A high-hardness anti-reflective hardening film and a method for preparing the same

Abstract

This invention discloses a high-hardness anti-reflective curing film and its preparation method. The curing film comprises, from bottom to top, a transparent substrate layer, a primer adhesion layer, an anti-reflective functional coating, and a dense curing coating; the curing film has a pencil hardness ≥9H and a reflectivity ≤1.0%. This invention also discloses the preparation method of the curing film and its application in display panels, automotive central control displays, smart wearable devices, optical lenses, or outdoor display terminals. This invention solves the problem of poor adhesion in multi-layer structures through the primer adhesion layer, and through the synergistic effect of the high-hardness dense curing coating and the anti-reflective functional coating, it maintains a hardness of 9H while reducing reflectivity to ≤1.0% and increasing light transmittance to over 98%, with a controllable process suitable for mass production.

Description

Technical Field

[0001] This invention relates to the field of optical functional thin film technology, specifically to a high-hardness anti-reflection hardening film and its preparation method. Background Technology

[0002] With the rapid development of display technology, display panels such as liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), and micro LEDs are placing increasingly higher demands on optical performance (high light transmittance, low reflectivity) and mechanical protection performance (scratch resistance, abrasion resistance). Anti-reflective (AR) curing films, as key materials for improving display clarity and reducing ambient light reflection, have become mainstream products in the industry.

[0003] However, existing AR curing film technology still suffers from the following technical shortcomings: To achieve anti-reflective effects, current AR curing films typically employ porous structures or low-refractive-index coatings. However, these coatings have low cross-linking density and poor mechanical strength, with pencil hardness generally only reaching 2H-5H, making them unable to withstand everyday scratches. Conversely, when high-cross-linking density and high-filler content curing coatings are used to pursue high hardness, the coating surface becomes dense, making it impossible to construct an effective porous structure or low-refractive-index layer, often resulting in reflectivity exceeding 2.0%. Currently, there are no AR curing film products that can simultaneously achieve a 9H pencil hardness and ≤1.0% reflectivity. Furthermore, AR curing films typically consist of multiple layers, including a curing layer and an AR layer. Poor material compatibility and weak interfacial bonding between different coatings can easily lead to interlayer delamination and failure under long-term use or high-temperature and high-humidity environments. The problem of insufficient interfacial bonding is particularly prominent between the curing layer and the AR layer due to differences in their chemical properties and surface energies, severely impacting the product's lifespan. Meanwhile, adding excessive amounts of inorganic porous particles to reduce reflectivity can lead to increased haze and decreased light transmittance; adding high-hardness fillers to increase hardness can damage the pore structure of the AR layer or increase the refractive index. Existing technologies struggle to achieve a balance between low reflectivity (≤1.0%), high light transmittance (≥98%), and high hardness (≥9H).

[0004] In conclusion, it is of great significance to develop an AR hardening film that can simultaneously achieve 9H pencil hardness, ≤1.0% reflectivity, high adhesion, good environmental stability, and has a simplified structure, controllable process, and is suitable for large-scale production. Summary of the Invention

[0005] The purpose of this invention is to overcome the limitations of existing AR hardening films, which struggle to simultaneously achieve a 9H pencil hardness and ≤1.0% reflectivity, and suffer from poor adhesion and delamination issues in multi-layered structures. This invention provides a high-hardness anti-reflective hardening film, comprising, from bottom to top, a transparent substrate layer, a base coating adhesion layer, an anti-reflective functional coating, and a high-hardness dense hardening coating. The hardened film has a pencil hardness ≥9H and a reflectivity ≤1.0%. This invention solves the interlayer adhesion problem through the base coating adhesion layer. Through the synergistic effect of the high-hardness dense hardening coating and the anti-reflective functional coating, it maintains a 9H hardness while reducing reflectivity to ≤1.0% and increasing light transmittance to over 98%. Furthermore, the process is controllable and suitable for mass production.

[0006] A first aspect of the present invention provides a high-hardness anti-reflective curing film, wherein the high-hardness anti-reflective curing film has a layered structure and comprises, from bottom to top: Transparent substrate layer; A primer adhesion layer is disposed on the transparent substrate layer; An anti-reflective functional coating is disposed on the primer adhesion layer. The anti-reflective functional coating is formed by ultraviolet light curing of an anti-reflective coating material, and by weight, the anti-reflective coating material comprises: Low refractive index silicone resin: 25-40 parts; porous nano-silica microspheres: 10-25 parts; high-functionality acrylate oligomer: 5-15 parts; reactive diluent: 5-15 parts; photoinitiator: 1-3 parts; dispersant: 0.2-0.6 parts; leveling agent: 0.1-0.4 parts; solvent: 20-30 parts; crosslinking agent: 0.3-1.0 parts; A dense hardened coating is disposed on the anti-reflective functional coating, wherein the pencil hardness of the dense hardened coating is ≥9H; The reflectivity of the high-hardness anti-reflective hardening film is ≤1.0%.

[0007] Furthermore, the thickness of the transparent substrate layer is 50-200μm, the light transmittance is ≥92%, and the haze is ≤0.5%; the thickness of the primer adhesion layer is 1-3μm; the thickness of the anti-reflective functional coating is 1-5μm; and the thickness of the dense hardening coating is 5-12μm.

[0008] Furthermore, the dense curing coating is formed by curing a dense curing paint with ultraviolet light. By weight, the dense curing paint comprises: 30-45 parts of high-functionality polyurethane acrylate oligomer; 15-25 parts of reactive diluent; 2-6 parts of surface-modified nano-silica; 3-8 parts of toughening modifier; 2-4 parts of photoinitiator; 0.2-0.8 parts of leveling agent; 0.1-0.5 parts of defoamer; 0.5-1.5 parts of adhesion promoter; and 15-25 parts of solvent.

[0009] High-functionality polyurethane acrylate oligomers are the main film-forming substances for dense, curable coatings. The number of acrylate double bonds in their molecular structure determines the crosslinking density and hardness of the coating. This application uses a blend of hexafunctional and nonafunctional polyurethane acrylates in a mass ratio of 1:1.0-1.3. Each molecule of the hexafunctional polyurethane acrylate contains 6 acrylate double bonds, while each molecule of the nonafunctional polyurethane acrylate contains 9 acrylate double bonds. The nonafunctional component provides higher crosslinking density and hardness, while the hexafunctional component regulates the system's flexibility and curing shrinkage. The blend of the two can simultaneously achieve high hardness and good flexibility.

[0010] Reactive diluents are used to adjust coating viscosity and participate in the construction of UV-cured crosslinking networks. This application uses a compound of TMPTA (trimethylolpropane triacrylate), PETTA (pentaerythritol tetraacrylate), and DPHA (dipentaerythritol hexaacrylate) in a mass ratio of (1.5-2.5):(0.5-1.5):(0.5-1.5). TMPTA is a trifunctional reactive diluent, providing a faster reaction rate and higher basic crosslinking density; PETTA is a tetrafunctional reactive diluent, increasing the crosslinking density; DPHA is a hexafunctional reactive diluent, containing ethoxy groups in its molecule, which can improve coating surface leveling and regulate curing shrinkage while providing high crosslinking density. The synergistic effect of these three diluents achieves a comprehensive balance of high hardness, high abrasion resistance, a smooth and even appearance, and low curing shrinkage.

[0011] Surface-modified nano-silica is used to improve the hardness and wear resistance of coatings. The nano-silica has a particle size of 15-30nm and is surface-modified with silane coupling agents (such as KH-570 and KH-560). After modification, the nanoparticles have acrylate groups on their surface that can participate in UV curing, which can form chemical bonds with oligomers and reactive diluents, preventing nanoparticle aggregation and ensuring the optical transparency of the coating.

[0012] Toughening modifiers are used to improve the brittleness of highly cross-linked coatings, enhancing their flexibility and impact resistance while maintaining high hardness. These toughening modifiers are aliphatic epoxy acrylates and / or polyether acrylates, whose molecular structures contain flexible segments that can form a microscopic flexible phase within the highly cross-linked network, absorbing and dispersing stress to prevent cracking during bending or impact.

