Chemical preparation process of AR antireflective film doped with functional nanoparticles

Abstract

This application relates to the field of optical film preparation technology, specifically disclosing a chemical preparation process for AR antireflective films doped with functional nanoparticles, including the following steps: Pretreatment: After fixing the substrate using a roll-to-roll machine, a flow rate of 2~4:1 is introduced. Ar / O2 A mixed gas is used for plasma treatment of the substrate at a transmission speed of 5-10 mm / min to obtain a treated material. Hydrolysis is then performed: anhydrous ethanol and deionized water are mixed in a volume ratio of 3-5:1 to form a mixed solvent. A silicon source precursor and catalyst are added, followed by the addition of silane coupling agent-modified metal oxide functional nanoparticles. In this application, silane coupling agent-modified metal oxide functional nanoparticles, along with the silicon source precursor and catalyst, are added to the mixed solvent. Pulsed ultrasonic hydrolysis is used to achieve in-situ bonding between the nanoparticles and the precursor, resulting in a film with uniform refractive index distribution and reduced reflectivity fluctuations.

Description

Technical Field

[0001] This application relates to the field of optical film preparation technology, and more specifically, to the chemical preparation process of AR antireflective films doped with functional nanoparticles. Background Technology

[0002] AR antireflective films, as a type of functional thin film that reduces light reflection and improves light transmission efficiency through optical interference principles, have become a core component of modern optical and electronic devices. In fields such as consumer electronics, new energy photovoltaics, and precision optical instruments, as devices develop towards flexibility, thinness, and multifunctionality, the performance requirements for AR antireflective films are becoming increasingly stringent. They not only need to achieve core optical properties such as low reflectivity and high transmittance in the visible light band, but also need to possess good mechanical stability, environmental adaptability, and compatibility for large-scale production.

[0003] Existing chemical preparation methods for AR antireflective films often employ a process route that involves pre-preparing functional nanoparticles and then mixing them with the film precursor. However, nanoparticles are prone to agglomeration due to insufficient compatibility between their surface properties and the precursor, making it difficult to achieve uniform dispersion. This results in uneven refractive index distribution and large fluctuations in reflectivity, which in turn affects the stability of optical performance. Summary of the Invention

[0004] To address the issues of uneven refractive index distribution and large reflectivity fluctuations in existing AR antireflective film chemical preparation processes, which affect the stability of optical performance, this application provides a chemical preparation process for AR antireflective films doped with functional nanoparticles.

[0005] The chemical preparation process of the AR antireflective film doped with functional nanoparticles provided in this application adopts the following technical solution: The chemical preparation process of AR antireflective film doped with functional nanoparticles includes the following steps: Pretreatment: After the substrate is fixed by a roll-to-roll unit, an Ar / O2 mixed gas with a volume ratio of 2~4:1 is introduced to perform plasma treatment at a substrate transport speed of 5~10mm / min to obtain the treated material; Hydrolysis preparation: Anhydrous ethanol and deionized water are mixed in a volume ratio of 3~5:1 to form a mixed solvent. After adding silicon source precursor and catalyst, silane coupling agent modified metal oxide functional nanoparticles are added. After pulse ultrasonic hydrolysis, a dispersion is obtained. Dip-coating defoaming: After the treated material is continuously dip-coated through a dispersion to form a wet film, it is defoamed by high-frequency ultrasound to obtain the coated material; Mixed curing: A N2 / O2 mixed gas with a volume ratio of 3~5:1 is introduced into the roll-to-roll unit to perform plasma curing of the coating material at a curing temperature of 50~90℃ to obtain a cured material; Irradiation and sealing: After irradiating the cured material with ultraviolet light with a wavelength of 240~260nm, it is continuously wound up, sealed and packaged, and stored in a dry and light-proof environment to complete the preparation.

[0006] By adopting the above technical solution, the functional nanoparticles of metal oxide modified with silane coupling agent are added together with silicon source precursors and catalysts into a mixed solvent. The nanoparticles and precursors are combined in situ using pulsed ultrasonic hydrolysis. At the same time, the surface activity of the substrate is optimized by Ar / O2 mixed gas plasma pretreatment, and bubble defects in the wet film are further eliminated by high-frequency ultrasonic debubbling. Then, N2 / O2 mixed gas low-temperature plasma curing is used to ensure uniform cross-linking of the film layer. Continuous processing is achieved by roll-to-roll unit. Therefore, the film layer has a uniform refractive index distribution and a reduced reflectivity fluctuation range. This solves the problem of uneven refractive index distribution and large reflectivity fluctuation range in the existing chemical preparation of AR antireflective films, which affects the stability of optical performance.

