0044] Figure 1 This is a flowchart illustrating a method for preparing an antibacterial display screen glass according to an embodiment of this application. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0046] Furthermore, the term "and / or" in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. Additionally, the character " / " in this article, unless otherwise specified, generally indicates that the preceding and following related objects have an "or" relationship.

[0047] The embodiments of this application will now be described in further detail with reference to the accompanying drawings.

[0048] Example 1:

[0049] A 100mm × 100mm × 0.55mm aluminosilicate cover glass was ultrasonically cleaned for 10 minutes with a neutral cleaning agent (Alconox® Liquinox®, 1% aqueous solution), ultrasonically rinsed three times with deionized water (5 minutes each time), and dried at 80℃ for 10 minutes. It was then placed in an oxygen plasma device and treated with 100W power and 20sccm oxygen flow rate for 30 seconds. Immediately afterward, it was transferred to a prepared quaternary ammonium silane solution, which was prepared by trimethylolpropionate hydrochloride (TMS). The mixture consisted of oxysilylpropyl dimethyl octadecyl ammonium chloride (1.0 wt%), ethanol / water (95 / 5, v / v), and acetic acid (adjusted to pH 4.0), and was pre-hydrolyzed for 30 min. A glass surface was treated with a dip-coating method, left to stand for 3 min, and then removed and spun dry at 1000 rpm for 10 s. The surface was then cured on an 80℃ hot plate for 30 min to obtain a contact sterilization layer (AFM measured a thickness of 10.2 ± 0.4 nm, XPS determined the N1s peak area to correspond to a quaternary ammonium salt surface density of 2.3 × 10¹). 4The layer was then deposited in a PECVD apparatus with TEOS and O2, RF power of 80W, deposition temperature of 90℃, and deposition time of 300s to obtain a SiOxCy transparent inorganic protective layer with a thickness of 30.5±0.6nm (refractive index of 1.48 measured by Ellipsometry, hardness of 8.2GPa measured by nanoindentation). Finally, the layer was deposited in a FAS-17 vapor chamber at 60℃ and 5Pa pressure for 20min, and then post-baked on a hot plate at 100℃ for 10min to obtain a fluorinated silane self-assembled anti-fingerprint layer with a thickness of 1.8±0.2nm (F / C atomic ratio of 0.31 measured by XPS, water contact angle of 112.3±1.2°). Tests showed that the sample had an average visible light (400–700 nm) transmittance of 92.4%, a haze of 0.27%, and antibacterial rates of 99.93% and 99.91% against Escherichia coli and Staphylococcus aureus, respectively (ISO22196). After 5000 wiping cycles with standard nonwoven fabric (load 5N), the antibacterial rates remained at 99.2% and 99.1%, respectively. The water contact angle remained at 108.5°, and the coefficient of friction decreased by 43.6% compared to the original glass.

[0050] Example 2:

[0051] With all other preparation conditions the same as in Example 1, only the thickness of the contact sterilization layer specified in this application was adjusted from 10.2 nm to 2.1 nm, i.e., the concentration of the quaternary ammonium silane solution was reduced to 0.15 wt%, while the remaining hydrolysis and curing conditions remained unchanged, thus obtaining the contact sterilization layer. The results showed that the product still possessed a clearly identifiable N1s XPS signal (area density 1.2 × 10⁻⁶). 14 The antibacterial rate was 99.0% against Escherichia coli and 99.2% against Staphylococcus aureus, with a transmittance of 92.6% and a haze of 0.25%, proving that the technical solution of the present invention can still be implemented and achieve basic antibacterial function at the lower limit of 2nm.

[0052] Example 3:

[0053] Under the same preparation conditions as in Example 1, only the thickness of the transparent inorganic protective layer specified in this application was adjusted from 30.5 nm to 59.8 nm, i.e., the PECVD deposition time was extended to 1180 s, to obtain the SiOxCy protective layer. The results show that the product has a thickness of 59.8 ± 0.7 nm, a transmittance of 92.1%, a haze of 0.29%, and antibacterial rates of 99.95% and 99.94%, respectively. After 5000 wipes, the antibacterial rates remained at 99.3% and 99.2%, demonstrating that the present invention can still balance optical performance and protective function at the upper limit of 60 nm.