[0013] Photoinitiators are used to absorb ultraviolet light energy and initiate the free radical polymerization reaction of acrylate double bonds, enabling rapid curing of the coating. This application uses photoinitiator 184 (1-hydroxycyclohexylphenyl ketone) and TPO (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) in a 1:1 mass ratio. Photoinitiator 184 is an α-hydroxyketone photoinitiator with a short absorption wavelength, suitable for surface curing; TPO is an acylphosphine oxide photoinitiator with a longer absorption wavelength (up to 400 nm or more), exhibiting excellent deep curing ability and low yellowing. The combination of the two achieves the dual effect of sufficient surface curing and complete deep curing.

[0014] Leveling agents are used to reduce the surface tension of coatings, improve leveling properties during the coating process, prevent defects such as pinholes and orange peel, and ensure a smooth and even coating surface. This application uses a polyether-modified siloxane leveling agent, which has good compatibility with polyurethane acrylate systems and does not affect the optical properties and adhesion of the coating.

[0015] Defoamers are used to eliminate air bubbles generated during coating formulation and application, preventing defects such as pinholes and bubbles in the coating. This application uses an organosilicon defoamer, which has good compatibility with the system and high defoaming efficiency.

[0016] Adhesion promoters are used to enhance the bonding force between the dense, hardened coating and the primer adhesion layer. This application employs a compound mixture of silane coupling agents KH-570 (γ-methacryloyloxypropyltrimethoxysilane) and KH-560 (γ-glycidyl etheroxypropyltrimethoxysilane). The methacryloyloxy group of KH-570 participates in the UV curing reaction, forming a chemical bond with the polyurethane acrylate system; the epoxy group of KH-560 reacts with active groups such as hydroxyl groups on the surface of the primer coating to form strong chemical bonds. The combination of these two agents achieves a bidirectional adhesion-enhancing effect, connecting the hardened layer to the primer coating.

[0017] Solvents are used to adjust the viscosity of the coating to suit the microgravure coating process. This application uses a mixed solvent of ethyl acetate, butanone, and isopropanol in a mass ratio of 2:2:1. The three solvents have different evaporation rates: ethyl acetate has a moderate evaporation rate, butanone has a relatively fast evaporation rate, and isopropanol has a slow evaporation rate and good wettability to the substrate. This mixture allows for gradient evaporation, preventing orange peel or pinholes in the coating due to excessively rapid solvent evaporation, while ensuring coating smoothness and drying efficiency.

[0018] Furthermore, the high-functionality polyurethane acrylate oligomer is a compound mixture of hexafunctional polyurethane acrylate and nonafunctional polyurethane acrylate, with a mass ratio of 1:1.0-1.3; and / or, the reactive diluent is a compound mixture of TMPTA, PETTA and DPHA, with a mass ratio of (1.5-2.5):(0.5-1.5):(0.5-1.5); and / or, the toughening modifier is an aliphatic epoxy acrylate and / or a polyether acrylate; and / or, the surface-modified nano silica is 15-30nm silica particles modified with a silane coupling agent.

[0019] Furthermore, the anti-reflective functional coating is formed by curing an anti-reflective coating with ultraviolet light. By weight, the anti-reflective coating comprises: 25-40 parts of low-refractive-index silicone resin; 10-25 parts of porous nano-silica microspheres; 5-15 parts of high-functionality acrylate oligomer; 5-15 parts of reactive diluent; 1-3 parts of photoinitiator; 0.2-0.6 parts of dispersant; 0.1-0.4 parts of leveling agent; 20-30 parts of solvent; and 0.3-1.0 parts of crosslinking agent.

[0020] Low-refractive-index silicone resins are the main film-forming materials for anti-reflective coatings. Their low refractive index (typically 1.40-1.45) helps reduce the overall reflectivity of the coating. This application uses a methacrylate-based silicone resin. This resin molecule contains methacrylate groups, which can participate in the UV curing reaction to form a cross-linked network. At the same time, the silicone backbone endows the coating with a low refractive index and good flexibility.

[0021] Hollow porous silica microspheres are the core component for further reducing the refractive index of the coating. These microspheres have a hollow, porous structure containing a large amount of air (refractive index approximately 1.0). When uniformly dispersed within a silicone resin matrix, they significantly reduce the effective refractive index of the coating. The microspheres have a particle size of 50-200 nm, smaller than the wavelength of visible light (380-780 nm), thus exhibiting good transmittance of visible light without causing significant scattering loss. The surface of the microspheres is hydrophobically modified to ensure good dispersibility within the silicone resin system, preventing agglomeration and guaranteeing the optical uniformity of the coating.

[0022] High-functionality acrylate oligomers are used to improve the adhesion and mechanical strength of anti-reflective coatings. This application uses trifunctional polyurethane acrylate, whose molecules contain three acrylate double bonds, which can form a cross-linked network after UV curing, firmly anchoring hollow porous microspheres in the coating, while enhancing the bonding force between the coating and the underlying primer and the upper dense hardened coating.

[0023] Reactive diluents are used to adjust the viscosity of coatings to suit the coating process and also participate in the construction of UV-cured crosslinking networks. This application uses a blend of TPGDA (tripropylene glycol diacrylate) and HDDA (1,6-hexanediol diacrylate). TPGDA has a viscosity of 10-20 mPa·s, and HDDA has a viscosity of 5-10 mPa·s. The blend of the two can reduce the viscosity of the coating while maintaining the flexibility and adhesion of the coating.

[0024] Photoinitiators are used to absorb ultraviolet light energy and initiate polymerization reactions, thereby curing the anti-reflective coating. This application uses a 1:1 mass ratio of photoinitiator TPO to 1173. TPO has a longer absorption wavelength, making it suitable for deep curing of thicker coatings; 1173 is an α-hydroxyketone photoinitiator with a shorter absorption wavelength, suitable for surface curing. The combination of these two photoinitiators achieves uniform curing of the coating from the surface inwards.

[0025] Dispersants are used to promote the uniform dispersion of hollow porous silica nanospheres in coatings and prevent microsphere aggregation. This application uses a polyurethane-type dispersant, whose molecules contain anchoring groups and solvation segments. The anchoring groups can be adsorbed on the surface of the microspheres, and the solvation segments provide steric hindrance, preventing the microspheres from approaching each other and agglomerating.

[0026] Leveling agents are used to improve the leveling properties during the coating process and prevent defects such as flow marks and orange peel from appearing on the coating. This application uses a fluorinated modified silicone leveling agent, whose fluorinated segments can reduce the surface tension of the coating and promote uniform shrinkage of the coating during the drying process, resulting in a smooth and even coating surface.

[0027] Solvents are used to adjust the viscosity of the coating to suit the coating process. This application uses a mixed solvent of ethyl acetate and propylene glycol methyl ether acetate (PMA) in a 1:1 mass ratio. Ethyl acetate has a moderate evaporation rate, while PMA has a slower evaporation rate; the mixture of the two allows for gradient evaporation, ensuring both coating smoothness and drying efficiency.

[0028] Crosslinking agents are used to enhance the cohesion and environmental stability of antireflective coatings. This application uses epoxy-based crosslinking agents, whose epoxy groups can react with active groups such as hydroxyl and carboxyl groups in silicone resins and acrylate oligomers to form additional crosslinking points, thereby enhancing the cohesion of the coating and its adhesion to adjacent coatings.

[0029] Furthermore, the porous nano-silica microspheres have a particle size of 50-200 nm, are hollow porous structures, and have a hydrophobic modified surface; and / or, the low refractive index silicone resin is a methacrylate-based silicone resin; and / or, the high-functionality acrylate oligomer is a trifunctional polyurethane acrylate.

[0030] Furthermore, it also includes a superhydrophobic and antifouling surface layer disposed on the dense, hardened coating; the superhydrophobic and antifouling surface layer is formed by ultraviolet light curing of the superhydrophobic and antifouling coating, and by weight, the superhydrophobic and antifouling coating comprises: 35-50 parts of fluorinated silane oligomer; 5-12 parts of low surface energy oleophobic additive; 1-4 parts of nano-abrasion-resistant particles; 5-12 parts of reactive diluent; 0.5-2 parts of photoinitiator; 0.1-0.3 parts of fluorine-modified leveling agent; 10-20 parts of solvent; and 0.2-1.0 parts of crosslinking agent. Furthermore, the thickness of the superhydrophobic and antifouling surface layer is 0.2-1.0 μm.

