Anti-reflection waterproof coating structure and preparation method thereof

Abstract

The invention discloses an anti-reflection waterproof coating structure and a preparation method thereof, and belongs to the technical field of optical thin films. The anti-reflection waterproof coating structure comprises a base material as well as an anti-reflection layer and a waterproof antifouling layer which are sequentially formed on the base material, the anti-reflection layer comprises a silicon dioxide layer, a titanium-silicon composite oxide gradient layer, a silicon dioxide layer, a zirconium oxide layer and a mesoporous silicon dioxide layer which are sequentially stacked from bottom to top. In addition, the invention further provides a preparation method of the anti-reflection waterproof coating structure, and the preparation method comprises the following steps: sequentially depositing five film layers on the base material by adopting a magnetron sputtering technology to form the anti-reflection layer; carrying out two-step interface treatment on the surface of the anti-reflection layer; carrying out ammonia plasma treatment and perfluoroalkyl silane vapor deposition; and forming an interface strengthening layer on the anti-reflection layer after interface treatment, and then preparing a hydrophobic antifouling layer on the interface strengthening layer. The anti-reflection waterproof coating structure provided by the invention has excellent long-term stability in a humid and hot environment.

Description

Technical Field

[0001] This invention relates to the field of optical thin film technology, specifically to an antireflective and waterproof coating structure and its preparation method. Background Technology

[0002] Anti-reflective coatings (AR coatings) and waterproof / fouling-resistant coatings (AF coatings) are widely used in optical display devices, protective glass, solar cell covers, and other fields. AR coatings mainly reduce surface reflection by optimizing the film structure and refractive index matching, while AF coatings achieve waterproof and stain-resistant functions through low surface energy materials.

[0003] In existing technologies, the bonding of AR (Anaerobic) and AF (Anaerobic) coatings faces numerous technical challenges. Traditional AR coatings often employ alternating layered structures of materials such as silicon dioxide and niobium pentoxide. However, significant lattice mismatch and differences in thermal expansion coefficients exist between these materials, leading to interfacial stress concentration and a tendency for delamination failure in humid and hot environments. Simultaneously, when the AF coating is directly deposited on the AR layer, the significant differences in their chemical properties result in weak interfacial adhesion, leading to insufficient wear resistance and severely impacting product lifespan.

[0004] For example, patent CN119684915A discloses an AR film structure, including an AR coating group, a hardening coating, a substrate layer, a color-changing coating, and a pressure-sensitive adhesive layer. The AR coating group comprises an AF coating and a functional coating. While this structure provides some anti-reflection effect, it does not solve the problem of interfacial stress matching between the AR layer and the AF layer, and its long-term environmental stability needs improvement.

[0005] Patent CN211972140U describes a wear-resistant AG+AR+AF glass, in which a Si3N4 layer is set on the surface of the antireflective coating as a bonding layer with the AF film. However, the adhesion between the Si3N4 layer and the underlying SiO2 layer is limited, and the refractive index of Si3N4 is relatively high (about 2.0), which is not conducive to achieving the optimal antireflective effect. At the same time, it is prone to hydrolysis in high humidity environments.

[0006] A common technical challenge in existing technologies is how to achieve a strong bond between the AR layer and the AF layer while maintaining high light transmittance, and how to ensure long-term stability under harsh environments such as high temperature and high humidity. In particular, the interfacial stress problem between high-refractive-index materials and low-refractive-index materials, as well as the delamination problem caused by water vapor penetration along the interface, have long remained unresolved. Summary of the Invention

[0007] The purpose of this invention is to overcome the above-mentioned technical deficiencies and provide an anti-reflective and waterproof coating structure and its preparation method, which solves the long-term stability problem of high refractive index difference interfaces in humid and hot environments in the prior art, and in particular, prevents interface delamination and optical performance degradation caused by water vapor penetration.

[0008] To achieve the above-mentioned technical objectives, the present invention provides an anti-reflective and waterproof coating structure, comprising a substrate and an anti-reflective layer and a waterproof and anti-fouling layer sequentially formed on the substrate; the anti-reflective layer comprises, from bottom to top, a silica layer, a titanium-silicon composite oxide gradient layer, a silica layer, a zirconium oxide layer and a mesoporous silica layer.