[0007] Preferably, in the pretreatment step, the substrate is a PI substrate with a thickness of 50~100μm or a glass substrate with a thickness of 1~3mm, and the vacuum degree of the plasma treatment is 1×10⁻⁶. -2 ~1×10 0 The treatment process involves a pressure of Pa, a total gas flow rate of 100-200 sccm, a power of 80-100 W, a treatment time of 10-15 s, and a surface hydroxyl density of the treated material ≥ 1.2 × 10⁻⁶. 15 pcs / cm 2 The contact angle is ≤30°.

[0008] By adopting the above technical solution, the substrate and plasma treatment work synergistically to control the cleanliness of the substrate surface, increase the surface hydroxyl density and reduce the contact angle, providing sufficient anchoring points for the subsequent interfacial bonding between the dispersion and the substrate, while ensuring that the substrate does not deform or get damaged during the treatment process.

[0009] Preferably, in the hydrolysis step, the silicon source precursor is tetraethyl orthosilicate with a concentration of 0.3~0.5 mol / L, the catalyst is citric acid with a final concentration of 0.05 mol / L, the temperature of the mixed solvent is 30~35℃, the stirring speed is 200~300 r / min, the stirring time is 10~15 min, and the functional nanoparticles are KH560 modified TiO2 with a particle size of 8~12 nm, an epoxy group grafting rate of 90%~95%, and an addition amount of 5%~10% of the total mass of the dispersion.

[0010] By adopting the above technical solution, the matching of tetraethyl orthosilicate, citric acid catalytic system and mixed solvent provides a stable reaction environment for in-situ hydrolysis. At the same time, the KH560 modified TiO2 nanoparticles of a specific particle size have excellent compatibility with the precursor, which not only ensures that the refractive index of the film meets the anti-reflection requirements, but also promotes the uniform combination of nanoparticles and precursor.

[0011] Preferably, in the hydrolysis step, the frequency of the pulsed ultrasound is 20~40kHz, the working cycle is (4~6)s / (1~3)s, the power is 40~60W, the ultrasonic hydrolysis time is 30~40min, the particle size variation coefficient of the dispersion is ≤15%, and the viscosity at 25℃ is 15~20mPa·s.

[0012] By adopting the above technical solution, the synergistic effect of pulsed ultrasound and hydrolysis can not only efficiently disperse the micro-agglomerates that may be formed by nanoparticles, but also avoid premature cross-linking of precursors caused by excessive ultrasound. At the same time, the particle size variation coefficient and viscosity of the dispersion are controlled to ensure the fluidity and uniformity of the dispersion in the subsequent coating process, thus providing a prerequisite for forming a film with consistent thickness and uniform refractive index.

[0013] Preferably, in the dip-coating defoaming step, the continuous dip-coating temperature is 25~30℃, the substrate immersion depth is 3~5cm, the immersion time is 3~5s, the lifting speed is 5~10mm / min, and the thickness of the wet film is 50~80μm.

[0014] By adopting the above technical solution, the wet film thickness and its uniformity are controlled by the synergy of dipping temperature, immersion depth, soaking time and lifting speed. At the same time, the appropriate wet film thickness provides sufficient space for the cross-linking reaction in the subsequent curing process, ensuring the structural integrity and optical performance stability of the cured film layer.

[0015] Preferably, in the dip-coating defoaming step, the frequency of the high-frequency ultrasound is 90~110kHz, the power is 25~35W, the distance between the ultrasound probe and the substrate is 5~8mm, the defoaming time is 5~10s, and the removal rate of microbubbles ≤50nm after defoaming is ≥99%.

[0016] By adopting the above technical solution, the high-frequency ultrasound, probe distance, and debubbling time work together to remove tiny air bubbles that are difficult to detect with the naked eye in the wet film, avoiding the formation of pores or light transmission defects in the cured film layer due to residual air bubbles, thus improving the density and optical uniformity of the film layer. At the same time, the gentle ultrasound parameters will not damage the structure of the wet film, ensuring the smoothness of the film layer surface.