[0031] Fluorinated silane oligomers are the main film-forming materials for superhydrophobic and antifouling coatings. Their fluorocarbon segments provide extremely low surface energy, making them the core component for achieving high hydrophobicity, oleophobicity, and anti-fingerprint properties. This application uses a blend of perfluoropolyether siloxane acrylate and dodecafluoroheptyl methacrylate. Perfluoropolyether siloxane acrylate has a high fluorine content and extremely low surface energy, providing excellent hydrophobicity, oleophobicity, and anti-fingerprint properties, but its reactivity is relatively low and its cost is high. Dodecafluoroheptyl methacrylate contains methacrylate groups that can participate in UV curing, exhibiting higher reactivity and improving crosslinking density and abrasion resistance, but its fluorine content is slightly lower. The blend of the two can improve the coating's reactivity, crosslinking density, and abrasion resistance while maintaining excellent hydrophobic and oleophobic properties.

[0032] Low surface energy oleophobic additives are used to further reduce the surface energy of the coating, enhancing its anti-fingerprint and easy-to-clean properties. This application employs perfluorooctyltrimethoxysilane and / or fluorocarbon resin. Perfluorooctyltrimethoxysilane is a small-molecule fluorosilane; its methoxy group can react with the hydroxyl groups in the coating or the active groups on the substrate surface to form strong chemical bonds, providing durable hydrophobic and oleophobic effects. Fluorocarbon resin is a high-molecular-weight fluoropolymer with extremely low surface energy, which imparts excellent antifouling properties to the coating. Both can be used alone or in combination.

[0033] Nanoscale wear-resistant particles are used to enhance the scratch resistance and abrasion resistance of superhydrophobic and antifouling surfaces. This application uses fluorosilicone-modified alumina with a particle size of 10-15 nm. Alumina itself has high hardness (Mohs hardness 9). After fluorosilicone modification, the particle surface has fluorine-containing groups, which have good compatibility with fluorinated silane oligomers and can be uniformly dispersed in the coating. Fluorosilicone-modified alumina can improve the hardness and abrasion resistance of the coating, and its surface fluorine-containing groups can participate in the construction of hydrophobic surfaces without affecting the water droplet angle of the coating. The fluorosilicone-modified alumina can be obtained commercially or prepared by dispersing nanoscale alumina in an ethanol solution of fluorinated silane (such as perfluorodecyltrimethoxysilane), heating under reflux, and then drying.

[0034] Reactive diluents are used to adjust the viscosity of superhydrophobic and antifouling coatings to adapt them to microgravure coating processes, while also participating in the construction of UV-cured crosslinking networks. This application uses TPGDA (tripropylene glycol diacrylate), a difunctional reactive diluent with moderate viscosity (10-20 mPa·s), good compatibility with fluorinated silane oligomers, and excellent flexibility and adhesion of the cured coating.

[0035] Photoinitiators are used to absorb ultraviolet light energy and initiate polymerization reactions, thereby curing superhydrophobic and antifouling surfaces. This application uses the photoinitiator TPO (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide). TPO is an acylphosphine oxide photoinitiator with a long absorption wavelength (up to 400 nm or more), good solubility in fluorine-containing systems, low susceptibility to yellowing, and excellent deep-curing ability, making it suitable for thin-layer curing of antifouling surfaces.

[0036] Fluorine-modified leveling agents are used to improve the leveling properties of fluorine-containing coatings and prevent defects such as pinholes and orange peel. Fluorine-modified leveling agents have good compatibility with fluorinated silane oligomers, which can effectively reduce the surface tension of the coating and promote uniform spreading of the coating film on the substrate surface.

[0037] Solvents are used to adjust the viscosity of the superhydrophobic and antifouling coating to adapt it to the microgravure coating process. This application uses a mixed solvent of fluorocarbon solvent and ethyl acetate in a 1:1 mass ratio. Fluorocarbon solvents have good solubility for fluorosilane oligomers, ensuring uniform dispersion of the coating components; the addition of ethyl acetate adjusts the evaporation rate and reduces costs.

[0038] Crosslinking agents are used to enhance the cohesion of the superhydrophobic and antifouling surface layer and its adhesion to the underlying AR coating. This application uses isocyanate-based crosslinking agents, whose isocyanate groups (-NCO) can react with fluorinated silane oligomers and active groups such as hydroxyl and carboxyl groups in the underlying AR coating to form chemical bonds, thereby improving the crosslinking density and interlayer adhesion of the coating.

[0039] Furthermore, the fluorinated silane oligomer is a compound mixture of perfluoropolyether siloxane acrylate and dodecafluoroheptyl methacrylate; the low surface energy oleophobic additive is perfluorooctyltrimethoxysilane and / or fluorocarbon resin; the nano-wear-resistant particles are 10-15 nm fluorosilicone modified alumina. The reactive diluent is TPGDA and / or HDDA.

[0040] A second aspect of the present invention provides a method for preparing the above-mentioned high-hardness anti-reflective hardening film, comprising the following steps: Step S1: Pre-treat the transparent substrate layer; Step S2: Apply a primer adhesion layer coating to the pretreated transparent substrate layer and dry it to form a primer adhesion layer; Step S3: Apply anti-reflective coating multiple times to the primer adhesion layer. After each application, perform segmented drying treatment, which includes a first stage of low-temperature drying and a second stage of high-temperature drying. The first stage of low-temperature drying is performed at a temperature of 40-60℃ for 0.5-1.5 minutes, and the second stage of high-temperature drying is performed at a temperature of 70-90℃ for 0.5-1.5 minutes. Then, cure with ultraviolet light to form an anti-reflective functional coating. S4: Apply a dense hardening coating onto the anti-reflective functional coating, and then dry and cure it with ultraviolet light to form a dense hardening coating; S5. Perform post-processing to obtain the high-hardness anti-reflective hardened film.

[0041] Furthermore, in step S1, the pretreatment includes dust removal and corona treatment, with a corona power of 1.5-3.0kW and a surface tension of 42-48mN / m after treatment.

[0042] Furthermore, in step S2, microgravure coating is used, with a coating speed of 10-20 m / min, a drying temperature of 60-80℃, and a drying time of 1-3 min.

[0043] Furthermore, in step S3, slit coating is used, with 3-5 coating passes, a coating speed of 5-12 m / min, a wet film thickness of 2-6 μm, and an ultraviolet curing energy of 300-500 mJ / cm². 2 .

[0044] Furthermore, in step S4, microgravure coating is used, with a coating speed of 8-15 m / min, a wet film thickness of 8-15 μm, a drying temperature of 70-90℃, a drying time of 2-3 min, and an ultraviolet curing energy of 500-700 mJ / cm². 2 .

[0045] Furthermore, in step S5, the post-treatment includes aging at room temperature for 12-24 hours.

[0046] Furthermore, it also includes applying a superhydrophobic and antifouling coating to the antireflective functional coating, followed by drying and ultraviolet curing to form a superhydrophobic and antifouling surface layer.

[0047] Furthermore, when applying the superhydrophobic and antifouling coating, a microgravure coating method is used, with a coating speed of 15-25 m / min, a wet film thickness of 0.5-1.2 μm, a drying temperature of 50-60℃, a drying time of 1 min, and an ultraviolet curing energy of 250-350 mJ / cm². 2 .

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This application sequentially comprises a primer adhesion layer, an anti-reflective functional coating, and a dense curing coating on a transparent substrate layer. The dense curing coating is a composite of a high-functionality polyurethane acrylate oligomer and surface-modified nano-silica, exhibiting high cross-linking density and high surface hardness, achieving a pencil hardness of 9H. The anti-reflective functional coating is a composite of a low-refractive-index silicone resin (refractive index 1.40-1.45) and hollow porous nano-silica microspheres (containing air internally, refractive index approximately 1.0), reducing the overall refractive index of the coating to 1.30-1.45. More importantly, this application places the anti-reflective functional coating beneath the dense curing coating (i.e., the hardness layer is the outermost layer, and the anti-reflective layer is the innermost layer). The dense curing coating, as the outermost layer, directly withstands external scratches and abrasion, exerting its 9H hardness protective function; the anti-reflective functional coating, as the inner layer, is unaffected by external mechanical damage, stably performing its low-refractive-index anti-reflective function. This functional layer separation design solves the technical problem of conflicting hardness and anti-reflective functions within the same coating in existing technologies. As shown in the embodiments, the hardened film of the present invention can simultaneously achieve 9H pencil hardness, ≤1.0% reflectivity, ≥97.5% light transmittance and ≤0.5% haze, breaking through the technical bottleneck that has long existed in this field.