[0009] In any embodiment, the TiO2 content in the titanium-silicon composite oxide gradient layer increases linearly from 25-30% to 70-75%, and the thickness is 12-18 nm.

[0010] In any embodiment, the waterproof and antifouling layer comprises, from bottom to top, an interface reinforcement layer and a hydrophobic antifouling layer; and / or, the substrate is glass.

[0011] In any embodiment, the interface reinforcement layer comprises amino-functionalized mesoporous silica nanoparticles and a perfluoroalkylsilane coupling agent; and / or, the hydrophobic and antifouling layer comprises a perfluoropolyether-modified silicone resin.

[0012] In any embodiment, the amino content of the amino-functionalized mesoporous silica nanoparticles in the interface reinforcement layer is 1.5-2.0 mmol / g, and the amino density is 1.8-2.2 amino groups / nm. 2 The particle size of the mesoporous silica nanoparticles is 8-12 nm.

[0013] In any embodiment, the perfluoroalkylsilane coupling agent is perfluorobutyltriethoxysilane.

[0014] In any embodiment, the perfluoropolyether segment of the perfluoropolyether modified silicone resin in the hydrophobic and antifouling layer accounts for 35-45 wt%, and the molecular weight of the perfluoropolyether modified silicone resin is 3000-5000 g / mol; and / or, the thickness of the hydrophobic and antifouling layer is 20-30 nm.

[0015] Furthermore, the present invention also proposes a method for preparing the above-mentioned antireflective and waterproof coating structure, comprising the following steps:

[0016] Five layers of film are sequentially deposited on a substrate using magnetron sputtering technology to form an antireflection layer;

[0017] The surface of the antireflection layer undergoes a two-step interface treatment: ammonia plasma treatment and perfluoroalkyl silane vapor deposition;

[0018] An interface-strengthening layer is formed by coating amino-functionalized mesoporous silica nanoparticles onto the antireflective layer after interface treatment, and then a hydrophobic and antifouling layer is obtained by spin-coating perfluoropolyether modified silicone resin onto the interface-strengthening layer.

[0019] In any embodiment, the preparation of the titanium-silicon composite oxide gradient layer in the five-layer film includes: co-sputtering with a SiO2 target and a TiO2 target, and controlling the target power to achieve a gradient change in TiO2 content from 30% to 70%, with a deposition thickness of 12-18 nm.

[0020] In any embodiment, in ammonia plasma treatment, the power is 300-500W and the time is 1-3 minutes; in perfluoroalkylsilane vapor deposition, deposition is carried out at 100-130°C for 5-15 minutes.

[0021] In any embodiment, the preparation of the interface strengthening layer includes: dispersing amino-functionalized mesoporous silica nanoparticles (particle size 10 nm, amino content 1.8 mmol / g) in ethanol to form a 2 wt% dispersion, coating the dispersion onto the surface of the interface-treated antireflection layer by spin coating (3000 rpm, 30 s), and curing at 100°C for 10 minutes.

[0022] In any embodiment, the preparation of the hydrophobic and antifouling layer includes: diluting a perfluoropolyether-modified silicone resin (40 wt% perfluoropolyether segments, 4000 g / mol molecular weight) to a solid content of 5 wt% (solvent is perfluorohexane), coating it onto the interface reinforcement layer by spin coating (2500 rpm, 30 s), and curing it at 120°C for 30 minutes.

[0023] Compared with existing technologies, the beneficial effects of this invention include: the anti-reflective and waterproof coating structure proposed in this invention, through the design of a titanium-silicon composite oxide gradient layer and an interface reinforcement layer, effectively releases interface stress. After a damp heat test (85℃ / 85%RH, 1000 hours), the light transmittance change is ≤0.1%, the adhesion remains at grade 0, and there is no delamination. The anti-reflective and waterproof coating structure proposed in this invention exhibits excellent long-term stability in damp heat environments.

[0024] Superior optical performance: By optimizing the antireflection layer thickness ratio and introducing a gradient refractive index design, an average transmittance of ≥98.9% and a reflectance of ≤0.7% are achieved in the visible light range (380-780nm), which is significantly better than traditional AR coatings;

[0025] Excellent waterproof and wear-resistant performance: water contact angle ≥115°, oil contact angle ≥75°, pencil hardness ≥9H, haze change ≤0.2% after 10,000 steel wool rubbing, far exceeding traditional structures.