[0054] Example 4:

[0055] With all other preparation conditions the same as in Example 1, only the thickness of the anti-fingerprint layer specified in this application was adjusted from 1.8 nm to 9.7 nm. Specifically, a fluorinated silicone coating (DowCorning® Q2-3069, 0.3 wt% ethanol solution) was spin-coated and baked at 100°C for 15 min to obtain the anti-fingerprint layer. The results showed that the product had a thickness of 9.7 ± 0.5 nm, a water contact angle of 110.5°, an oil contact angle of 65.2°, a transmittance of 92.2%, a haze of 0.28%, and antibacterial rates of 99.92% and 99.90%, respectively. This demonstrates that the present invention can maintain a balance between optical and oleophobic properties even at the upper limit of 10 nm.

[0056] Example 5:

[0057] With all other preparation conditions the same as in Example 1, only the pre-hydrolysis pH value specified in this application was adjusted from 4.0 to 3.0, while the other concentration, temperature, and time conditions remained unchanged, resulting in a contact sterilization layer. The results showed that the product thickness was 9.8 ± 0.5 nm, and the quaternary ammonium salt areal density determined by XPS was 2.2 × 10¹⁸. 4 The antibacterial rate was 99.91% and 99.89% at cm⁻², proving that the hydrolysis reaction was still controllable at the lower limit of pH 3 and the film quality was not significantly affected.

[0058] Example 6:

[0059] With all other preparation conditions the same as in Example 1, only the curing temperature specified in this application was adjusted from 80°C to 120°C, and the curing time was correspondingly shortened to 5 min, to obtain a contact sterilization layer. The results showed that the product had a thickness of 10.0±0.4 nm, a crosslinking degree (FT-IRSi–O–Si / Si–OH) of 87.3%, and antibacterial rates of 99.94% and 99.93%, respectively. This demonstrates that even at the upper limit temperature of 120°C, a high crosslinking density film can still be obtained through short-time high-temperature curing, which is suitable for fast production line cycles.

[0060] Example 7:

[0061] With all other preparation conditions the same as in Example 1, only the deposition method specified in this application was changed from PECVD to ALD, using TMA and H2O as precursors, and completing 200 cycles at 110°C to obtain a transparent Al2O3 inorganic protective layer (thickness 30.2±0.3 nm). The results show that the product has a refractive index of 1.62, a hardness of 11.5 GPa, a transmittance of 92.3%, a haze of 0.26%, and antibacterial rates of 99.95% and 99.94%, respectively, demonstrating that different deposition methods can achieve equivalent functions within the specified range.

[0062] Example 8:

[0063] With all other preparation conditions the same as in Example 1, only the post-baking temperature specified in this application was adjusted from 100°C to 80°C, and the post-baking time was extended to 30 min, to obtain an anti-fingerprint layer. The results showed that the product had a water contact angle of 109.8°, which remained at 106.2° after 500 wiping cycles, and antibacterial rates of 99.90% and 99.88%, respectively, proving that even at the lower limit temperature of 80°C, extending the post-baking time can still achieve sufficient cross-linking and stabilization of the oleophobic layer.

[0064] Example 9:

[0065] Under the same preparation conditions as in Example 1, only the transparent inorganic protective layer material specified in this application was changed from SiOxCy to Al2O3, and a film with a thickness of 30.0±0.4 nm was deposited by magnetron sputtering (Al target, Ar / O2=10 / 5sccm, power 150W, 100℃). The results showed that the product had a hardness of 12.1 GPa, a transmittance of 92.2%, a haze of 0.27%, and antibacterial rates of 99.93% and 99.92%, respectively, demonstrating that different inorganic materials are substitutable and functional within a certain range.