[0049] 2. This application features a primer adhesion layer specifically designed between the transparent substrate layer and the anti-reflective functional coating. This layer, 1-3 μm thick, is formed by thermosetting a modified polyurethane acrylate emulsion. The primer adhesion layer bonds to the PET substrate surface through both physical anchoring and chemical bonding. Simultaneously, the active groups on its surface (such as hydroxyl and carboxyl groups) react with the crosslinking agent (epoxy-based) in the anti-reflective functional coating to form chemical bonds, achieving interlayer adhesion at grade 0 according to GB / T 9286-1998 standard. Furthermore, the adhesion promoter (KH-570 and KH-560 compounded) in the dense curing coating provides a bidirectional adhesion-enhancing effect, connecting the curing layer above and the anti-reflective layer below, further strengthening the interlayer bond. As shown in the examples, the adhesion of this invention remains at grade 0 after high temperature and high humidity (85℃ / 85%RH, 500h) and thermal cycling (-20℃~80℃, 100 cycles), with a reflectivity change ≤0.2%.

[0050] 3. This application can further provide a superhydrophobic and antifouling surface layer on the dense hardened coating. This surface layer contains fluorinated silane oligomers and nano-abrasion-resistant particles, giving the film anti-fingerprint, antifouling, and oleophobic functions. As shown in the examples, the static water droplet angle is ≥115°, the oil droplet angle is ≥90°, and there are no visible scratches after 1000 cycles of rubbing with 1kg of #0000 steel wool.

[0051] 4. This application adopts a fully wet roll-to-roll coating process (microgravure + slot coating), and each layer is formed by coating + UV curing. It has low equipment investment, high production efficiency, and is suitable for large-scale industrial production. Attached Figure Description

[0052] Figure 1 This is a schematic diagram of the layer structure of the high-hardness anti-reflection hardening film in Embodiment 1 of the present invention.

[0053] The markings in the diagram are: 1-Transparent substrate layer; 2-Adhesion primer layer; 3-Anti-reflective functional coating; 4-Dense hardened coating; 5-Superhydrophobic and anti-fouling surface layer. Detailed Implementation

[0054] The present invention will now be described in further detail with reference to specific embodiments. However, this should not be construed as limiting the scope of the present invention to the following embodiments; all technologies implemented based on the content of the present invention fall within the scope of the present invention.

[0055] To better understand the technical solutions of the above embodiments, the following more detailed experimental examples are provided for further explanation. Those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this disclosure. Where specific techniques or conditions are not specified in the examples, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0056] I. Raw material sources and general preparation methods The main sources of the raw materials used in the following examples and comparative examples are as follows: Optical grade PET film: Toray Industries, Japan, model XG7PL2, thickness 125μm.

[0057] Hexafunctional polyurethane acrylate: Changxing Materials, model 6195-100.

[0058] Nine-functional polyurethane acrylate: Sartoma, model CN9010.

[0059] Surface-modified nano silica: Evonik, model Aerosil R972 (KH-570 modified, particle size 16nm).

[0060] Hollow porous nano-silica microspheres: Nanjing Tianxing New Materials, model TSP-H100 (particle size 100nm, hydrophobic modification).

[0061] Perfluoropolyether siloxane acrylate: Daikin, model OPTOOL DAC-HP.

[0062] Dodecafluoroheptyl methacrylate: Harbin Xuejia, model Actyflon-G04.

[0063] Other ingredients such as TMPTA, PETTA, DPHA, TPGDA, HDDA, photoinitiator 184, TPO, 1173, toughening modifier, adhesion promoter KH-570 / KH-560, leveling agent, defoamer, and dispersant are all commercially available industrial products.

[0064] The preparation methods for each coating are as follows: Preparation of high-hardness, dense, and hardening coating: Weigh each component according to the weight parts, stir the high-functionality polyurethane acrylate oligomer, reactive diluent, and toughening modifier at 500-800 r / min for 30 min; add surface-modified nano-silica and disperse at 1200-1500 r / min for 1 h; add photoinitiator, leveling agent, defoamer, adhesion promoter, and solvent and stir for 20 min; filter through a 400-mesh screen and set aside.

[0065] Preparation of anti-reflective coating: Stir low refractive index silicone resin, porous nano silica microspheres, and high-functionality acrylate oligomer at 600 r / min for 30 min; add reactive diluent, photoinitiator, dispersant, leveling agent, and solvent and stir for 20 min; add crosslinking agent and stir for 10 min; filter through a 500 mesh screen and set aside.

[0066] Preparation of superhydrophobic and antifouling coating: Stir fluorinated silane oligomer, low surface energy oleophobic additive, and nano wear-resistant particles for 30 min; add reactive diluent, photoinitiator, fluorinated leveling agent and solvent and stir for 15 min; add crosslinking agent and stir for 10 min; filter with a 500 mesh screen and set aside.

[0067] In the following examples and comparative examples, the coating and curing process of each coating adopts a continuous roll-to-roll coating production line, the coating method is microgravure coating or slot coating, and UV curing uses a high-pressure mercury lamp (wavelength 365nm).

[0068] Performance testing methods The test methods for each performance item in the following embodiments and comparative examples are as follows: Pencil hardness test: According to GB / T 6739-2006 standard, a pencil hardness tester is used with a load of 500g. Mitsubishi brand pencils are used, and the test is considered qualified if there are no scratches.

[0069] Reflectance test: The reflectance of vertically incident light was tested using an ultraviolet-visible spectrophotometer in accordance with GB / T 2680-2021 standard.

[0070] Transmittance test: The total transmittance was tested using a UV-Vis spectrophotometer in accordance with GB / T 2680-2021 standard.

[0071] Haze test: The test was conducted using a haze meter in accordance with the GB / T 2410-2003 standard.

[0072] Static water droplet angle test: The contact angle of 5 μL of deionized water on the sample surface was measured using a contact angle meter.

[0073] Static oil droplet angle test: The contact angle of 5μL medical paraffin oil on the sample surface was tested using a contact angle measuring instrument.

[0074] Adhesion test: According to GB / T 9286-1998 standard, the test is conducted using a cross-cut adhesion tester and 3M tape, with grade 0 being the best grade.

[0075] Abrasion resistance test: A steel wool abrasion tester was used with #0000 steel wool, a load of 1kg, and 1000 cycles of reciprocating friction. After friction, the abrasion was observed under a 10x magnifying glass to check for any visible scratches.

[0076] High temperature and high humidity aging test: The product was placed in a constant temperature and humidity chamber at 85℃ and 85% relative humidity for 500 hours. After the test, the adhesion and other properties were retested.

[0077] Thermal cycling test: A high and low temperature test chamber is used to cycle between -20℃ and 80℃ for 2 hours per cycle (or simply "100 cycles in total"). After the test, the optical and mechanical properties are retested.

[0078] Cross-sectional thickness test: Field emission scanning electron microscope was used to observe the coating cross-section. The thickness was measured at least 5 different locations for each sample, and the average value was calculated.

[0079] Example 1 This embodiment provides a high-hardness anti-reflective hardening film, such as Figure 1 As shown, from bottom to top, it includes: a transparent substrate layer 1, a primer adhesion layer 2, an anti-reflective functional coating 3, a dense hardening coating 4, and a superhydrophobic and anti-fouling surface layer 5.

[0080] Transparent substrate layer 1: Optical grade PET film with a thickness of 125μm, light transmittance of 92.5% and haze of 0.3%.

[0081] Primer adhesion layer 2: formed by thermosetting modified polyurethane acrylate emulsion, with a thickness of 2μm.

[0082] Anti-reflective coating 3: Formed by UV curing of anti-reflective coating, with a thickness of 3μm. The coating formulation (parts by weight) is as follows: 32 parts low refractive index silicone resin, 18 parts hollow porous nano-silica microspheres (particle size 100nm), 10 parts trifunctional polyurethane acrylate, 6 parts TPGDA, 6 parts HDDA, 1 part photoinitiator TPO, 1 part 1173, 0.4 parts dispersant, 0.2 parts leveling agent, 25 parts solvent (ethyl acetate: propylene glycol methyl ether acetate = 1:1), and 0.6 parts epoxy crosslinking agent.

[0083] Dense Hardening Coating 4: Formed by UV curing of a high-hardness dense hardening coating, with a thickness of 8μm. The coating formulation (parts by weight) is as follows: 20 parts hexafunctional polyurethane acrylate, 20 parts nonafunctional polyurethane acrylate, 10 parts TMPTA, 5 parts PETTA, 5 parts DPHA, 4 parts surface-modified nano silica, 5 parts toughening modifier, 1.5 parts photoinitiator 184, 1.5 parts TPO, 0.5 parts leveling agent, 0.3 parts defoamer, 0.5 parts adhesion promoters KH-570 and KH-560, and 20 parts solvent (ethyl acetate:butanone:isopropanol = 2:2:1).