[0026] Extremely low water vapor permeability: Through mesoporous structure and dense interface design, water vapor permeability is reduced to below 0.05 g / m²·day, which is 86% lower than that of traditional structures.

[0027] The preparation process is mature and reliable: all preparation steps use mature equipment and processes, which are easy to mass-produce and have a high product yield. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the anti-reflective and waterproof coating structure of Embodiment 1 of the present invention.

[0029] Figure 2 This is a comparison diagram of the transmittance curves of the anti-reflective and waterproof coating structures in the visible light region of Embodiment 1 and Comparative Example 1 of the present invention.

[0030] Figure 3 This is a comparison diagram of the haze change after wear resistance test of the antireflective and waterproof coating structure of Embodiment 1 and Comparative Example 1 of the present invention.

[0031] Figure 4 This is a comparison diagram of the changes in water contact angle after damp heat testing of the antireflective and waterproof coating structures of Embodiment 1 and Comparative Example 1 of the present invention.

[0032] Figure 5 This is a photograph of the water contact angle of the anti-reflective and waterproof coating structure in Embodiment 1 of the present invention.

[0033] Explanation of reference numerals in the attached figures: 0, substrate; 1, antireflective layer; 11, silica layer; 12, titanium-silicon composite oxide gradient layer; 13, silica layer; 14, zirconium oxide layer; 15, mesoporous silica layer; 2, waterproof and antifouling layer; 21, interface reinforcement layer; 22, hydrophobic and antifouling layer. Detailed Implementation

[0034] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is also expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0035] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0036] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0037] This specific embodiment provides an antireflective and waterproof coating structure, including a substrate and an antireflective layer and a waterproof and antifouling layer sequentially formed on the substrate; the antireflective layer includes, from bottom to top, a silica layer, a titanium-silicon composite oxide gradient layer, a silica layer, a zirconium oxide layer, and a mesoporous silica layer; the TiO2 content in the titanium-silicon composite oxide gradient layer increases linearly from 25-30% to 70-75%, and the thickness is 12-18 nm; the waterproof and antifouling layer includes, from bottom to top, an interface reinforcement layer and a hydrophobic antifouling layer; the interface reinforcement layer contains amino-functionalized mesoporous silica nanoparticles and a perfluoroalkyl silane coupling agent; the hydrophobic antifouling layer contains a perfluoropolyether-modified silicone resin; the amino content of the amino-functionalized mesoporous silica nanoparticles in the interface reinforcement layer is 1.5-2.0 mmol / g, and the amino density is 1.8-2.2 amines / nm. 2 The mesoporous silica nanoparticles have a particle size of 8-12 nm; the perfluoroalkyl silane coupling agent is perfluorobutyltriethoxysilane; the perfluoropolyether modified silicone resin in the hydrophobic and antifouling layer has a perfluoropolyether segment ratio of 35-45 wt% and a molecular weight of 3000-5000 g / mol; the thickness of the hydrophobic and antifouling layer is 20-30 nm; and the substrate is glass.

[0038] This specific embodiment also proposes a method for preparing the above-mentioned antireflective and waterproof coating structure, including the following steps:

[0039] Five layers of film were sequentially deposited on the substrate using magnetron sputtering technology to form an antireflection layer; the preparation of the titanium-silicon composite oxide gradient layer in the five layers included: co-sputtering with SiO2 and TiO2 targets, and controlling the target power to achieve a gradient change in TiO2 content from 30% to 70%, with a deposition thickness of 12-18 nm;

[0040] The surface of the antireflection layer is subjected to a two-step interface treatment: ammonia plasma treatment and perfluoroalkylsilane vapor deposition; in the ammonia plasma treatment, the power is 300-500W and the time is 1-3 minutes; in the perfluoroalkylsilane vapor deposition, the deposition is carried out at 100-130℃ for 5-15 minutes.

[0041] An interface-strengthening layer is formed by coating amino-functionalized mesoporous silica nanoparticles onto the antireflective layer after interface treatment, and then a hydrophobic and antifouling layer is obtained by spin-coating perfluoropolyether modified silicone resin onto the interface-strengthening layer.

[0042] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0043] In this invention, the terms "some embodiments," "this embodiment," and examples are used to describe a subset of all possible embodiments. However, it is understood that "some embodiments" can be the same subset or different subsets of all possible embodiments and can be combined with each other without conflict.

