Wear-resistant glass and manufacturing method thereof
The glass structure with a porous optical adjustment layer using silicon and high-refractive-index materials enhances abrasion resistance and maintains transparency by absorbing frictional energy, addressing the degradation issue in existing fingerprint-resistant glass.
Patent Information
- Application Number
- CN202510409223.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-02
- Publication Date
- 2025-07-15
AI Technical Summary
The existing anti-fingerprint glass has poor friction resistance during use, and the anti-fingerprint layer is prone to failure due to friction wear after about 3 months.
An optical adjustment layer with a hole structure is provided between the base material layer and the base layer. The hole structure formed by silicon oxide and a high refractive index material is used to enhance the friction resistance of the fingerprint layer, and an interlaced stack of silicon oxide and high refractive index material is used in the optical adjustment layer to reduce the reflectivity and maintain the optical transmittance.
It improves the friction resistance of the anti-fingerprint layer, reduces the generation and expansion of surface cracks, increases the adhesion density, maintains optical transmittance and color-free function, and extends the service life.
Smart Images
Figure CN120309192A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of glass manufacturing, and particularly to a wear-resistant glass and a manufacturing method thereof. Background Art
[0002] Existing fingerprint-proof glass mainly includes a fingerprint-proof layer, a primer layer, and a glass substrate. Among them, the end group structures of the primer layer, the glass substrate, and the fingerprint-proof layer are similar, so good connection can be achieved between the layers. During the friction process, the fingerprint-proof glass strongly depends on the wear-resistant characteristics of the fingerprint-proof layer, and the silica primer layer has no buffering effect on the resistance generated during the friction process. Therefore, after about 3 months of normal use, the fingerprint-proof layer will fail due to friction and wear. The existing fingerprint-proof glass has poor friction resistance. Summary of the Invention
[0003] In view of this, an object of the present invention is to provide a wear-resistant glass and a manufacturing method thereof, which can improve the friction resistance of fingerprint-proof glass and maintain the function of micro-transparency and no color difference.
[0004] On the one hand, the present invention provides a wear-resistant glass, which includes:
[0005] a substrate layer, an optical adjustment layer disposed on the substrate layer and having a cavity structure, a primer layer disposed on the optical adjustment layer, and a fingerprint-proof layer disposed on the primer layer;
[0006] The material forming the cavity structure includes silicon oxide and a high refractive index material; the high refractive index material refers to a material with a refractive index higher than that of the substrate layer.
[0007] Optionally, the optical adjustment layer includes at least one mixed layer of silicon oxide and a high refractive index material.
[0008] Optionally, the optical adjustment layer includes at least one silicon oxide layer disposed on the substrate layer and at least one high refractive index material layer disposed on the silicon oxide layer.
[0009] Optionally, the high refractive index material is one or more of aluminum oxide, niobium pentoxide, titanium dioxide, or silicon carbide.
[0010] Optionally, the thickness range of the optical adjustment layer includes 5 - 80 nm.
[0011] Optionally, the equivalent refractive index range of the optical adjustment layer is 1.47 - 1.57.
[0012] Optionally, the material of the fingerprint-proof layer includes a mixture of perfluoropolyether siloxane and short-chain fluorinated oil.
[0013] Optionally, the thickness range of the primer layer includes 5 - 25 nm.
[0014] Optionally, the thickness range of the fingerprint-proof layer includes 10 - 50 nm.
[0015] On the other hand, the present invention provides a method for manufacturing wear-resistant glass, which is applied to manufacture the wear-resistant glass described above, and includes the following steps:
[0016] Clean the substrate layer with deionized water;
[0017] Evaporate an optical adjustment layer on the cleaned substrate layer by means of electron gun thermal evaporation; the materials in the electron gun are silicon oxide and high refractive index materials;
[0018] Evaporate an underlayer on the optical adjustment layer, and coat a fingerprint-proof layer on the underlayer to obtain the wear-resistant glass.
