Azp plastic evaporation coating surface process
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YIHAOJIE OPTICS(SUZHOU) CO LTD
- Filing Date
- 2026-03-18
- Publication Date
- 2026-06-26
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of plastic surface coating technology, specifically to the AZP plastic evaporation coating surface process. Background Technology
[0002] On the surface of transparent optical resins such as AZP (acrylic resin) and PMMA (polymethyl methacrylate), metal layers (such as aluminum, silver, gold, chromium, etc.) are deposited using conventional coating processes (such as thermal evaporation, electron beam evaporation, magnetron sputtering, etc.). However, due to the inherent characteristics of these resins, such as low surface energy (insufficient wettability), chemical inertness (inability to form chemical bonds), poor thermal stability, and mismatched coefficients of thermal expansion (resulting in huge interfacial tensile stress during cooling), the film layer suffers from problems such as poor adhesion, easy cracking or peeling, making it difficult to meet the stable adhesion required for industrial applications.
[0003] Therefore, how to develop a suitable coating process for AZP surfaces to obtain a film with strong adhesion requires further exploration. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides an AZP plastic evaporation coating surface process.
[0005] The objective of this invention can be achieved through the following technical solutions: The AZP plastic evaporation coating surface process includes the following steps: Step (1): After hot pressing the AZP optical resin, cool it to room temperature to obtain a base film layer; immerse the base film layer in isopropanol, disperse it ultrasonically, dry it under vacuum, and then treat it with argon plasma to obtain a pretreated base film layer. Step (2): Place the pretreated substrate film in the evaporation coating machine, control the temperature and initial vacuum of the pretreated substrate film, place the film material s in the tungsten boat, close the baffle, turn on the power to heat and increase the evaporation current, remove the baffle, control the evaporation vacuum, deposit, anneal, and cool with the furnace to obtain the first film layer. Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat, start the ion source, apply bias voltage to bombard the first film layer, then adjust the electron beam power, turn on ion plating, deposit, anneal, cool with the furnace, and obtain the Ti3O5 film layer. Step (4): Maintain vacuum, turn off electron beam, turn on RF power supply and gas flow controller, use high-purity titanium as target material, introduce mixed gas, set sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum level, place the high-purity SiO2 in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen, adjust the ion beam energy and beam current density, deposit, anneal for 1-2 hours, cool with the furnace to form a SiO2 film layer, thus completing the AZP plastic evaporation coating surface process.
[0006] The AZP plastic evaporation coating surface process includes the following specific steps: Step (1): Hot-press AZP optical resin for 40-45 min, cool to room temperature to obtain a base film layer; immerse the base film layer in isopropanol, ultrasonically disperse for 5-10 min, vacuum dry for 2-4 h, and then treat with argon plasma for 5-10 min to obtain a pretreated base film layer. Furthermore, the hot pressing is performed at a temperature of 130-135℃ and a pressure of 8-12MPa; the cooling rate is 0.5-0.7℃ / min; and the thickness of the base film is 0.8-1.2mm. Furthermore, the ultrasonic dispersion power is 200-300W and the frequency is 20-30kHz; the vacuum drying temperature is 60-80℃; and the argon plasma treatment pressure is 10-15Pa and the power is 150-200W. Step (2): Place the pretreated substrate film in the evaporation coating machine, control the temperature and initial vacuum of the pretreated substrate film, place the film material s in the tungsten boat, close the baffle, turn on the power to heat and increase the evaporation current, maintain for 5-10 minutes, remove the baffle, control the evaporation vacuum, deposit, anneal for 1-2 hours, cool with the furnace, and obtain the first film layer. Furthermore, the temperature of the pretreated substrate film is controlled