[0044] If the application documents contain similar descriptions such as "first / second", the following explanation shall be added: In the following description, the terms "first / second / third" are used only to distinguish similar objects and do not represent a specific ordering of objects. It is understood that "first / second / third" may be interchanged in a specific order or sequence where permitted, so that the embodiments described herein can be implemented in an order other than that illustrated or described herein.

[0045] In this embodiment, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, object A and / or object B can represent three situations: object A exists alone, object A and object B exist simultaneously, and object B exists alone.

[0046] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0047] The sol-gel process in the following embodiments includes:

[0048] Step 1: Preparation of precursor sol

[0049] 1.0 mol of tetraethyl orthosilicate (TEOS), 0.25 mol of cetyltrimethylammonium bromide (CTAB), 20 mol of anhydrous ethanol, and 8 mol of deionized water were mixed. The pH was then adjusted to 3.5-4.0 with hydrochloric acid (0.1 mol / L). The CTAB and ethanol-water mixture (volume ratio 3:1) was stirred and dissolved at 35±2℃ for 30 minutes. TEOS was slowly added dropwise to the template agent solution, while 0.1 mol / L hydrochloric acid was added dropwise to maintain the pH at 3.5-4.0. The mixture was hydrolyzed at 40℃ for 2 hours, and then aged at 25℃ for 24 hours.

[0050] Step 2: Sol-gel conversion and film forming

[0051] Spin coating process parameters: Substrate pretreatment: oxygen plasma treatment (power 300W, time 2 minutes); Spin coating speed: first stage 800 rpm / 10s, second stage 3000 rpm / 30s

[0052] Ambient temperature: 23±2℃; Ambient humidity: 35±5% RH; Sol viscosity: 3.5±0.5 mPa·s; Film thickness control: adjusted by sol concentration and spin coating speed; Gelation process:

[0053] Gel temperature: 25℃; gel time: 30 minutes; relative humidity: 50% RH (precisely controlled by a humidity controller); gel conversion index: no surface reflection, non-sticky to the touch;

[0054] Step 3: Template agent removal and pore structure shaping

[0055] Under a nitrogen-oxygen mixed atmosphere (nitrogen to oxygen volume ratio 4:1), the temperature was increased from 25°C to 80°C at a heating rate of 1°C / min, then increased from 80°C to 150°C at a heating rate of 0.5°C / min, and held at 150°C for 2 hours. After that, the temperature was increased from 150°C to 350°C at a heating rate of 1°C / min, then increased from 350°C to 450°C at a heating rate of 0.5°C / min, and held at 450°C for 4 hours, and then cooled to room temperature.

[0056] Step 4: Post-treatment and surface modification; treat at 300°C for 1 hour under a nitrogen atmosphere to eliminate surface silanol groups and improve hydrophobicity.

[0057] The amino-functionalized mesoporous silica nanoparticles in the following examples were prepared by a post-grafting method. This method can precisely control the density and distribution of amino functional groups and avoid the functional group embedding problem that may occur in the co-condensation method.

[0058] Specific preparation process steps and parameters

[0059] Step 1: Preparation of mesoporous silica nanoparticles: hexadecyltrimethylammonium bromide (CTAB), purity ≥99%; tetraethyl orthosilicate (TEOS), purity ≥98%; ammonia water, concentration 28wt%; a mixed solvent of deionized water and anhydrous ethanol (volume ratio 1:1).

[0060] Process parameters: Reaction temperature: Mix the above components at 30±2℃ for 2 hours with CTAB concentration of 10g / L, TEOS:CTAB molar ratio of 4:1 and ammonia concentration of 0.5mol / L; then age at 40℃ for 24 hours; then increase the temperature to 550℃ at 1℃ / min and hold for 6 hours to obtain the intermediate product.

[0061] Intermediate product characteristics: Average particle size: 10±2 nm; Pore size distribution: 2.5±0.3 nm; BET specific surface area: 550±30 m² 2 / g; Pore volume: 0.8±0.1cm 3 / g;

[0062] Step 2: Amine functionalization reaction; Amination reagent: 3-aminopropyltriethoxysilane (APTES), purity ≥99%; Solvent: anhydrous toluene, moisture content ≤50ppm

[0063] Catalyst: Triethylamine, purity ≥ 99.5%;

[0064] The above components were mixed under anhydrous and oxygen-free conditions (nitrogen protection) with a silane concentration of 8 vol% and a triethylamine concentration of 1% of the total volume of the system. The mixture was then reacted at 110 ± 5 °C for 12 hours. The mass ratio of APTES to SiO2 was 0.5:1. After washing and drying, the amino-functionalized mesoporous silica nanoparticles were obtained.