[0017] Preferably, in the mixing and curing step, the vacuum degree of the plasma curing is 1×10⁻⁶. -1 ~5×10 -1The curing conditions are as follows: Pa, total gas flow rate 150~250 sccm, plasma power 50~80 W, curing time 30~60 s, and Si-O-Si bond crosslinking density of the cured material ≥2.5×10⁻⁶. 22 pcs / cm 3 The gelation rate is ≥95%.

[0018] By adopting the above technical solution and using plasma curing in a low-temperature environment, the Si-O-Si bonds in the film layer are fully cross-linked while avoiding thermal deformation of the substrate, thereby increasing the gelation rate and cross-linking density of the film layer and enhancing its mechanical strength, density and environmental stability.

[0019] Preferably, in the irradiation sealing step, the power of the ultraviolet light irradiation is 15~25W, the irradiation distance is 10~15cm, the irradiation time is 5~10min, the temperature during irradiation is ≤30℃, the relative humidity is ≤50%, and the ring-opening rate of the epoxy groups on the surface of the nanoparticles of the cured material after irradiation is ≥90%.

[0020] By adopting the above technical solution and using UV irradiation parameters in conjunction with ambient temperature and humidity, the cross-linking structure of the film layer can be further strengthened, and the epoxy groups on the surface of nanoparticles can be efficiently activated, thereby achieving synergy between the core function of anti-reflection and the additional functions of nanoparticles.

[0021] Preferably, in the irradiation sealing step, the winding tension of the continuous winding is 15~25N, the unwinding tension is 10~20N, and the packaging is sealed with polyethylene film and contains silica gel desiccant.

[0022] By adopting the above technical solutions, the film layer is prevented from stretching, wrinkling or interlayer adhesion during the winding process by controlling the winding tension and unwinding tension, thus ensuring the flatness and structural integrity of the finished film layer. The combination of sealed packaging and silica gel desiccant can effectively isolate external moisture and pollutants, prevent the film layer from absorbing moisture or being contaminated with impurities during storage and transportation, and maintain the stability of the film layer performance.

[0023] Preferably, in the irradiation sealing step, the storage temperature is 15~25℃ and the relative humidity is ≤40%.

[0024] By adopting the above technical solutions and using specific storage temperature and humidity conditions, the aging, moisture absorption, or performance degradation of the film layer can be inhibited, the core optical performance and mechanical stability of the film layer can be maintained for a long time, and the product shelf life can be extended.

[0025] In summary, this application has the following beneficial effects: 1. Because this application adds silane coupling agent-modified metal oxide functional nanoparticles, silicon source precursors, and catalysts to a mixed solvent, and uses pulsed ultrasonic hydrolysis to achieve in-situ bonding between nanoparticles and precursors, while optimizing substrate surface activity through Ar / O2 mixed gas plasma pretreatment, further eliminating bubble defects in the wet film through high-frequency ultrasonic debubbling, and ensuring uniform cross-linking of the film layer through N2 / O2 mixed gas low-temperature plasma curing, and achieving continuous processing through a roll-to-roll unit, the effect of uniform refractive index distribution and reduced reflectivity fluctuation is achieved. This solves the problem of uneven refractive index distribution and large reflectivity fluctuation in existing AR antireflective film chemical preparation, which affects the stability of optical performance.

[0026] 2. This application replaces traditional high-temperature curing with low-temperature plasma curing, and with the synergistic effect of N2 / O2 mixed gas, it avoids thermal deformation of the substrate and promotes full cross-linking of the film layer, enhancing the mechanical strength and bending resistance of the film layer, thus achieving a dual guarantee of flexible substrate adaptation and film layer structural stability.

[0027] 3. This application achieves anti-reflection function and additional functions simultaneously in a single film layer by combining KH560 modified functional nanoparticles with UV post-treatment. This eliminates the need for multi-step coating, avoids interlayer stress mismatch, and broadens the product's adaptability to different scenarios. Attached Figure Description

[0028] Figure 1 This is a flowchart of the chemical preparation process of the AR antireflective film doped with functional nanoparticles provided in this application. Detailed Implementation

[0029] The present application will be further described in detail below with reference to the accompanying drawings and embodiments.

[0030] Technical Concept: As a core component of optical and electronic devices, the performance of AR antireflective films directly affects the overall effect of the devices. Traditional AR antireflective film preparation processes using functional nanoparticles often involve pre-preparing nanoparticles and then mixing them with the film precursor. However, the surface properties of the nanoparticles are not sufficiently compatible with the precursor, making them prone to aggregation and difficult to disperse uniformly. This results in uneven refractive index distribution and poor optical performance stability.