[0084] Superhydrophobic and antifouling surface layer 5: Formed by UV curing of superhydrophobic and antifouling coating, with a thickness of 0.5μm. The coating formulation (parts by weight) is as follows: 25 parts perfluoropolyether siloxane acrylate, 20 parts dodecafluoroheptyl methacrylate, 8 parts perfluorooctyltrimethoxysilane, 2.5 parts fluorosilicone modified alumina (particle size 12nm), 8 parts TPGDA, 1.2 parts photoinitiator TPO, 0.2 parts fluorine modified leveling agent, 15 parts solvent (fluorocarbon solvent: ethyl acetate = 1:1), and 0.5 parts isocyanate crosslinking agent.

[0085] Preparation method: S1: The PET substrate is subjected to dust removal and corona pretreatment with a corona power of 2.2kW, resulting in a surface tension of 45mN / m after treatment. In some embodiments, the corona power is 1.5-3.0kW, and the surface tension after treatment is 42-48mN / m, which can be adjusted adaptively.

[0086] S2: Apply the primer adhesion coating using a microgravure plate at a speed of 15 m / min, and dry at 70°C for 2 min to form primer adhesion layer 2. Alternatively, apply the primer adhesion coating using a microgravure plate at a speed of 15 m / min, and dry at 70°C for 2 min, followed by heat curing to form primer adhesion layer 2. In some embodiments, the coating speed is 10-20 m / min, the drying temperature is 60-80°C, and the drying time is 1-3 min, which can be adjusted accordingly.

[0087] S3: The anti-reflective coating is applied to the primer adhesion layer in three coats using a slotted-slot coating method at a speed of 8 m / min. Each coat produces a wet film thickness of 4 μm. After each coat, a segmented drying process is performed, comprising a first stage of low-temperature drying at 50°C for 1 min and a second stage of high-temperature drying at 80°C for 1 min. After the final coat and drying, it is cured under ultraviolet light at an energy of 400 mJ / cm², forming the anti-reflective functional coating 3. In some embodiments, the number of coats is 3-5, the coating speed is 5-12 m / min, the wet film thickness is 2-6 μm, and the ultraviolet curing energy is 300-500 mJ / cm². 2 It can be adapted.

[0088] S4: A high-hardness, dense, hardening coating is applied using a microgravure coating process at a speed of 10 m / min, a wet film thickness of 10 μm, and dried at 80°C for 2.5 min. Curing is then performed using UV energy of 600 mJ / cm² to form a dense, hardened coating 4. In some embodiments, the coating speed is 8-15 m / min, the wet film thickness is 8-15 μm, the drying temperature is 70-90°C, the drying time is 2-3 min, and the UV curing energy is 500-700 mJ / cm². 2 It can be adapted.

[0089] S5: A superhydrophobic and antifouling coating is applied using a microgravure coating process at a speed of 20 m / min, a wet film thickness of 0.8 μm, and dried at 55°C for 1 min. It is then cured with UV energy of 300 mJ / cm² to form a superhydrophobic and antifouling surface layer 5. In some embodiments, the coating speed is 15-25 m / min, the wet film thickness is 0.5-1.2 μm, the drying temperature is 50-60°C, the drying time is 1 min, and the UV curing energy is 250-350 mJ / cm². 2 It can be adjusted adaptively.

[0090] S6: The obtained product is cured at room temperature for 18 hours (in some embodiments, a curing time of 12-24 hours may be selected) to eliminate internal stress and obtain a high-hardness anti-reflective hardened film.

[0091] Performance testing: The performance of the hardened film obtained in this embodiment was tested as follows: pencil hardness 9H, reflectivity 0.9%, light transmittance 97.6%, haze 0.5%, static water droplet angle 118°, static oil droplet angle 94°, adhesion grade 0. After 1000 cycles of reciprocating rubbing with #0000 steel wool under a 1kg load, no visible scratches were observed under a 10x magnifying glass. After high temperature and high humidity (85℃ / 85%RH, 500h) and thermal cycling (-20℃~80℃, 100 cycles), the reflectivity change was ≤0.2%, and the adhesion grade remained 0.

[0092] Example 2 Transparent substrate layer 1: 50μm thick.

[0093] Primer adhesion layer 2: 1μm thick.

[0094] Anti-reflective coating 3: Thickness 1μm. Formulation: 25 parts low refractive index silicone resin, 10 parts porous microspheres, 5 parts trifunctional acrylate, 2.5 parts each of TPGDA and HDDA, 0.5 parts each of photoinitiator TPO and 1173, 0.2 parts dispersant, 0.1 parts leveling agent, 20 parts solvent, and 0.3 parts crosslinking agent.

[0095] High-hardness, dense, hardened coating 4: 5μm thickness. Formulation: 15 parts hexafunctional, 15 parts nonafunctional, 7.5 parts TMPTA, 3.75 parts PETTA, 3.75 parts DPHA, 2 parts surface-modified nano-silica, 3 parts toughening modifier, 1.0 part each of photoinitiator 184 and TPO, 0.2 parts leveling agent, 0.1 part defoamer, 0.25 parts each of adhesion promoter, and 15 parts solvent.

[0096] Superhydrophobic and antifouling surface layer 5: Thickness 0.2μm. Formulation: 17.5 parts perfluoropolyether siloxane, 17.5 parts dodecyl fluoroheptyl ester, 5 parts oleophobic additive, 1 part nano wear-resistant particles, 5 parts TPGDA, 0.5 parts TPO, 0.1 parts fluorine-modified leveling agent, 10 parts solvent, and 0.2 parts crosslinking agent.

[0097] Preparation method: S1: The PET substrate is subjected to dust removal and corona pretreatment with a corona power of 1.5kW and a surface tension of 42mN / m after treatment.

[0098] S2: Apply the primer adhesion coating using a micro-gravure plate at a speed of 10 m / min and dry at 60°C for 1 min to form primer adhesion layer 2.

[0099] S3: A slot-coating anti-reflective coating is applied in four coats at a speed of 8 m / min, resulting in a wet film thickness of 4 μm. Each coat is followed by a segmented drying process, comprising a first stage of low-temperature drying at 40°C for 1.5 min and a second stage of high-temperature drying at 70°C for 1.5 min, with a UV energy of 400 mJ / cm². 2 Curing forms an anti-reflective coating 3.

[0100] S4: High-hardness, dense, and hardening coating is applied using a micro-gravure coating at a speed of 10 m / min, with a wet film thickness of 10 μm. The coating is dried at 80℃ for 2.5 min and cured with UV energy of 600 mJ / cm² to form a dense, hardened coating 4.

[0101] S5: Superhydrophobic and antifouling coating is applied using a micro-gravure coating at a speed of 20m / min, with a wet film thickness of 0.8μm. It is dried at 55℃ for 1min and cured with UV energy of 300mJ / cm² to form a superhydrophobic and antifouling surface layer 5.

[0102] S6: The obtained product is cured at room temperature for 18 hours to eliminate internal stress and obtain a high-hardness anti-reflective hardened film.

[0103] Performance testing: Pencil hardness 9H, reflectivity 1.2%, light transmittance 98.0%, haze 0.5%, water droplet angle 115°, oil droplet angle 90°, adhesion grade 0, no scratches after 800 cycles of steel wool rubbing, reflectivity change ≤0.2% after environmental aging, adhesion grade 0.

[0104] Example 3 Transparent substrate layer 1: 200μm thick.

[0105] Primer adhesion layer 2: 3μm thick.

[0106] Anti-reflective coating 3: Thickness 5μm. Formulation: 40 parts low refractive index silicone resin, 25 parts porous microspheres, 15 parts trifunctional acrylate, 7.5 parts each of TPGDA and HDDA, 1.5 parts each of photoinitiator TPO and 1173, 0.6 parts dispersant, 0.4 parts leveling agent, 30 parts solvent, and 1.0 part crosslinking agent.