[0019] Implementing the present invention includes the following beneficial effects: By setting an optical adjustment layer with a cavity structure between the substrate layer and the underlayer, cavity toughening is achieved by using the cavity structure formed by silicon oxide and high refractive index materials. When stress is applied to the fingerprint-proof layer, the cavity structure in the silicon oxide and high refractive index materials can absorb part of the energy, thereby reducing the generation and expansion of cracks on the surface of the fingerprint-proof layer during non-rigid friction. The denseness of the optical adjustment layer decreases and the corresponding voids increase, which will improve the surface toughness of the optical adjustment layer and enhance the friction resistance of the optical adjustment layer; the cavity structure increases the specific surface area of the fingerprint-proof layer attached, improves the attachment density on the surface of the fingerprint-proof layer, and achieves the effect of enhancing the friction resistance of the fingerprint-proof layer; and the silicon oxide and high refractive index materials used in the optical adjustment layer belong to the staggered stacking of different refractive index materials, realizing the destructive interference of light within the visible light wavelength range (360 - 740 nm), thereby reducing the reflectivity, ensuring the optical transmittance of the entire wear-resistant glass, and maintaining the colorless function and antireflection effect of the wear-resistant glass. Description of the Drawings
[0020] Figure 1 is a schematic structural diagram of a wear-resistant glass provided by an embodiment of the present invention;
[0021] Figure 2 is a schematic structural diagram of an optical adjustment layer provided by an embodiment of the present invention;
[0022] Figure 3 is a schematic structural diagram of another optical adjustment layer provided by an embodiment of the present invention;
[0023] Figure 4 is a manufacturing flow chart of a wear-resistant glass provided by an embodiment of the present invention;
[0024] Figure 5 is a schematic diagram of the principle of cavity toughening provided by an embodiment of the present invention;
[0025] Figure 6 It is a schematic diagram of the transmittance of glasses with different optical wavelengths provided by an embodiment of the present invention. Detailed implementation manners
[0026] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. For the step numbers in the following embodiments, they are only set for the convenience of explanation and illustration, and no limitation is imposed on the order between steps. The execution order of each step in the embodiments can be adaptively adjusted according to the understanding of those skilled in the art.
[0027] The terms used in the embodiments of this application are only for the purpose of describing specific embodiments and are not intended to limit the embodiments of this application. The singular forms "a", "the" and "said" used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term "and / or" used herein refers to and includes any or all possible combinations of one or more of the associated listed items.
[0028] When the following description refers to the accompanying drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this application. On the contrary, they are merely examples of devices and methods consistent with some aspects of this application as detailed in the appended claims. In the description of this application, it should be understood that the terms "first", "second", etc. are only used to distinguish similar objects and do not have to be used to describe a specific order or sequence, nor can they be understood as indicating or implying relative importance. For those of ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances.
[0029] In addition, in the description of this application, unless otherwise specified, "a variety of" means two or more.
[0030] In some embodiments, as Figure 1 shown, Figure 1 It is a schematic diagram of the structure of a wear-resistant glass provided by an embodiment of the present invention. An embodiment of the present invention provides a wear-resistant glass, which includes:
[0031] A substrate layer, an optical adjustment layer provided on the substrate layer and having a cavity structure, an undercoat layer provided on the optical adjustment layer, and an anti-fingerprint layer provided on the undercoat layer;
[0032] The materials forming the hole structure include silicon oxide and high refractive index materials. Among them, the proportion of the hole volume in the hole structure can be, but is not limited to, 0.5% - 5%, especially 1.5% - 3%, such as 2.0%. The high refractive index material refers to a material with a refractive index higher than that of the substrate layer. For example, if the refractive index of the substrate layer is 1.52, the refractive index of the high refractive index material is greater than 1.52.
[0033] Among them, the high refractive index material can be, but is not limited to, one or more of aluminum oxide (Al2O3), niobium pentoxide (Nb2O5), titanium dioxide (TiO2), or silicon carbide (Si3N4). Specifically, the thickness range of the optical adjustment layer can be, but is not limited to, 5 - 80 nm. The thickness here refers to the overall thickness of the optical adjustment layer. In the embodiments of the present invention, embodiments with the thickness of the optical adjustment layer less than 10 nm, 10 - 30 nm, 30 - 50 nm, and greater than 50 nm are also provided, and their anti-friction performance is better than that of the anti-friction glass in the background art.
[0034] The equivalent refractive index range of the optical adjustment layer can be, but is not limited to, 1.47 - 1.57, which is close to the refractive index of the substrate layer.
[0035] As Figure 2 shown, Figure 2 is a schematic structural diagram of an optical adjustment layer. In the figure, A represents one or more of Al2O3, Nb2O5, TiO2, Si3N4, and B represents silicon oxide (SiO2). The optical adjustment layer includes at least one mixed layer of silicon oxide and high refractive index materials. Among them, the mixed layer means mixing silicon oxide and high refractive index materials to obtain a mixture. In the mixture, the volume proportion of the high refractive index material is 0 - 5%. The optical adjustment layer is a film layer of this mixture.
[0036] As Figure 3 shown, Figure 3It is a schematic structural diagram of another optical adjustment layer. In the figure, A represents one or more of Al2O3, Nb2O5, TiO2, and Si3N4, and B represents silicon dioxide (SiO2). In another solution, the optical adjustment layer includes at least one silicon dioxide layer disposed on the substrate layer and at least one high refractive index material layer disposed on the silicon dioxide layer. Among them, the thickness range of the A layer can be, but is not limited to, 5 - 80 nm, such as 10 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm; the thickness range of the B layer can be, but is not limited to, 5 - 25 nm, such as 10 nm, 12 nm, 15 nm, 18 nm, 20 nm. For example, a SiO2 layer disposed on the substrate layer and an Al2O3 disposed on the silicon dioxide layer, or a SiO2 layer disposed on the substrate layer and a mixed layer of Al2O3, Nb2O5, TiO2, Si3N4, and SiC disposed on the silicon dioxide layer.