at 35-40℃; the initial vacuum degree is ≤2.5×10⁻⁶. -3 Pa; membrane material S is SiO or MgF2; increase the evaporation current to 540-560 mA; evaporation vacuum degree is 1.8 × 10⁻⁶. -2 Pa-2.0×10 -2 Pa; deposition rate of 0.3-0.5 nm / s; annealing temperature of 70-75℃; thickness of the first film layer of 30-40 nm; Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas for 10-12s, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat for 5-10min, start the ion source, apply bias voltage to bombard the first film layer for 15-20s, then adjust the electron beam power, turn on ion plating, deposit, anneal for 1-2h, cool with the furnace, and obtain the Ti3O5 film layer; Furthermore, the rate at which the anti-evaporation current decreases to zero is 10-20 mA / min; the flow rate of argon gas is 5-10 sccm; the electron beam power during preheating is 1-2 kW; the volume ratio of argon to oxygen in the ion source is 95:5; the bias voltage is 300-310 V; and the power of the electron beam is adjusted to 4-6 kW. Furthermore, the conditions for ion plating are: bias voltage of 100-150V and ion current density of 0.1-0.3mA / cm². 2 The deposition rate is 0.1-0.3 nm / s, and the vacuum degree during deposition is ≤5×10⁻⁶. -4 Pa; annealing temperature is 75-80℃; thickness of Ti3O5 film is 40-50nm; Step (4): Maintain vacuum, turn off electron beam, turn on RF power supply and gas flow controller, use high-purity titanium as target material, introduce mixed gas, set sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; Furthermore, maintain a vacuum level ≤ 5 × 10⁻⁶. -4 Pa, sputtering power of 200-300W, substrate bias voltage of -120V to -80V, and working gas pressure of 0.5-1.0Pa; Furthermore, during the deposition process, the mixed gas includes Ar, N2, and O2, with an Ar flow rate of 35-45 sccm and a ratio of Ar flow rate to total N2 and O2 flow rate of 7-8:2-3. The N2 and O2 flow rate ratio is adjusted sequentially from 1:2 to 1:4, 1:6, 1:8, and 1:10, with the N2 and O2 flow rate ratio adjusted every 3-5 nm of deposition, resulting in a deposition rate of 0.05-0.1 nm / s. TiO2 x N y The thickness of the transition film is 15-25 nm; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum, place the high-purity SiO2 in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen, adjust the ion beam energy and beam current density, deposit, anneal for 1-2 hours, cool with the furnace to form a SiO2 film layer, thus completing the AZP plastic evaporation coating surface process. Furthermore, maintain a vacuum level ≤ 5 × 10⁻⁶. -4 Pa; preheat to evaporation temperature of 1650-1750℃; evaporation rate of 0.05-0.1 nm / s; pure oxygen flow rate of 8-12 sccm; Furthermore, the ion beam energy is 80-120 eV, the beam current density is 2-4 mA / cm², the deposition rate is 0.08-0.15 nm / s, the annealing temperature is 80-85℃, and the SiO₂ film thickness is 40-50 nm.
[0007] This invention discloses an AZP plastic evaporation coating surface process. The process involves hot-pressing AZP optical resin into a base film, washing, drying, and plasma-treating the base film to obtain a pretreated base film; depositing a resistive evaporation coating material S onto the pretreated base film to obtain a first film layer; using the synergistic effect of electron beam evaporation and ion-assisted plating, depositing a Ti3O5 film layer onto the first film layer; and finally, depositing TiO2 onto the Ti3O5 film layer using sputtering deposition technology to obtain TiO2. x N y Transition film layer; finally, through the synergistic effect of electron beam evaporation and ion-coated plating, a transition film layer is formed on TiO2. x N y A SiO2 film is deposited on the transition film layer to complete the AZP plastic evaporation coating surface process.
[0008] The beneficial effects of this invention are: 1. Low-refractive-index SiO or MgF2 film materials are used on the pretreated substrate film layer made of AZP optical resin. SiO not only has low surface energy, but can also form Si-OC bonds with the plasma-treated AZP surface, which significantly enhances its interfacial bonding force. The low surface energy characteristics of MgF2 can reduce the internal stress of the film layer. Using a barrier evaporation coating can reduce the damage of electron beam to AZP resin and avoid softening, carbonization or molecular chain breakage of AZP resin.