[0031] To address this issue, this application incorporates silane coupling agent-modified metal oxide functional nanoparticles and silicon-based precursor catalysts into a mixed solvent. Pulsed ultrasonic hydrolysis enables in-situ bonding between the nanoparticles and the precursor, suppressing agglomeration at its source. A specific ratio of mixed gas plasma is used to pretreat the substrate, enhancing surface activity and providing favorable conditions for interfacial bonding. Combined with a low-temperature plasma curing process, substrate deformation is avoided while promoting full cross-linking of the film. High-frequency ultrasonic defoaming eliminates wet film defects, and UV post-treatment enhances functional activation. The entire process is integrated into a roll-to-roll unit for continuous production, simplifying process steps while ensuring stable performance. This successfully constructs a preparation process that balances optical performance, mechanical stability, and the demands of large-scale production.

[0032] Unless otherwise specified, all experimental methods used below are conventional methods. All materials, reagents, methods, and instruments used, unless otherwise specified, are conventional materials, reagents, methods, and instruments in this field, which can be obtained commercially or prepared according to literature methods by those skilled in the art.

[0033] To better understand the above technical solutions, the technical solutions of the present invention will be clearly and completely described below in conjunction with embodiments.

[0034] The following is a further description with reference to the embodiments: Example 1: The chemical preparation process of AR antireflective film doped with functional nanoparticles includes the following steps: Pretreatment: After the substrate is fixed by a roll-to-roll unit, an Ar / O2 mixed gas with a volume ratio of 3:1 is introduced to perform plasma treatment at a substrate transport speed of 7.5 mm / min to obtain the treated material; Hydrolysis preparation: Anhydrous ethanol and deionized water were mixed in a volume ratio of 4:1 to form a mixed solvent. After adding silicon source precursor and catalyst, silane coupling agent modified metal oxide functional nanoparticles were added. After pulse ultrasonic hydrolysis, a dispersion was obtained. Dip-coating defoaming: After the treated material is continuously dip-coated through a dispersion to form a wet film, it is defoamed by high-frequency ultrasound to obtain the coated material; Hybrid curing: A N2 / O2 mixed gas with a volume ratio of 4:1 is introduced into the roll-to-roll unit to perform plasma curing of the coating material at a curing temperature of 70°C to obtain a cured material; Irradiation and sealing: After irradiating the cured material with ultraviolet light at a wavelength of 250nm, it is continuously wound up, sealed and packaged, and stored in a dry and light-proof environment to complete the preparation.

[0035] In the pretreatment step, the substrate is a 75μm thick PI substrate or a 2mm thick glass substrate, and the vacuum degree of the plasma treatment is 1×10⁻⁶. -1Pa, total gas flow rate 150 sccm, power 90 W, treatment time 12.5 s, surface hydroxyl density of the treated material ≥ 1.2 × 10⁻⁶ 15 pcs / cm 2 The contact angle is ≤30°.

[0036] In the hydrolysis step, the silicon source precursor was tetraethyl orthosilicate with a concentration of 0.4 mol / L, the catalyst was citric acid with a final concentration of 0.05 mol / L, the temperature of the mixed solvent was 32.5℃, the stirring speed was 250 r / min, the stirring time was 12.5 min, and the functional nanoparticles were KH560 modified TiO2 with a particle size of 10 nm, an epoxy group grafting rate of 92.5%, and an addition amount of 7.5% of the total mass of the dispersion.

[0037] In the hydrolysis step, the frequency of pulsed ultrasound is 30kHz, the working cycle is (5)s / (2)s, the power is 50W, the ultrasonic hydrolysis time is 35min, the particle size variation coefficient of the dispersion is ≤15%, and the viscosity at 25℃ is 17.5mPa·s.

[0038] In the dip-coating defoaming step, the continuous dip-coating temperature was 27.5℃, the substrate immersion depth was 4cm, the immersion time was 4s, the lifting speed was 7.5mm / min, and the wet film thickness was 65μm.

[0039] In the defoaming step, the frequency of high-frequency ultrasound is 100kHz, the power is 30W, the distance between the ultrasound probe and the substrate is 6.5mm, the defoaming time is 7.5s, and the removal rate of microbubbles ≤50nm after defoaming is ≥99%.