[0065] Example 1

[0066] Combination Figure 1 This embodiment proposes an antireflective and waterproof coating structure, including a substrate and an antireflective layer 1 and a waterproof and antifouling layer 2 formed sequentially on the substrate 0; the antireflective layer includes a silica layer 11, a titanium-silicon composite oxide gradient layer 12, a silica layer 13, a zirconium oxide layer 14 and a mesoporous silica layer 15 stacked sequentially from bottom to top; the waterproof and antifouling layer 2 includes an interface reinforcement layer 21 and a hydrophobic and antifouling layer 22 sequentially from bottom to top.

[0067] The anti-reflective and waterproof coating structure in this embodiment is obtained by the following steps:

[0068] Substrate pretreatment: Corning Gorilla Glass (size 100mm×100mm×1mm) was selected as the substrate, cleaned with neutral detergent, rinsed with deionized water, ultrasonically cleaned with isopropyl alcohol for 15 minutes, and dried with nitrogen.

[0069] Antireflection layer preparation: Five layers were sequentially deposited on the substrate using a magnetron sputtering system:

[0070] First silicon dioxide layer: 80nm thick, sputtering power 3kW, argon atmosphere, pressure 0.3Pa;

[0071] The second titanium-silicon composite oxide gradient layer: SiO2 target and TiO2 target co-sputtering is used, and the TiO2 content is linearly increased from 30% to 70% through the existing technology of programmed power control steps, with a thickness of 15nm;

[0072] The third silicon dioxide layer: 35nm thick, with the same process parameters as the first silicon dioxide layer;

[0073] The fourth zirconium oxide layer: 20 nm thick, was sputtered by Zr target reaction at a power of 3.5 kW in an argon-oxygen mixed atmosphere (Ar:O2=4:1).

[0074] The fifth layer is a mesoporous silica layer with a thickness of 10 nm. It is prepared by sol-gel process using CTAB (hexadecyltrimethylammonium bromide) as a template agent. The particle size of the mesoporous silica is 8-12 nm.

[0075] Two-step interface treatment: ammonia plasma treatment: power 400W, time 2 minutes; perfluorobutyltriethoxysilane vapor deposition: deposition in a vacuum chamber at 120°C for 10 minutes;

[0076] Preparation of interface reinforcement layer: Amino-functionalized mesoporous silica nanoparticles (particle size 10 nm, amino content 1.8 mmol / g) were dispersed in ethanol to form a 2 wt% dispersion, which was then coated onto the surface of the interface-treated antireflection layer by spin coating (3000 rpm, 30 s) and cured at 100 °C for 10 minutes.

[0077] Preparation of hydrophobic and antifouling layer: Dilute perfluoropolyether modified silicone resin (perfluoropolyether segment content 40wt%, molecular weight 4000g / mol) to 5wt% solid content (solvent is perfluorohexane), apply it to the interface reinforcement layer by spin coating (spin speed 2500rpm, time 30s), and cure at 120℃ for 30 minutes.

[0078] Example 2

[0079] This embodiment proposes an antireflective and waterproof coating structure, including a substrate and an antireflective layer and a waterproof and antifouling layer formed sequentially on the substrate; the antireflective layer includes a silica layer, a titanium-silicon composite oxide gradient layer, a silica layer, a zirconium oxide layer and a mesoporous silica layer stacked sequentially from bottom to top; the waterproof and antifouling layer includes an interface reinforcement layer and a hydrophobic antifouling layer from bottom to top.

[0080] The preparation method of the antireflective and waterproof coating structure in this embodiment is the same as that in Example 1, and the obtained antireflective and waterproof coating structure is as follows:

[0081] The antireflective layer consists of a first silica layer with a thickness of 75 nm, a second titanium-silicon composite oxide gradient layer with a thickness of 12 nm, a third silica layer with a thickness of 30 nm, a fourth zirconium oxide layer with a thickness of 18 nm, and a fifth mesoporous silica layer with a thickness of 8 nm. The amino content of the amino-functionalized mesoporous silica nanoparticles in the interface reinforcement layer is 1.5 mmol / g; and the perfluoropolyether modified silicone resin in the hydrophobic and antifouling layer comprises 35 wt% perfluoropolyether segments.