[0107] High-hardness, dense, hardened coating 4: 12μm thick. Formulation: 22.5 parts hexafunctional, 22.5 parts nonafunctional, 12.5 parts TMPTA, 6.25 parts PETTA, 6.25 parts DPHA, 6 parts surface-modified nano-silica, 8 parts toughening modifier, 2.0 parts each of photoinitiator 184 and TPO, 0.8 parts leveling agent, 0.5 parts defoamer, 0.75 parts each of adhesion promoter, and 25 parts solvent.

[0108] Superhydrophobic and antifouling surface layer 5: Thickness 1.0μm. Formulation: 25 parts perfluoropolyether siloxane, 25 parts dodecyl fluoroheptyl ester, 10 parts oleophobic additive, 4 parts nano wear-resistant particles, 12 parts TPGDA, 2.0 parts TPO, 0.3 parts fluorine-modified leveling agent, 20 parts solvent, and 1.0 part crosslinking agent.

[0109] Preparation method: S1: The PET substrate is subjected to dust removal and corona pretreatment with a corona power of 1.5kW and a surface tension of 42mN / m after treatment.

[0110] S2: Apply the primer adhesion coating using a micro-gravure plate at a speed of 10 m / min and dry at 60°C for 1 min to form primer adhesion layer 2.

[0111] S3: A slot-coated anti-reflective coating is applied in four coats at a speed of 8 m / min, resulting in a wet film thickness of 4 μm. Each coat is followed by a segmented drying process, comprising a first stage of low-temperature drying at 60°C for 0.5 min and a second stage of high-temperature drying at 90°C for 0.5 min, with a UV energy of 400 mJ / cm². 2 Curing forms an anti-reflective coating 3.

[0112] S4: High-hardness, dense, and hardening coating is applied using a micro-gravure coating at a speed of 10 m / min, with a wet film thickness of 10 μm. The coating is dried at 80℃ for 2.5 min and cured with UV energy of 600 mJ / cm² to form a dense, hardened coating 4.

[0113] S5: Superhydrophobic and antifouling coating is applied using a micro-gravure coating at a speed of 20m / min, with a wet film thickness of 0.8μm. It is dried at 55℃ for 1min and cured with UV energy of 300mJ / cm² to form a superhydrophobic and antifouling surface layer 5.

[0114] S6: The obtained product is cured at room temperature for 18 hours to eliminate internal stress and obtain a high-hardness anti-reflective hardened film.

[0115] Performance testing: Pencil hardness 9H, reflectivity 0.8%, light transmittance 98.5%, haze 0.3%, water droplet angle 119°, oil droplet angle 96°, adhesion grade 0, no scratches after 1000 cycles of steel wool rubbing, reflectivity change ≤0.2% after environmental aging, adhesion grade 0.

[0116] Example 4 Compared with Example 1, Example 4 only changed the ratio of hexa- and nine-functional compounds; the other preparation processes were exactly the same as those in Example 1.

[0117] (1) Ratio 1:0.8: Pencil hardness 9H, reflectivity 0.8%, microcracks when folded.

[0118] (2) Ratio 1:1.0: Same as Example 1, pencil hardness 9H, reflectivity 0.9%, no cracks when folded.

[0119] (3) Ratio 1:1.15: Pencil hardness 9H, reflectivity 0.85%, excellent flexibility.

[0120] (4) Ratio 1:1.3: Same as Example 4, pencil hardness 9H, reflectivity 0.8%, no cracks when folded.

[0121] (5) Ratio 1:1.5: Pencil hardness 9H, reflectivity 0.9%, cracks when folded, adhesion level 1.

[0122] A 6 / 9 functionality blend ratio within the range of 1:1.0-1.3 can simultaneously achieve 9H hardness, good flexibility, and grade 0 adhesion. Below 1:1.0, the coating becomes brittle, and above 1:1.5, flexibility and adhesion decrease.

[0123] Example 5 The only difference from Example 1 is the mass ratio of TMPTA, PETTA, and DPHA in the dense hardening coating (the ratio of the three is adjusted while keeping the total amount of reactive diluent at 20 parts by weight). The other components and preparation process are exactly the same as in Example 1.

[0124] (1) Ratio A: TMPTA:PETTA:DPHA = 1.5:1.5:1.0 (mass ratio); Performance: Pencil hardness 9H, reflectivity 0.85%, smooth coating appearance, no cracks when folded.

[0125] (2) Ratio B: TMPTA:PETTA:DPHA = 2.5:0.5:1.0 (mass ratio); Performance: Pencil hardness 9H, reflectivity 0.75%, smooth coating appearance, no cracks when folded.

[0126] (3) Ratio C: TMPTA:PETTA:DPHA = 2.0:1.0:1.0 (mass ratio); Performance: Pencil hardness 9H, reflectivity 0.9%, smooth coating appearance, no cracks when folded.

[0127] Example 6 The only difference from Example 1 is the ratio of KH-570 to KH-560. The total amount of adhesion promoter remains unchanged at 1.0 parts by weight. All other components and preparation processes are exactly the same as in Example 1.

[0128] The results of the tests for each ratio and adhesion are as follows: (1) Use only KH-570 (1.0 copy), do not use KH-560. Initial adhesion: Grade 1; Adhesion after high temperature and high humidity (85℃ / 85%RH, 500h): Grade 2.

[0129] (2) Use only KH-560 (1.0 copy), do not use KH-570. Initial adhesion: Grade 1; Adhesion after high temperature and high humidity (85℃ / 85%RH, 500h): Grade 2.

[0130] (3) The mass ratio of KH-570 to KH-560 is 1:2 (0.33 parts of KH-570 and 0.67 parts of KH-560). Initial adhesion: Grade 0; Adhesion after high temperature and high humidity (85℃ / 85%RH, 500h): Grade 1.

[0131] (4) The mass ratio of KH-570 to KH-560 is 2:1 (0.67 parts of KH-570 and 0.33 parts of KH-560). Initial adhesion: Grade 0; Adhesion after high temperature and high humidity (85℃ / 85%RH, 500h): Grade 0.

[0132] (5) The mass ratio of KH-570 to KH-560 is 1:1 (0.5 parts of KH-570 and 0.5 parts of KH-560). The formulation of Example 1 has an initial adhesion grade of 0 and an adhesion grade of 0 after exposure to high temperature and humidity (85℃ / 85%RH, 500h).

[0133] The adhesion test is conducted according to GB / T 9286-1998 standard. Grade 0 is the best (the cut edge is completely smooth and no piece falls off), Grade 1 is when a small piece falls off at the cut intersection (the area of ​​the fall off is <5%), and Grade 2 is when the area of ​​the fall off is 5-15%.

[0134] When KH-570 or KH-560 is used alone, the initial adhesion is only grade 1, which drops to grade 2 after high temperature and humidity, indicating that a single adhesion promoter is difficult to provide a stable and reliable interfacial bond. When the two are used in combination, the initial adhesion can be improved to grade 0, and when the ratio is 1:1 to 2:1, it can still maintain grade 0 after high temperature and humidity, showing the best environmental stability.

[0135] Comparative Example 1 The difference from Example 1 is that the primer adhesion layer 2 is omitted, and the anti-reflective coating is directly applied to the pretreated PET substrate.

[0136] Preparation method: A transparent substrate layer 1 identical to that in Example 1 was used. The substrate was subjected to dust removal and corona pretreatment. The application and curing of the primer adhesion layer 2 in Example 1 were omitted, and steps S3 to S6 were performed directly, with the coating and curing parameters being exactly the same as in Example 1.

[0137] Performance test results: Pencil hardness: 9H; Reflectivity: 0.8%; Light transmittance: 98.0%; Haze: 0.5%; Initial adhesion (cross-cut test): Grade 1; Adhesion after high temperature and high humidity (85℃ / 85%RH, 500h): Grade 2 (edge ​​delamination); Adhesion after thermal cycling (-20℃~80℃, 100 times): Grade 2; Steel wool rubbing (#0000, 1kg, 1000 times): Scratches appear after 800 times.

[0138] Comparative Example 2 The difference from Example 1 is that the high-functionality polyurethane acrylate oligomers in the dense curing coating are either only hexafunctional or only nonfunctional, and are not compounded. The preparation process is the same as in Example 1.

[0139] Preparation method: Option 2-1: Use only hexafunctional polyurethane acrylate (40 parts), without using nonfunctional polyurethane.

[0140] Option 2-2: Use only nine-functional polyurethane acrylate (40 parts), without using hexafunctional acrylate.

[0141] The remaining components are the same as in Example 1, and the coating and curing process is the same as in Example 1.