[0037] The thickness range of the primer layer can be, but is not limited to, 5 - 25 nm, and the materials include, but are not limited to, SiO2. The primer layer is mainly used to enhance the bonding force between the substrate layer and the anti-fingerprint (AF) layer and plays a good connecting and transitional role.
[0038] The materials mainly included in the AF layer include a mixture of perfluoropolyether siloxane and short-chain fluorinated oil. In the mixture, the perfluoropolyether siloxane with a Z-shaped chain structure is the main agent, and its molecular structure is: CF3 - O - (CF2 - CF2 - O)m - (CF2 - O)n - CF3 - Si(OR)x, accounting for 0% - 20% and having a molecular weight of 2500 - 8000; the short-chain fluorinated oil is a diluent, and the short-chain fluorinated oil has a low molecular weight perfluoropolyether structure without a siloxane end and has similar compatibility with AF, accounting for 80% - 95% and having a molecular weight of 300 - 2000. In addition, the mixture also includes an additive accounting for 0 - 5%, and the total proportion of the main agent and the additive is 5% - 20%. Among them, the proportion represents the molar mass proportion.
[0039] Optionally, the thickness range of the anti-fingerprint layer can be, but is not limited to, 10 - 50 nm.
[0040] On the other hand, as Figure 4 shown, Figure 4 is a flowchart for manufacturing a wear-resistant glass. The embodiment of the present invention provides a method for manufacturing a wear-resistant glass, which is applied to manufacture the wear-resistant glass described above and includes the following steps:
[0041] S1. Clean the substrate layer with deionized water.
[0042] Specifically, before coating, the substrate layer is cleaned with deionized water. The specific process is to fix the substrate layer on the carrier plate of the coating machine, evacuate it to a vacuum of <3E-3 Pa through a mechanical pump and a Roots pump system, and perform plasma cleaning on the substrate layer using pure Ar (argon). The cleaning power can be 1 - 4 kW.
[0043] S2. Evaporate an optical adjustment layer on the cleaned substrate layer by means of electron gun thermal evaporation.
[0044] Among them, the materials in the electron gun are silicon oxide and high refractive index materials.
[0045] Specifically, it is divided into two cases. The first case: If the optical adjustment layer includes at least one mixed layer of silicon oxide and high refractive index materials, mix silicon oxide and high refractive index materials to obtain a mixture, add the mixture into the electron gun, and evaporate the optical adjustment layer on the cleaned substrate layer.
[0046] The second case: The optical adjustment layer includes at least one silicon oxide layer disposed on the substrate layer and at least one high refractive index material layer disposed on the silicon oxide layer. First, add silicon oxide into the electron gun and evaporate the silicon oxide layer on the cleaned substrate layer, and then add the high refractive index material into the electron gun and evaporate the high refractive index material layer on the silicon oxide layer.
[0047] Among them, the high refractive index material is the same as the previous explanation and will not be elaborated here.
[0048] S3. Evaporate a primer layer on the optical adjustment layer, and coat an anti-fingerprint layer on the primer layer to obtain scratch-resistant glass.
[0049] Specifically, add silicon oxide into the electron gun, evaporate the primer layer on the optical adjustment layer, and finally coat an anti-fingerprint layer on the primer layer to obtain scratch-resistant glass with high wear resistance and micro anti-reflection effect. Among them, anti-reflection means increasing the transmittance.
[0050] To better understand the technology of the embodiments of the present invention, the hole toughening is now explained:
[0051] As Figure 5 shown, Figure 5 is a schematic diagram of hole toughening. In the figure, Hole represents point defects. When the thickness of the optical adjustment layer reaches the level where it can completely cover the substrate and form continuous stacking, if the excitation energy of the atoms / molecules of the evaporation source is not sufficient to make them reach the ideal surface sites, point defects with atomic deficiencies will be left in the local space lattice of the optical adjustment layer. The accumulation of defects will further form a three-dimensional hole structure. The hole structure will absorb part of the energy during the process of the optical adjustment layer being subjected to external forces, thereby reducing the generation and expansion of surface cracks in the optical adjustment layer during the non-rigid friction process, achieving the improvement of the friction resistance of the optical adjustment layer.