[0009] 2. A Ti3O5 film is deposited on the first film layer to avoid directly depositing Ti3O5 on the surface of the pretreated substrate. This avoids severe interfacial stress caused by abrupt changes in thermal mismatch modulus, which could lead to film cracking or peeling. Using a Ti3O5 film layer enables high refractive index optical functions. Then, on the surface of the Ti3O5 film layer, the N2 and O2 flow ratio is controlled by an RF magnetron sputtering process to form a TiO2-like structure that continuously transitions from a TiN-like structure (refractive index approximately 2.4) to a TiO2-like structure (refractive index approximately 1.8). x N y The transition film layer achieves a smooth transition of refractive index, alleviates stress concentration between the Ti3O5 film layer and the SiO2 film layer, and reduces the risk of peeling.
[0010] 3. The first film layer formed by SiO or MgF2 has a low refractive index, stress buffer and enhanced adhesion. Together with the high refractive index core layer formed by Ti3O5 and the low refractive index antireflection protective layer formed by SiO2, it forms a "low-high-low" refractive index gradient. This is not only beneficial for broadband optical antireflection, but also effectively disperses interfacial stress and improves the environmental durability and reliability of the overall film system. Detailed Implementation
[0011] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0012] Example 1 The AZP plastic evaporation coating surface process includes the following specific steps: Step (1): Hot-press AZP optical resin (supplier: Asahi Kasei Corporation) for 40 min, cool to room temperature to obtain a base film layer; immerse the base film layer in 500 mL isopropanol, ultrasonically disperse for 5 min, vacuum dry for 2 h, and then treat with argon plasma for 5 min to obtain a pretreated base film layer; the hot-pressing temperature is 130℃ and the pressure is 8 MPa; the cooling rate is 0.5℃ / min; the thickness of the base film layer is 0.8 mm; the ultrasonic dispersion power is 200 W and the frequency is 20 kHz; the vacuum drying temperature is 60℃; the argon plasma treatment pressure is 10 Pa and the power is 150 W; Step (2): Place the pretreated substrate film in an evaporation coating machine (supplier: Optical Coating Machine for Plastic Substrates, Guangchi Technology (Shanghai) Co., Ltd.), control the temperature and initial vacuum of the pretreated substrate film, place the film material s in a tungsten boat, close the baffle, apply electricity to heat and increase the resistance current, maintain for 5 minutes, remove the baffle, control the resistance vacuum, deposit, anneal for 1 hour, and cool with the furnace to obtain the first film layer; control the temperature of the pretreated substrate film layer to be 35℃; the initial vacuum degree is 2.5×10 - 3 Pa; membrane material s is SiO; resistance current increased to 540mA; resistance vacuum degree is 1.8×10 -2 Pa; deposition rate of 0.3 nm / s; annealing temperature of 70 °C; thickness of the first film layer of 30 nm; Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas for 10s, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat for 5min, start the ion source, apply a bias voltage to bombard the first film layer for 15s, then adjust the electron beam power, turn on ion plating, deposit, anneal for 1h, and cool with the furnace to obtain the Ti3O5 film layer; the rate at which the evaporation current decreases to zero is 10mA / min; the flow rate of introduced argon gas is 5sccm; the electron beam power during preheating is 1kW; the volume ratio of argon to oxygen in the ion source is 95:5; the bias voltage is 300V; the electron beam power is adjusted to 4kW; the conditions for ion plating are: bias voltage of 100V and ion current density of 0.1mA / cm.2 The deposition rate was 0.1 nm / s; the vacuum level during deposition was 5 × 10⁻⁶. -4 Pa; annealing temperature is 75℃; thickness of Ti3O5 film is 40nm; Step (4): Maintain vacuum, turn off the electron beam, turn on the RF power supply and gas flow controller, use a high-purity titanium target (supplier: Baoji Yingzhibo Metal Materials Co., Ltd., circular target specification 60) as the target