[0082] Example 3

[0083] This embodiment proposes an antireflective and waterproof coating structure, including a substrate and an antireflective layer and a waterproof and antifouling layer formed sequentially on the substrate; the antireflective layer includes a silica layer, a titanium-silicon composite oxide gradient layer, a silica layer, a zirconium oxide layer and a mesoporous silica layer stacked sequentially from bottom to top; the waterproof and antifouling layer includes an interface reinforcement layer and a hydrophobic antifouling layer from bottom to top.

[0084] The preparation method of the antireflective and waterproof coating structure in this embodiment is the same as that in Example 1, and the obtained antireflective and waterproof coating structure is as follows:

[0085] The antireflective layer consists of a first silica layer with a thickness of 85 nm, a second titanium-silicon composite oxide gradient layer with a thickness of 18 nm, a third silica layer with a thickness of 40 nm, a fourth zirconium oxide layer with a thickness of 22 nm, and a fifth mesoporous silica layer with a thickness of 12 nm. The interface reinforcement layer contains 2.0 mmol / g of amino-functionalized mesoporous silica nanoparticles. The hydrophobic and antifouling layer contains 45 wt% perfluoropolyether modified silicone resin.

[0086] Comparative Example 1

[0087] This comparative example prepared the AR+AF coating according to the method of Example 1 in the patent with patent publication number CN119684915A.

[0088] Comparative Example 2

[0089] This comparative example prepared an AR+AF coating according to the method of Example 1 of patent publication number CN211972140U.

[0090] Comparative Example 3 (Single TiO2 layer)

[0091] This comparative example proposes an antireflective and waterproof coating structure, prepared using the same method as in Example 1, except that the titanium-silicon composite oxide gradient layer is replaced with a single titanium dioxide layer:

[0092] A single titanium dioxide layer: 15 nm thick, TiO2 target power 3.0 kW, refractive index approximately 2.30.

[0093] Comparative Example 4 (Single SiO2 layer)

[0094] This comparative example proposes an antireflective and waterproof coating structure, prepared using the same method as in Example 1, except that the titanium-silicon composite oxide gradient layer is replaced with a single silicon dioxide layer:

[0095] A single silicon dioxide layer: 25 nm thick, SiO2 target power 3.0 kW, refractive index approximately 1.46.

[0096] Test standard description:

[0097] Transmittance / Reflectance: Measured using a PerkinElmer Lambda 950 UV-Vis-NIR spectrophotometer;

[0098] Contact angle: A Dataphysics OCA20 contact angle measuring instrument was used, employing the seated drop method;

[0099] Pencil hardness: tested according to ASTM D3363 standard;

[0100] Abrasion resistance test: using a Taber linear abrasion tester, load 500g, CS-10F steel wool;

[0101] Adhesion: Tested according to ASTM D3359 cross-cut adhesion test;

[0102] Damp heat test: Conditions 85℃ / 85%RH, duration 1000 hours.

[0103] The samples prepared in Examples 1-3 and Comparative Examples 1-4 were tested for performance according to the above test standards, and the results are as follows:

[0104] Table 1: Optical Performance Test Results

[0105]

[0106] Table 2: Test Results of Mechanical and Waterproof Performance

[0107]

[0108] Table 3: Environmental stability test results (85℃ / 85%RH, 1000 hours)

[0109]

[0110] Results Analysis

[0111] Combined with Table 1-3 and Figure 2-4 It can be seen that Embodiments 1-3 of the present invention are significantly superior to Comparative Examples 1-4 in terms of optical performance, mechanical performance, waterproof performance, and environmental stability. Combined with... Figure 5 It can also be seen that the anti-reflective and waterproof coating structure prepared in Example 1 has excellent hydrophobic properties.

[0112] Specifically, the present invention provides the necessary high refractive index components to achieve excellent anti-reflection effect (average transmittance 98.7-98.9%) through the design of a titanium-silicon composite oxide gradient layer, and effectively releases interfacial stress through the gradient refractive index design, avoiding the problems of poor interfacial bonding and poor hygrothermal stability as in Comparative Example 3 (single TiO2 layer).