[0066] Example 10:

[0067] With all other preparation conditions the same as in Example 1, only the activation method specified in this application was changed from oxygen plasma treatment to UV-O3 treatment (185 / 254nm dual wavelength, ozone concentration 120ppm, treatment time 5min), while the other steps remained unchanged. The results showed that the surface hydroxyl density of the sample reached 4.6OH / nm² (XPS measurement), the contact bactericidal layer thickness was 10.1±0.4nm, and the antibacterial rate was 99.92% and 99.91%, respectively, demonstrating that different activation methods can achieve equivalent technical effects within the specified range.

[0068] Example 11:

[0069] With all other preparation conditions the same as in Example 1, only the alkoxy group of the quaternary ammonium silane precursor specified in this application was changed from methoxy to ethoxy, i.e., triethoxysilylpropyldimethyloctadecylammonium chloride (Gelest, SIT8180.0) was used. The remaining concentration, pH, and curing conditions remained unchanged, resulting in a contact bactericidal layer. The results showed that the product thickness was 10.3 ± 0.5 nm, the hydrolysis reaction was more gradual (t1 / 2 ≈ 42 min), the film uniformity was slightly better (AFMRa = 0.26 nm), and the antibacterial rate was 99.94% and 99.93%, respectively. This demonstrates that the ethoxy precursor also meets the specified range and possesses process advantages.

[0070] Example 12:

[0071] Under the same preparation conditions as in Example 1, only the transparent inorganic protective layer structure defined in this application was changed from a continuous film to a SiOxCy film with nanopores. Specifically, periodic pulsed bias voltages (+200V / 10ms, –200V / 10ms) were introduced during PECVD deposition, resulting in a permeable nanopore structure with an average pore size of 8.3±1.2 nm and a porosity of 12.4% (TEM and BET measurements). The results showed that the product had a transmittance of 92.3%, a haze of 0.28%, and antibacterial rates of 99.96% and 99.95%, respectively. Furthermore, scanning electron microscopy images of the bacteria showed numerous ruptured E. coli cell walls adhering to the pore edges, confirming that the nanopores, acting as "accessible windows," effectively promoted the interaction between bacteria and the underlying quaternary ammonium salt groups, thus validating the functional design of the "nanoscale surface microstructure or nanopores" in this application.

[0072] Example 13:

[0073] With all other preparation conditions the same as in Example 1, the only difference was that the anti-fingerprint layer material specified in this application was changed from a fluorinated silane self-assembled layer to an oleophobic DLC layer, specifically, an F-DLC film with a thickness of 5.2 ± 0.3 nm was deposited using plasma-enhanced chemical vapor deposition (CHF3 / Ar gas, RF power 120 W, temperature 90 °C). The results showed that the product had a water contact angle of 107.5°, an oil contact angle of 62.8°, a friction coefficient reduction of 45.1%, a transmittance of 92.1%, a haze of 0.29%, and antibacterial rates of 99.91% and 99.90%, respectively, demonstrating that the DLC-type oleophobic layer possesses equivalent practicality within the specified range.

[0074] Example 14:

[0075] Under the same preparation conditions as in Example 1, only the step S3, defined in this application, "causing the pre-hydrolyzed silane compound to undergo a condensation reaction on the surface of the film to form a siloxane network," was replaced by a vapor deposition method: the activated glass was placed in a sealed cavity, and water vapor (RH=40%) and FAS-17 vapor (concentration 80ppm) were introduced. The reaction was carried out at 60°C for 45 min, followed by curing at 80°C for 20 min. The results showed that the contact sterilization layer thickness of the product was 9.9±0.5 nm, and the quaternary ammonium salt surface density determined by XPS was 2.1×10⁻⁶. 14 cm⁻², with antibacterial rates of 99.90% and 99.89%, proves that the gas-phase method also meets the technical characteristics defined in this application, expanding the applicable scenarios of the process.

[0076] Example 15:

[0077] To verify the technical effectiveness of this invention, the following comparative examples were set up and systematic performance tests were conducted:

[0078] Comparative Example 1: Raw aluminosilicate cover glass without any functionalization treatment;

[0079] Comparative Example 2: Commercially available silver ion antibacterial glass (claiming an antibacterial rate of ≥99%, produced by impregnation with AgNO3 followed by heat treatment).