[0040] In the mixed curing step, the vacuum degree of plasma curing is 2.5 × 10⁻⁶. -1 Pa, total gas flow rate 200 sccm, plasma power 65 W, curing time 450 s, Si-O-Si bond crosslinking density of the cured material ≥ 2.5 × 10⁻⁶ 22 pcs / cm 3 The gelation rate is ≥95%.

[0041] In the irradiation sealing step, the power of ultraviolet light irradiation is 20W, the irradiation distance is 12.5cm, the irradiation time is 7.5min, the temperature during irradiation is ≤30℃, the relative humidity is ≤50%, and the ring-opening rate of epoxy groups on the surface of nanoparticles of the cured material after irradiation is ≥90%.

[0042] During the irradiation sealing process, the continuous winding tension is 20N, the unwinding tension is 15N, and the packaging uses polyethylene film for sealing with built-in silica gel desiccant.

[0043] During the irradiation sealing process, the storage temperature is 20℃ and the relative humidity is ≤40%.

[0044] Example 2: The difference between this embodiment and Embodiment 1 above is that: The chemical preparation process of AR antireflective film doped with functional nanoparticles includes the following steps: Pretreatment: After the substrate is fixed by a roll-to-roll unit, a mixture of Ar / O2 gas with a volume ratio of 4:1 is introduced to perform plasma treatment at a substrate transport speed of 10 mm / min to obtain the treated material. Hydrolysis preparation: Anhydrous ethanol and deionized water were mixed in a volume ratio of 5:1 to form a mixed solvent. After adding silicon source precursor and catalyst, silane coupling agent modified metal oxide functional nanoparticles were added. After pulse ultrasonic hydrolysis, a dispersion was obtained. Dip-coating defoaming: After the treated material is continuously dip-coated through a dispersion to form a wet film, it is defoamed by high-frequency ultrasound to obtain the coated material; Mixed curing: A N2 / O2 mixed gas with a volume ratio of 5:1 is introduced into the roll-to-roll unit to perform plasma curing of the coating material at a curing temperature of 90℃, thereby obtaining a cured material; Irradiation and sealing: After irradiating the cured material with ultraviolet light at a wavelength of 260nm, it is continuously wound up, sealed and packaged, and stored in a dry and light-proof environment to complete the preparation.

[0045] Example 3: The difference between this embodiment and Embodiment 1 above is that: The chemical preparation process of AR antireflective film doped with functional nanoparticles includes the following steps: Pretreatment: After the substrate is fixed by a roll-to-roll unit, a mixed gas of Ar / O2 with a volume ratio of 2:1 is introduced to perform plasma treatment at a substrate transport speed of 5 mm / min to obtain the treated material; Hydrolysis preparation: Anhydrous ethanol and deionized water were mixed in a volume ratio of 3:1 to form a mixed solvent. After adding silicon source precursor and catalyst, silane coupling agent modified metal oxide functional nanoparticles were added. After pulse ultrasonic hydrolysis, a dispersion was obtained. Dip-coating defoaming: After the treated material is continuously dip-coated through a dispersion to form a wet film, it is defoamed by high-frequency ultrasound to obtain the coated material; Hybrid curing: A N2 / O2 mixed gas with a volume ratio of 3:1 is introduced into the roll-to-roll unit to perform plasma curing of the coating material at a curing temperature of 50°C to obtain a cured material; Irradiation and sealing: After irradiating the cured material with ultraviolet light of 240nm wavelength, it is continuously wound up, sealed and packaged, and stored in a dry and light-proof environment to complete the preparation.

[0046] Example 4: The difference between this embodiment and Embodiment 1 above is that: In the hydrolysis step, the frequency of pulsed ultrasound is 40kHz, the working cycle is 6s / 3s, the power is 60W, and the ultrasonic hydrolysis time is 40min. In the defoaming step of the dip coating, the frequency of the high-frequency ultrasound is 110kHz, the power is 35W, and the defoaming time is 10s. In the mixed curing step, the N2 / O2 volume ratio is 5:1, the curing temperature is 80℃, and the curing time is 60s.

[0047] The remaining steps are the same as in Example 1.

[0048] Example 5: The difference between this embodiment and Embodiment 1 above is that: In the mixed curing step, the curing temperature is 50℃, the plasma power is 80W, and the curing time is 30s; During the irradiation sealing process, the ultraviolet light power was 25W, the irradiation distance was 10cm, and the irradiation time was 10min. In the hydrolysis step, the amount of functional nanoparticles added is 10% of the total mass of the dispersion.