[0113] Meanwhile, by introducing a mesoporous silica layer and an interface reinforcement layer, this invention creates a robust interface that combines physical anchoring and chemical bonding, significantly improving wear resistance (the haze changes by only 0.2-0.3% after 10,000 cycles of steel wool friction) and exhibiting extremely low water vapor permeability, demonstrating excellent stability in harsh humid and hot environment tests.

[0114] Compared with Comparative Example 4 (single SiO2 layer), the present invention achieves significantly better optical performance while maintaining good interfacial adhesion through composite layer design, demonstrating the necessity and superiority of gradient composite layer design.

[0115] The antireflective and waterproof coating structure and its preparation method provided by this invention, through the innovative design of a titanium-silicon composite oxide gradient layer and the synergistic effect of a mesoporous silica layer and an interface reinforcement layer, successfully solve the long-standing technical problems in existing technologies, such as interface stress concentration and poor humid heat stability caused by water vapor penetration. Experimental data show that the coating of this invention is significantly superior to existing products in terms of optical performance, mechanical properties, waterproof performance, and environmental stability, and has significant industrial application value and market prospects.

[0116] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An antireflective and waterproof coating structure, characterized in that, It includes a substrate and an antireflective layer and a waterproof and antifouling layer formed sequentially on the substrate; the antireflective layer includes a silica layer, a titanium-silicon composite oxide gradient layer, a silica layer, a zirconium oxide layer and a mesoporous silica layer stacked sequentially from bottom to top.

2. The anti-reflective and waterproof coating structure according to claim 1, characterized in that, The TiO2 content in the titanium-silicon composite oxide gradient layer increases linearly from 25-30% to 70-75%, and the thickness is 12-18 nm.

3. The anti-reflective and waterproof coating structure according to claim 1, characterized in that, The waterproof and antifouling layer comprises, from bottom to top, an interface reinforcement layer and a hydrophobic antifouling layer; and / or, the substrate is glass.

4. The anti-reflective and waterproof coating structure according to claim 3, characterized in that, The interface reinforcement layer comprises amino-functionalized mesoporous silica nanoparticles and a perfluoroalkyl silane coupling agent; and / or, the hydrophobic and antifouling layer comprises a perfluoropolyether modified silicone resin.

5. The anti-reflective and waterproof coating structure according to claim 4, characterized in that, The amino content of the amino-functionalized mesoporous silica nanoparticles in the interface reinforcement layer is 1.5-2.0 mmol / g, and the amino density is 1.8-2.2 amino groups / nm. 2 The particle size of the mesoporous silica nanoparticles is 8-12 nm.

6. The anti-reflective and waterproof coating structure according to claim 4, characterized in that, The perfluoroalkylsilane coupling agent is perfluorobutyltriethoxysilane.

7. The anti-reflective and waterproof coating structure according to claim 4, characterized in that, The hydrophobic and antifouling layer contains 35-45 wt% perfluoropolyether modified silicone resin, and the molecular weight of the perfluoropolyether modified silicone resin is 3000-5000 g / mol; and / or the thickness of the hydrophobic and antifouling layer is 20-30 nm.

8. A method for preparing an antireflective and waterproof coating structure as described in any one of claims 1-7, characterized in that, Includes the following steps: Five layers of film are sequentially deposited on a substrate using magnetron sputtering technology to form an antireflection layer; The surface of the antireflection layer undergoes a two-step interface treatment: ammonia plasma treatment and perfluoroalkyl silane vapor deposition; An interface-strengthening layer is formed by coating amino-functionalized mesoporous silica nanoparticles onto the antireflective layer after interface treatment, and then a hydrophobic and antifouling layer is obtained by spin-coating perfluoropolyether modified silicone resin onto the interface-strengthening layer.

9. The preparation method according to claim 8, characterized in that, The preparation of the titanium-silicon composite oxide gradient layer in the five-layer film includes: co-sputtering with SiO2 and TiO2 targets, and controlling the target power to achieve a gradient change of TiO2 content from 30% to 70%, with a deposition thickness of 12-18 nm.

10. The preparation method according to claim 8, characterized in that, In ammonia plasma treatment, the power is 300-500W and the time is 1-3 minutes; in perfluoroalkylsilane vapor deposition, deposition is carried out at 100-130℃ for 5-15 minutes.

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