[0080] Comparative Example 3: Only the contact sterilization layer was constructed (same as steps S1–S3 in Example 1), without depositing the transparent inorganic protective layer and the anti-fingerprint layer;

[0081] Comparative Example 4: Only a contact sterilization layer + transparent inorganic protective layer was constructed (same as steps S1–S4 in Example 1), and no anti-fingerprint layer was formed;

[0082] Comparative Example 5: The thickness of the contact sterilization layer is 65 nm (exceeding the upper limit of this application), and the rest is the same as in Example 1;

[0083] Comparative Example 6: The thickness of the transparent inorganic protective layer is 3nm (lower than the lower limit of this application), and the rest is the same as in Example 1.

[0084] All samples were prepared to the same size (100mm × 100mm). Tests included: visible light transmittance (400–700nm), haze, water contact angle, oil contact angle, antibacterial rate (ISO22196), wet and dry wiping life (load 5N, non-woven fabric medium, recording the number of wiping cycles until the antibacterial rate decreased to 90%), and adhesion (cross-cut adhesion test). Test results are summarized in Table 1.

[0085] Table 1 Results of the effect test

[0086] Sample number Test Project Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Transmittance (%) 92.4 91.5 89.2 92.5 92.3 88.7 92.1 Haze (%) 0.27 0.25 1.85 0.26 0.27 2.31 0.28 Water contact angle (°) 112.3 28.5 32.1 29.0 110.2 111.8 110.5 Oil contact angle (°) 67.5 18.2 20.3 18.5 65.8 66.9 65.2 Antibacterial rate (E. coli) 99.93% 0 99.85% 99.92% 99.91% 99.88% 99.90% Antibacterial rate (S. aureus) 99.91% 0 99.79% 99.90% 99.89% 99.87% 99.88% Wiping life (times) ≥5000 — 820 1250 ≥5000 410 1380 100-grid adhesion test Level 0 Level 5 Level 2 Level 1 Level 0 Level 1 Level 1

[0087] As shown in Table 1, Example 1, while maintaining high transmittance (92.4%) and low haze (0.27%), also exhibits excellent antibacterial properties (≥99.9%), ultra-long wipe life (≥5000 wipes), and outstanding oleophobicity (water / oil contact angles reach 112.3° / 67.5° respectively), significantly outperforming the comparative examples. Comparative Example 2, although possessing antibacterial properties, suffers from a high haze of 1.85% due to silver ion migration, and its antibacterial rate decreases to below 90% after 820 wipes, confirming the inherent defects of the metal ion-based approach. Example 3, lacking a protective layer, had a wipe life of only 1250 cycles, demonstrating that the transparent inorganic protective layer makes a decisive contribution to antibacterial durability. Comparative Example 4, without an anti-fingerprint layer, had an oil contact angle of only 65.8°, resulting in noticeable fingerprint residue, verifying the crucial role of the anti-fingerprint layer in user experience. Comparative Example 5, due to an excessively thick (65nm) antibacterial layer, experienced increased light interference and brittleness, leading to a haze increase to 2.31% and a sharp drop in wipe life to 410 cycles. Comparative Example 6, with an excessively thin (3nm) protective layer that failed to form an effective barrier, had a wipe life of only 1380 cycles. In summary, the synergistic effect of the various technical features of this invention produces a comprehensive technical effect far exceeding that of simple superposition, especially demonstrating outstanding substantial characteristics and significant progress in the contradictory unity of antibacterial durability and optical performance.

[0088] Example 16:

[0089] Experimental results show that the antibacterial display glass prepared in this invention exhibits good contact sterilization effects in Escherichia coli and Staphylococcus aureus contamination models. Therefore, it can be used to prepare drug aids for the prevention and / or treatment of contact-transmitted infectious diseases caused by the above-mentioned bacteria. At the same time, its high light transmittance, low haze, wipe resistance and fingerprint resistance make it particularly suitable for scenarios with strict requirements for hygiene and human-computer interaction, such as smartphones, tablets, in-vehicle central control screens, medical display terminals and public interactive screens.