[0049] The remaining steps are the same as in Example 1.

[0050] Comparative Example 1: Pretreatment: Ar gas plasma cleaning was used, with a gas flow rate of 150 sccm, a power of 90W, and a treatment time of 12.5s; Dispersion preparation: TiO2 nanoparticles (10 nm in diameter) were first prepared by hydrothermal method, and then mixed with TEOS hydrolysate (0.4 mol / L concentration), and polycarboxylate dispersant (0.5% by mass fraction) was added. The mixture was then dispersed by conventional ultrasonication (20 kHz, 30 min). Coating and curing: After dip coating, cure at 350℃ for 60 minutes; Post-processing: No UV irradiation, directly rolled up and packaged.

[0051] Comparative Example 2: The difference between this comparative example and Example 1 is that: Without any pretreatment step, the substrate was directly subjected to ultrasonic cleaning with ethanol (40kHz, 10min) before entering the dip coating process; the remaining steps were the same as in Example 1.

[0052] Comparative Example 3: The difference between this comparative example and Example 1 is that: In the hydrolysis step, a pre-prepared TiO2 nanoparticle + post-mixing mode was adopted, without pulsed ultrasonic hydrolysis, and only by stirring and dispersing at 250 r / min for 30 min; the remaining steps were the same as in Example 1.

[0053] Comparative Example 4: The difference between this comparative example and Example 1 is that: In the mixing and curing step, the N2 / O2 volume ratio is 6:1; the remaining steps are the same as in Example 1.

[0054] Performance testing: Reflectivity: The average reflectivity in the visible light band (400~800nm) was measured using a spectrophotometer; Transmittance: The average transmittance in the visible light band (400~800nm) was measured using a spectrophotometer; Film adhesion: Tested according to GB / T 9286-1998 cross-cut test (cross-cut spacing 1mm, tape peeling 3 times), rating standard: 5B (no peeling) ~ 0B (complete peeling); Nanoparticle aggregation rate: The percentage of aggregated particles (particle size > 50 nm) in 100 fields of view was determined by transmission electron microscopy (TEM). Bending resistance: For PI substrates, bend repeatedly with a radius of curvature of 2mm, and record the number of bends at which the film layer first peels off; Membrane porosity: The membrane porosity was determined using the nitrogen adsorption-desorption method.

[0055] Table 1 ; As can be seen from Examples 1 to 5 and Comparative Example 1, and in conjunction with Table 1, the in-situ hydrolysis and pulsed ultrasound dispersion method combined with the low-temperature plasma curing process adopted in this application, compared with the traditional process of pre-preparing nanoparticles, mixing, and then high-temperature curing, can effectively improve the dispersion state of nanoparticles in the film layer, promote uniform cross-linking of the film layer, and thus simultaneously optimize the optical and mechanical properties of the film layer. Through the synergy of each step, agglomeration is reduced, while avoiding the adverse effects of high temperature on the substrate and film layer structure.

[0056] As can be seen from Example 1 and Comparative Example 2, and Table 1, the surface activity of the substrate is enhanced after plasma treatment with mixed gas, which provides more favorable conditions for the bonding between the dispersion and the substrate, thereby strengthening the bonding force between the film and the substrate and improving the mechanical stability of the film.

[0057] Combining Example 1 and Comparative Example 3 with Table 1, it can be seen that the pulsed ultrasound treatment in the hydrolysis step can ensure the uniform dispersion of nanoparticles. The pulsed ultrasound can break up any micro-agglomerations that may form in the nanoparticles, and at the same time, it works in synergy with the in-situ hydrolysis process to promote the full binding of nanoparticles and precursors.

[0058] As can be seen from Example 1 and Comparative Example 4, and Table 1, the ratio of N2 / O2 mixed gas in the curing step can work in synergy with parameters such as curing temperature and power to promote the full cross-linking of chemical bonds in the film layer, and ensure the compactness and mechanical strength of the film layer.

[0059] As can be seen from Examples 1 to 5 and Table 1, different parameter combinations in this application can all produce high-performance AR antireflective films. Through the synergy of each process step, the film layer can maintain a good level in terms of optical performance and mechanical stability, which can meet the needs of large-scale production.