[0142] Performance test results: Option 2-1 (six senses only): Pencil hardness 9H, flexibility (180° fold) cracks when folded, adhesion grade 0.

[0143] Option 2-2 (Nine-Functionality Only): Pencil hardness 8H, flexibility (180° fold) cracks when folded, adhesion grade 0.

[0144] Comparative analysis with Example 1: Neither hexafunctionality nor nonafunctionality alone can simultaneously achieve 9H hardness and good flexibility (cracking upon folding). This application uses a blend of hexafunctionality and nonafunctionality in the range of 1:1.0-1.3, achieving a balance between hardness and flexibility.

[0145] Comparative Example 3 The difference from Example 1 is that the antireflective coating uses hollow porous nano-silica microspheres (100 nm in diameter, without hydrophobic modification) that have not undergone surface hydrophobic modification, while the other components are the same as in Example 1.

[0146] Preparation method: The same process steps as in Example 1 were used, except that unmodified porous nano-silica microspheres were used when formulating the antireflective coating. All other process parameters were the same as in Example 1.

[0147] Performance test results: Dispersion state of porous microspheres in coating: slight agglomeration, settling after standing for 30 min; reflectivity: 1.2%; transmittance: 97.5%; haze: 0.7%; reflectivity after high temperature and high humidity (85℃ / 85%RH, 500h): 1.9%; adhesion after high temperature and high humidity: Grade 1.

[0148] Comparative Example 4 Comparative Example 4-1 The difference from Example 1: the reactive diluent in the dense hardening coating is a single component, while the other components are the same as in Example 1.

[0149] Preparation method: Option 4-11: Use only TMPTA (20 doses); Option 4-12: Use only PETTA (20 doses); Option 4-13: Use only DPHA (20 doses) The remaining process steps are the same as in Example 1.

[0150] Performance test results: Option 4-11 (TMPTA only): Pencil hardness 8H, 800 scratches from steel wool abrasion (1000 times), smooth coating appearance.

[0151] Option 4-12 (PETTA only): Pencil hardness 8H, 700 scratches after 1000 steel wool rubbing cycles, smooth coating appearance.

[0152] Option 4-13 (DPHA only): Pencil hardness 9H, no scratches after 1000 steel wool rubbing cycles, severe orange peel appearance of the coating, and micro-cracks in flexibility.

[0153] Comparative analysis with Example 1: The hardness (8H) was insufficient with only TMPTA or only PETTA; DPHA alone resulted in severe orange peel and decreased flexibility. This application uses a 2:1:1 blend of TMPTA, PETTA, and DPHA, achieving a hardness of 9H, a smooth and even appearance, and good flexibility.

[0154] Comparative Example 5 The difference from Example 1 is that the active diluent in the dense hardening coating is a single-functionality diluent, while the remaining components are the same as in Example 1.

[0155] Preparation method: Option 5-1: Use only a monofunctional diluent (isoborneol acrylate IBOA, 20 parts). Option 5-2: Use only the bifunctional diluent (HDDA, 20 parts) Option 5-3: Use only the trifunctional diluent (TMPTA, 20 parts) The remaining process steps are the same as in Example 1.

[0156] Performance test results: Option 5-1 (IBOA): Pencil hardness 6H, scratches after 600 cycles of steel wool rubbing, low cross-linking density.

[0157] Option 5-2 (HDDA): Pencil hardness 7H, scratches after 800 cycles of steel wool rubbing, medium crosslinking density.

[0158] Option 5-3 (TMPTA): Pencil hardness 8H, no scratches after 1000 cycles of steel wool rubbing, and micro-cracks in flexibility.

[0159] Example 1 (TMPTA:PETTA:DPHA=2:1:1): Pencil hardness 9H, no scratches after 1000 cycles of steel wool friction, flexible without cracks, and smooth coating.

[0160] Comparative Example 6 The difference from Example 1: The high-functionality polyurethane acrylate oligomer of the dense hardened coating 4 adopts a dual-functionality + hexafunctionality compound scheme (mass ratio 1:1), and the other components are consistent with those of Example 1.

[0161] Preparation method: 20 parts of difunctional polyurethane acrylate and 20 parts of hexafunctional polyurethane acrylate were used as the oligomer system. The photoinitiator was a mixture of 184 and TPO (same as in Example 1). The remaining components were the same as in Example 1. The coating and curing process parameters were the same as in Example 1.

[0162] Performance test results: Pencil hardness: 7H; Steel wool abrasion (#0000, 1kg, 1000 times): Scratches appear after 800 times; Flexibility (180° fold): No cracks; Adhesion: Grade 0.

[0163] Comparative Example 7 The only difference from Example 1 is that the anti-reflective coating is formed by a single thick coating method, that is, a wet film thickness of 12 μm is applied in one coat, and the drying conditions are constant temperature drying at 80°C for 2 min. The UV curing conditions are the same as in Example 1. All other components are exactly the same as in Example 1.

[0164] Performance test results: Pencil hardness: 9H; Reflectivity: 1.8%; Light transmittance: 96.2%; Haze: 1.2%; Coating appearance: Slight orange peel; Adhesion: Grade 0; Steel wool rubbing (#0000, 1kg, 1000 times): No scratches after 1000 times; Reflectivity after high temperature and high humidity (85℃ / 85%RH, 500h): 2.1%; Adhesion after high temperature and high humidity: Grade 0.

[0165] Comparative Example 7, using a single-coat thick layer method, showed significantly higher reflectivity than Example 1, and a marked increase in haze. This indicates that the rapid evaporation of solvent during the single-coat thick layer process caused the hollow porous silica nanospheres to agglomerate or settle in the coating, resulting in uneven microsphere dispersion and thus increased scattering and decreased antireflection effect. This application employs a multi-coat thin layer method, with each wet film thickness being only 4 μm. This effectively avoids microsphere agglomeration and settling during the thick coating process, resulting in more uniform microsphere dispersion in the coating and thus achieving lower reflectivity and lower haze.

[0166] Comparative Example 8 The only difference from Example 1 is that the layer order of the anti-reflective coating and the dense curing coating is reversed, i.e., from bottom to top, they are: PET substrate, primer adhesion layer, dense curing coating, and anti-reflective coating. The formulation, thickness, and coating process parameters of each layer are consistent with those of Example 1.

[0167] Performance test results: Pencil hardness: 5H; Reflectivity: 0.8%; Light transmittance: 98.2%; Haze: 0.5%; Initial adhesion: Grade 0; Steel wool rubbing (#0000, 1kg, 1000 times): Obvious scratches appeared after 200 times, and the coating peeled off locally after 800 times; Reflectivity after high temperature and high humidity (85℃ / 85%RH, 500h): 0.9%; Adhesion after high temperature and high humidity: Grade 1.

[0168] Comparative Example 8 placed the anti-reflective coating on the outermost layer. Although the reflectivity remained low, the pencil hardness dropped sharply to 5H, indicating severely insufficient abrasion resistance. This may be because the anti-reflective coating contains a large number of hollow, porous nano-silica microspheres, resulting in a loose coating structure and low cross-linking density. This structure cannot provide effective mechanical protection, and the loose porous structure is easily damaged during friction, leading to coating peeling. In contrast, this application places a dense, hardened coating on the outermost layer, utilizing its high cross-linking density and high filler content to provide a hardness of 9H and excellent abrasion resistance (no scratches after 1000 cycles). Simultaneously, the anti-reflective coating is placed on the inner layer to protect it from external mechanical damage, ensuring stable anti-reflective performance.

[0169] Comparative Example 9 The only difference from Example 1 is that the anti-reflective coating is applied in the same three-coat method as in Example 1, but the drying after each coating is done at a constant temperature (80°C for 2 minutes), without segmented drying, and the total drying time is the same as in Example 1. The remaining components are exactly the same as in Example 1.

[0170] Performance test results: Pencil hardness: 9H; Reflectivity: 1.6%; Light transmittance: 96.8%; Haze: 0.8%; Coating appearance: Slight orange peel; Adhesion: Grade 0; Steel wool rubbing (#0000, 1kg, 1000 times): No scratches after 1000 times; Reflectivity after high temperature and high humidity (85℃ / 85%RH, 500h): 1.9%; Adhesion after high temperature and high humidity: Grade 0.