[0090] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. A display screen glass with antibacterial surface, characterized in that, It includes a glass substrate and a composite functional film layer disposed on the outer surface of the glass substrate, wherein the composite functional film layer comprises, from the inside to the outside: The contact sterilization layer is a siloxane network layer formed by the hydrolysis and condensation of a silane compound containing quaternary ammonium salt groups on the surface of a glass substrate and its covalent bonding with hydroxyl groups on the surface of the glass substrate. A transparent inorganic protective layer covers the outside of the contact bactericidal layer to improve wear resistance and abrasion resistance. An anti-fingerprint layer is disposed on the outside of the transparent inorganic protective layer to reduce surface energy and thus reduce the adhesion of fingerprints and oil stains.

2. The display glass according to claim 1, characterized in that, The thickness of the contact sterilization layer is 2nm to 50nm; The quaternary ammonium salt groups in the contact sterilization layer are provided by a quaternary ammonium salt silane precursor with a trialkoxysilyl group, wherein the alkoxy group of the quaternary ammonium salt silane precursor is methoxy and / or ethoxy.

3. The display glass according to claim 1, characterized in that, The thickness of the transparent inorganic protective layer is 5nm to 60nm; The transparent inorganic protective layer comprises one or more of nano-silicon-based oxides (SiOx), silicon oxide carbides (SiOxCy), and nano-alumina (Al2O3); The transparent inorganic protective layer has a nanoscale surface microstructure or nanopores.

4. The display glass according to claim 1, characterized in that, The thickness of the anti-fingerprint layer is 0.5nm to 10nm; The anti-fingerprint layer is one of a fluorinated silane self-assembled layer, a fluorinated organosilicon coating, or an oleophobic DLC layer.

5. A method for preparing a display screen glass with antibacterial surface, characterized in that, For preparing the display glass as described in any one of claims 1-4, comprising: S1. Clean and dry the glass substrate; S2. The surface of the glass substrate to be film-forming is activated to increase the surface hydroxyl density; S3. Forming a contact sterilization layer on the surface of the film to be formed: hydrolyzing and condensing a silane compound containing quaternary ammonium salt groups on the surface of the film to be formed and covalently bonding it with the surface hydroxyl groups to form a siloxane network layer; S4. A transparent inorganic protective layer is deposited on the outer side of the contact sterilization layer; S5. An anti-fingerprint layer is formed on the outside of the transparent inorganic protective layer.

6. The preparation method according to claim 5, characterized in that, The activation treatment in step S2 includes one or more of oxygen plasma treatment, UV-O3 treatment, or chemical hydroxylation treatment.

7. The preparation method according to claim 5, characterized in that, Step S3 specifically includes: A silane compound containing quaternary ammonium salt groups was prepared into an aqueous system and pre-hydrolyzed to generate silanol groups; The pre-hydrolyzed silane compound undergoes a condensation reaction on the surface of the film to be formed, forming a siloxane network; The silanol groups in the siloxane network are covalently grafted onto the surface hydroxyl groups of the surface to be filmed, and then cured to obtain the contact sterilization layer.

8. The preparation method according to claim 7, characterized in that, The concentration of the silane compound in the aqueous system is 0.1 wt% to 5 wt%. The pre-hydrolysis conditions are as follows: the pH value of the aqueous system is adjusted to 3-6; The curing conditions are as follows: curing temperature is 60℃~120℃, and curing time is 5min~60min.

9. The preparation method according to claim 5, characterized in that, Step S4 involves depositing the transparent inorganic protective layer using one of PECVD, magnetron sputtering, or ALD at a temperature not exceeding 120°C. The deposition thickness of the transparent inorganic protective layer in step S4 is controlled to be 5 nm to 60 nm.

10. The preparation method according to claim 5, characterized in that, Step S5 involves forming the anti-fingerprint layer using fluorinated silane vapor deposition or solution self-assembly, followed by a post-baking treatment at 80°C to 120°C to enhance stability.

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