[0052] The embodiments of the present invention also have the following beneficial effects:
[0053] In the embodiments of the present invention, an optical adjustment layer with a cavity structure is arranged between the substrate layer and the primer layer, and cavity toughening is realized by using the cavity structure formed by silicon oxide and a high refractive index material. When stress is applied to the fingerprint-proof layer, the cavity structures in the silicon oxide and the high refractive index material can absorb part of the energy, thereby reducing the generation and expansion of cracks on the surface of the fingerprint-proof layer during the non-rigid friction process, increasing the specific surface area of the attachment of the fingerprint-proof layer, improving the attachment density on the surface of the fingerprint-proof layer, achieving the effect of enhancing the friction resistance of the fingerprint-proof layer, and a high refractive index material is used in the optical adjustment layer, which can ensure the optical transmittance of the entire wear-resistant glass and maintain the micro-transparent and colorless function of the wear-resistant glass.
[0054] In addition, the embodiments of the present invention conduct experiments under four conditions where the thickness of the optical adjustment layer is less than 10nm, 10 - 30nm, 30 - 50nm, and greater than 50nm, which are represented by Example 1, Example 2, Example 3, and Example 4 respectively, and the fingerprint-proof glass in the background technology is added as a control group, which is Comparative Example 1. The experimental conditions for color difference and transmittance are set according to the regulations of the International Commission on Illumination. Under the condition of normal incidence, in the (L*, a*, b*) colorimetric system, a color difference meter is used for testing, with the reflection color value a value ±1, b value ±1, and the transmitted color value a value ±1, b value ±1.
[0055] The experimental results are shown in Table 1 and Figure 6 as shown. In Table 1, WC represents the water contact angle. Figure 6 is a schematic diagram of the transmittance of each glass with different light wavelengths. The vertical coordinate is the transmittance, and the horizontal coordinate is the light wavelength. The black line represents the comparative example, the blue line represents Example 1, the yellow line represents Example 2, and the green line represents Example 3.
[0056] Table 1
[0057]
[0058] According to Table 1 and Figure 6 it can be seen that the performances of Example 1, Example 2, Example 3, and Example 4 in terms of transmittance, dynamic friction coefficient, and rubber friction limit are all better than those of Comparative Example 1. In addition, in the experiment, the wear-resistant glass provided by the embodiments of the present invention has no film layer peeling phenomenon, the cross-cut test ≥ 4B, and in the light wavelength range of 380 - 780nm, the reflectivity of this wear-resistant glass < 8.6%.
[0059] This shows that the coated glass has no color difference, and the optical adjustment layer is applicable to the substrate layers of 2D, 2.5D, and 3D curved glass. Among them, 2D, 2.5D, and 3D represent the curvature of the curved glass.
[0060] The above is a specific description of the preferred embodiment of the present invention. However, the present invention is not limited to the described embodiment. Those skilled in the art can also make various equivalent deformations or substitutions without departing from the spirit of the present invention. These equivalent deformations or substitutions are all included within the scope defined by the claims of this application.
Claims
1. A wear-resistant glass, characterized in that, The wear-resistant glass includes: a substrate layer, an optical adjustment layer disposed on the substrate layer and having a cavity structure, a primer layer disposed on the optical adjustment layer, and an anti-fingerprint layer disposed on the primer layer; The material forming the cavity structure includes silicon oxide and a high refractive index material; the high refractive index material refers to a material having a refractive index higher than that of the substrate layer.
2. The wear-resistant glass according to claim 1, wherein, The optical adjustment layer includes at least one mixed layer of silicon oxide and a high refractive index material.
3. The wear-resistant glass according to claim 1, characterized in that, The optical adjustment layer includes at least one silicon oxide layer disposed on the substrate layer and at least one high refractive index material layer disposed on the silicon oxide layer.
4. The wear-resistant glass according to claim 1, wherein The high refractive index material is one or more of aluminum oxide, niobium pentoxide, titanium dioxide, or silicon carbide.
5. The wear-resistant glass according to claim 1, wherein The thickness range of the optical adjustment layer includes 5-80 nm.
6. The wear-resistant glass according to claim 1, wherein The equivalent refractive index range of the optical adjustment layer is 1.47 to 1.
57.
7. The wear-resistant glass according to claim 1, wherein The material of the anti-fingerprint layer includes a mixture of perfluoropolyether siloxane and short-chain fluorinated oil.
8. The wear-resistant glass according to claim 1, wherein, The thickness range of the primer layer includes 5-25 nm.
9. The wear-resistant glass according to claim 1, characterized in that, The thickness range of the anti-fingerprint layer includes 10-50 nm.
10. A manufacturing method of wear-resistant glass, characterized in that, When applied to fabricate the wear-resistant glass according to any one of claims 1-9, the method includes the following steps: Clean the substrate layer with deionized water; Evaporate the optical adjustment layer on the cleaned substrate layer by means of electron gun thermal evaporation; the materials in the electron gun are silicon oxide and a high refractive index material; Evaporate the primer layer on the optical adjustment layer and coat the anti-fingerprint layer on the primer layer to obtain the wear-resistant glass.