[0060] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A chemical preparation process for AR antireflective films doped with functional nanoparticles, characterized in that, Includes the following steps: Pretreatment: After the substrate is fixed by a roll-to-roll unit, an Ar / O2 mixed gas with a volume ratio of 2~4:1 is introduced to perform plasma treatment at a substrate transport speed of 5~10mm / min to obtain the treated material; Hydrolysis preparation: Anhydrous ethanol and deionized water are mixed in a volume ratio of 3~5:1 to form a mixed solvent. After adding silicon source precursor and catalyst, silane coupling agent modified metal oxide functional nanoparticles are added. After pulse ultrasonic hydrolysis, a dispersion is obtained. Dip-coating defoaming: After the treated material is continuously dip-coated through a dispersion to form a wet film, it is defoamed by high-frequency ultrasound to obtain the coated material; Mixed curing: A N2 / O2 mixed gas with a volume ratio of 3~5:1 is introduced into the roll-to-roll unit to perform plasma curing of the coating material at a curing temperature of 50~90℃ to obtain a cured material; Irradiation and sealing: After irradiating the cured material with ultraviolet light with a wavelength of 240~260nm, it is continuously wound up, sealed and packaged, and stored in a dry and light-proof environment to complete the preparation. In the pretreatment step, the substrate is a PI substrate with a thickness of 50~100μm or a glass substrate with a thickness of 1~3mm, and the vacuum degree of the plasma treatment is 1×10⁻⁶. -2 ~1×10 0 The treatment process involves a pressure of Pa, a total gas flow rate of 100-200 sccm, a power of 80-100 W, a treatment time of 10-15 s, and a surface hydroxyl density of the treated material ≥ 1.2 × 10⁻⁶. 15 pcs / cm 2 Contact angle ≤ 30°; In the hydrolysis step, the silicon source precursor is tetraethyl orthosilicate with a concentration of 0.3~0.5 mol / L, the catalyst is citric acid with a final concentration of 0.05 mol / L, the temperature of the mixed solvent is 30~35℃, the stirring speed is 200~300 r / min, the stirring time is 10~15 min, and the functional nanoparticles are KH560 modified TiO2 with a particle size of 8~12 nm, an epoxy group grafting rate of 90%~95%, and an addition amount of 5%~10% of the total mass of the dispersion. In the hydrolysis step, the frequency of the pulsed ultrasound is 20~40kHz, the working cycle is (4~6)s / (1~3)s, the power is 40~60W, the ultrasonic hydrolysis time is 30~40min, the particle size variation coefficient of the dispersion is ≤15%, and the viscosity at 25℃ is 15~20mPa・s. In the dip-coating defoaming step, the continuous dip-coating temperature is 25~30℃, the substrate immersion depth is 3~5cm, the immersion time is 3~5s, the lifting speed is 5~10mm / min, and the thickness of the wet film is 50~80μm. In the dip-coating defoaming step, the frequency of the high-frequency ultrasound is 90~110kHz, the power is 25~35W, the distance between the ultrasound probe and the substrate is 5~8mm, the defoaming time is 5~10s, and the removal rate of microbubbles ≤50nm after defoaming is ≥99%; In the hybrid curing step, the vacuum degree of the plasma curing is 1×10⁻⁶. -1 ~5×10 -1 The curing conditions are as follows: Pa, total gas flow rate 150~250 sccm, plasma power 50~80 W, curing time 30~60 s, and Si-O-Si bond crosslinking density of the cured material ≥2.5×10⁻⁶. 22 pcs / cm 3 gelation rate ≥95%; In the irradiation sealing step, the power of the ultraviolet light irradiation is 15~25W, the irradiation distance is 10~15cm, the irradiation time is 5~10min, the temperature during irradiation is ≤30℃, the relative humidity is ≤50%, and the ring-opening rate of the epoxy groups on the surface of the nanoparticles of the cured material after irradiation is ≥90%.

2. The chemical preparation process of the AR antireflective film doped with functional nanoparticles according to claim 1, characterized in that: In the irradiation sealing step, the winding tension of the continuous winding is 15~25N, the unwinding tension is 10~20N, and the packaging is sealed with polyethylene film and contains silica gel desiccant.

3. The chemical preparation process of the AR antireflective film doped with functional nanoparticles according to claim 1, characterized in that: During the irradiation sealing step, the storage temperature is 15~25℃ and the relative humidity is ≤40%.

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