[0171] Comparative Example 9, using a constant-temperature drying method, exhibited significantly higher reflectivity than Example 1, lower transmittance, and higher haze, with a slight orange peel effect on the coating surface. Under constant-temperature drying conditions, the solvent evaporates at a single rate, resulting in consistent solvent evaporation rates on the coating surface and within the coating itself. This prevents effective microstructure control, leading to poor uniformity of the hollow porous microspheres' distribution within the coating and inadequate anti-reflection effect. Furthermore, rapid solvent evaporation degrades the coating surface's leveling properties, resulting in orange peel defects. This application employs a segmented drying process. The low-temperature stage allows for slow pre-curing of the coating surface and gradual solvent evaporation, preventing rapid surface skinning. The high-temperature stage accelerates the evaporation of remaining solvent and promotes complete cross-linking and curing reactions. This gradient heating drying method ensures both a smooth and even coating appearance and uniform dispersion of the hollow porous microspheres, allowing the anti-reflection coating to fully exert its anti-reflection effect, reducing reflectivity to below 1.0%.

[0172] In summary, the high-hardness anti-reflective hardening film provided by this invention achieves both high hardness and low reflectivity: through the synergistic core structure of "base coating adhesion layer 2, dense hardening coating 4, and anti-reflective functional coating 3", it realizes the dual requirements of 9H pencil hardness and ≤1.0% reflectivity, solving the technical problem of the conflict between hardness and AR performance in the prior art.

[0173] Excellent protective performance: The superhydrophobic and antifouling surface layer 5 gives the film high anti-fingerprint, antifouling and oleophobic functions, with a static water droplet angle ≥115° and an oil droplet angle ≥90°.

[0174] High adhesion and environmental stability: The second layer of the primer adhesion layer solves the technical problems of easy peeling and delamination of multi-layer structures, with an adhesion level of 0. The performance does not significantly decrease after high temperature and high humidity and cold and heat cycling.

[0175] The process is simple and suitable for large-scale production: It adopts a continuous micro-gravure + slot coating composite process, which is a fully wet coating process. Compared with the dry coating process, it has a lower cost and is suitable for roll-to-roll mass production.

[0176] Wide range of applications: The high-hardness anti-reflective curing film of this invention can be widely used in display panels (including liquid crystal displays, organic light-emitting diode displays, Micro LED displays, etc.), vehicle central control displays, smart wearable devices, optical lenses and outdoor display terminals.

[0177] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-hardness anti-reflective hardening film, characterized in that, The high-hardness anti-reflective hardening film has a layered structure, comprising, from bottom to top: Transparent substrate layer; A primer adhesion layer is disposed on the transparent substrate layer; An anti-reflective functional coating is disposed on the primer adhesion layer. The anti-reflective functional coating is formed by ultraviolet light curing of an anti-reflective coating material, and by weight, the anti-reflective coating material comprises: Low refractive index silicone resin: 25-40 parts; porous nano-silica microspheres: 10-25 parts; high-functionality acrylate oligomer: 5-15 parts; reactive diluent: 5-15 parts; photoinitiator: 1-3 parts; dispersant: 0.2-0.6 parts; leveling agent: 0.1-0.4 parts; solvent: 20-30 parts; crosslinking agent: 0.3-1.0 parts; A dense hardened coating is disposed on the anti-reflective functional coating, wherein the pencil hardness of the dense hardened coating is ≥9H; The reflectivity of the high-hardness anti-reflective hardening film is ≤1.0%.

2. The high-hardness anti-reflective hardening film according to claim 1, characterized in that, The thickness of the transparent substrate layer is 50-200μm, the light transmittance is ≥92%, and the haze is ≤0.5%. The thickness of the primer adhesion layer is 1-3 μm; The thickness of the anti-reflective coating is 1-5 μm; The thickness of the dense hardened coating is 5-12 μm.

3. The high-hardness anti-reflective hardening film according to claim 1, characterized in that, The dense hardening coating is formed by curing a dense hardening coating with ultraviolet light. By weight, the dense hardening coating comprises: High-functionality polyurethane acrylate oligomer: 30-45 parts; Reactive diluent: 15-25 parts; Surface-modified nano-silica: 2-6 parts; Toughening modifier: 3-8 parts; Photoinitiator: 2-4 parts; Leveling agent: 0.2-0.8 parts; Defoamer: 0.1-0.5 parts; Adhesion promoter: 0.5-1.5 parts; Solvent: 15-25 parts.

4. The high-hardness anti-reflective hardening film according to claim 3, characterized in that, The high-functionality polyurethane acrylate oligomer is a compound mixture of hexafunctional polyurethane acrylate and nonafunctional polyurethane acrylate, with a mass ratio of 1:1.0-1.3; and / or, the reactive diluent is a compound mixture of TMPTA, PETTA and DPHA, with a mass ratio of (1.5-2.5):(0.5-1.5):(0.5-1.5); and / or, the toughening modifier is an aliphatic epoxy acrylate and / or a polyether acrylate; and / or, the surface-modified nano silica is 15-30nm silica particles modified with a silane coupling agent.

5. The high-hardness anti-reflective hardening film according to claim 1, characterized in that, The porous nano-silica microspheres have a particle size of 50-200 nm, a hollow porous structure, and a surface modified with hydrophobicity.

6. The high-hardness anti-reflective hardening film according to claim 5, characterized in that, The low-refractive-index silicone resin is a methacrylate-based silicone resin; and / or, the high-functionality acrylate oligomer is a trifunctional polyurethane acrylate.

7. The high-hardness anti-reflective hardening film according to any one of claims 1-6, characterized in that, It also includes a superhydrophobic and antifouling surface layer disposed on the dense hardened coating; The superhydrophobic and antifouling surface layer is formed by ultraviolet light curing of a superhydrophobic and antifouling coating. By weight, the superhydrophobic and antifouling coating comprises: Fluorosilane oligomers: 35-50 parts; Low surface energy oleophobic additive: 5-12 parts; Nano-wear-resistant particles: 1-4 parts; Reactive diluent: 5-12 parts; Photoinitiator: 0.5-2 parts; Fluorine-modified leveling agent: 0.1-0.3 parts; Solvent: 10-20 parts; Crosslinking agent: 0.2-1.0 parts.

8. The high-hardness anti-reflective hardening film according to claim 7, characterized in that, The fluorinated silane oligomer is a compound mixture of perfluoropolyether siloxane acrylate and dodecafluoroheptyl methacrylate; the low surface energy oleophobic additive is perfluorooctyltrimethoxysilane and / or fluorocarbon resin; the nano-wear-resistant particles are 10-15 nm fluorosilicone modified alumina.

9. A method for preparing a high-hardness anti-reflective hardening film as described in any one of claims 1-8, characterized in that, Includes the following steps: Step S1: Pre-treat the transparent substrate layer; Step S2: Apply a primer adhesion layer coating to the pretreated transparent substrate layer and dry it to form a primer adhesion layer; Step S3: Apply anti-reflective coating multiple times onto the primer adhesion layer, and then dry and cure with ultraviolet light to form an anti-reflective functional coating. S4: Apply a dense hardening coating onto the anti-reflective functional coating, and then dry and cure it with ultraviolet light to form a dense hardening coating; S5. Perform post-processing to obtain the high-hardness anti-reflective hardened film.

10. The preparation method according to claim 9, characterized in that, In step S1, the pretreatment includes dust removal and corona treatment, with a corona power of 1.5-3.0 kW, resulting in a surface tension of 42-48 mN / m after treatment; and / or, In step S2, microgravure coating is used at a coating speed of 10-20 m / min, a drying temperature of 60-80℃, and a drying time of 1-3 min; and / or, In step S3, the anti-reflective coating is applied to the primer adhesion layer in 3-5 layers using a slot coating method. Each layer has a wet film thickness of 2-6 μm. After each application, a segmented drying process is performed, comprising a first stage of low-temperature drying and a second stage of high-temperature drying. The first stage of low-temperature drying is at 40-60℃ for 0.5-1.5 min, and the second stage of high-temperature drying is at 70-90℃ for 0.5-1.5 min. After the final application and drying, the coating is cured under ultraviolet light with an energy of 300-500 mJ / cm². The coating speed is 5-12 m / min; and / or... In step S4, microgravure coating is used, with a coating speed of 8-15 m / min, a wet film thickness of 8-15 μm, a drying temperature of 70-90℃, a drying time of 2-3 min, and an ultraviolet curing energy of 500-700 mJ / cm². 2 ; and / or, In step S5, the post-treatment includes aging at room temperature for 12-24 hours.

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