material, introduce mixed gas, set the sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; maintain vacuum level of 5×10 -4 The sputtering power was 200W, the substrate bias was -120V, and the working gas pressure was 0.5Pa. During deposition, the mixed gas included Ar, N2, and O2, with an Ar flow rate of 35 sccm and a ratio of Ar flow rate to total N2 and O2 flow rate of 7:3. The N2 and O2 flow rate ratio was adjusted sequentially from 1:2 to 1:4, 1:6, 1:8, and 1:10, with the N2 and O2 flow rate ratio adjusted every 3 nm of deposition. The deposition rate was 0.05 nm / s. TiO2 x N y The thickness of the transition film is 15 nm; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum level, place high-purity SiO2 (supplier: Tim (Beijing) New Material Technology Co., Ltd., 200 mesh) in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen (supplier: Qingdao Xin'en Gas Co., Ltd., 10L), adjust the ion beam energy and beam current density, deposit, anneal for 1 hour, cool with the furnace to form a SiO2 film layer, thus completing the AZP plastic evaporation coating surface process; maintain the vacuum level at 5×10 -4 Pa; preheating to evaporation temperature of 1650℃; evaporation rate of 0.05nm / s; pure oxygen flow rate of 8sccm; ion beam energy of 80eV and beam current density of 2mA / cm²; deposition rate of 0.08nm / s; annealing temperature of 80℃; SiO2 film thickness of 40nm.
[0013] Example 2 The AZP plastic evaporation coating surface process includes the following specific steps: Step (1): Hot-press AZP optical resin (supplier: Asahi Kasei Corporation) for 43 min, cool to room temperature to obtain a base film layer; immerse the base film layer in 500 mL isopropanol, ultrasonically disperse for 8 min, vacuum dry for 3 h, and then treat with argon plasma for 8 min to obtain a pretreated base film layer; the hot-pressing temperature is 133℃ and the pressure is 10 MPa; the cooling rate is 0.6℃ / min; the thickness of the base film layer is 1.0 mm; the ultrasonic dispersion power is 250 W and the frequency is 25 kHz; the vacuum drying temperature is 70℃; the argon plasma treatment pressure is 13 Pa and the power is 180 W; Step (2): Place the pretreated substrate film in an evaporation coating machine (supplier: Optical Coating Machine for Plastic Substrates, Guangchi Technology (Shanghai) Co., Ltd.), control the temperature and initial vacuum of the pretreated substrate film, place the film material s in a tungsten boat, close the baffle, apply electricity to increase the resistance current, maintain for 8 minutes, remove the baffle, control the resistance vacuum, deposit, anneal for 1.5 hours, and cool with the furnace to obtain the first film layer; control the temperature of the pretreated substrate film layer to be 37℃; the initial vacuum degree is 2.5×10 -3 Pa; membrane material S is MgF2; the evaporation current is increased to 550mA; the evaporation vacuum degree is 1.9×10 -2 Pa; deposition rate of 0.4 nm / s; annealing temperature of 73 °C; thickness of the first film layer of 35 nm; Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas for 11s, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat for 8min, start the ion source, apply a bias voltage to bombard the first film layer for 17s, then adjust the electron beam power, turn on ion plating, deposit, anneal for 1.5h, and cool with the furnace to obtain the Ti3O5 film layer; the rate at which the evaporation current decreases to zero is 15mA / min; the flow rate of introduced argon gas is 8sccm; the electron beam power during preheating is 1.5kW; the volume ratio of argon to oxygen in the ion source is 95:5; the bias voltage is 305V; the electron beam power is adjusted to 5kW; the conditions for ion plating are: bias voltage of 130V and ion current density of 0.2mA / cm. 2 The deposition rate was 0.2 nm / s; the vacuum level during deposition was 5 × 10⁻⁶. -4 Pa; annealing temperature was 77℃; thickness of Ti3O5 film was 45nm; Step (4): Maintain vacuum, turn off the electron beam, turn on the RF power supply and gas flow controller, use a high-purity titanium target (supplier: Baoji Yingzhibo Metal Materials Co., Ltd., circular target specification 60) as the target material, introduce mixed gas, set the sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; maintain vacuum level of 5×10 -4The sputtering power was 250W, the substrate bias was -100V, and the working gas pressure was 0.8Pa. During deposition, the mixed gas included Ar, N2, and O2, with an Ar flow rate of 40 sccm and a ratio of Ar flow rate to total N2 and O2 flow rate of 7.5:2.5. The N2 and O2 flow rate ratio was adjusted sequentially from 1:2 to 1:4, 1:6, 1:8, and 1:10, with the N2 and O2 flow rate ratio adjusted every 4 nm of deposition. The deposition rate was 0.08 nm / s. TiO2 x N y The thickness of the transition film is 20 nm; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum level, place high-purity SiO2 (supplier: Tim (Beijing) New Material Technology Co., Ltd., 200 mesh) in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen (supplier: Qingdao Xin'en Gas Co., Ltd., 10L), adjust the ion beam energy and beam current density, deposit, anneal for 1.5 hours, cool with the furnace to form a SiO2 film layer, thus completing the AZP plastic evaporation coating surface process; maintain the vacuum level at 5×10 -4 Pa; preheating to evaporation temperature of 1700℃; evaporation rate of 0.08nm / s; pure oxygen flow rate of 10sccm; ion beam energy of 100eV and beam current density of 3mA / cm²; deposition rate of 0.11nm / s; annealing temperature of 83℃; SiO2 film thickness of 45nm.
[0014] Example 3 The AZP plastic evaporation coating surface process includes the following specific steps: Step (1): Hot-press AZP optical resin (supplier: Asahi Kasei Corporation) for 45 min, cool to room temperature to obtain a base film layer; immerse the base film layer in 500 mL isopropanol, ultrasonically disperse for 10 min, vacuum dry for 4 h, and then treat with argon plasma for 10 min to obtain a pretreated base film layer; the hot-pressing temperature is 135℃ and the pressure is 12 MPa; the cooling rate is 0.7℃ / min; the thickness of the base film layer is 1.2 mm; the ultrasonic dispersion power is 300 W and the frequency is 30 kHz; the vacuum drying temperature is 80℃; the argon plasma treatment pressure is 15 Pa and the power is 200 W; Step (2): Place the pretreated substrate film in an evaporation coating machine (supplier: Optical Coating Machine for Plastic Substrates, Guangchi Technology (Shanghai) Co., Ltd.), control the temperature and initial vacuum of the pretreated substrate film, place the film material s in a tungsten boat, close the baffle, apply electricity to heat and increase the resistance current, maintain for 10 min, remove the baffle, control the resistance vacuum, deposit, anneal for 2 h, cool with the furnace to obtain the first film layer; control the temperature of the pretreated substrate film layer to 40℃; the initial vacuum degree to 2.5×10 -3 Pa; membrane material s is SiO; resistance current increased to 560mA; resistance vacuum degree is 2.0×10 -2 Pa; deposition rate of 0.5 nm / s; annealing temperature of 75 °C; thickness of the first film layer of 40 nm; Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas for 12s, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat for 10min, start the ion source, apply a bias voltage to bombard the first film layer for 20s, then adjust the electron beam power, turn on ion plating, deposit, anneal for 2h, and cool with the furnace to obtain the Ti3O5 film layer; the rate at which the evaporation current decreases to zero is 20mA / min; the flow rate of introduced argon gas is 10sccm; the electron beam power during preheating is 2kW; the volume ratio of argon to oxygen in the ion source is 95:5; the bias voltage is 310V; the electron beam power is adjusted to 6kW; the conditions for ion plating are: bias voltage of 150V and ion current density of 0.3mA / cm. 2 The deposition rate was 0.3 nm / s; the vacuum level during deposition was 5 × 10⁻⁶. -4 Pa; annealing temperature is 80℃; thickness of Ti3O5 film is 50nm; Step (4): Maintain vacuum, turn off the electron beam, turn on the RF power supply and gas flow controller, use a high-purity titanium target (supplier: Baoji Yingzhibo Metal Materials Co., Ltd., circular target specification 60) as the target material, introduce mixed gas, set the sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; maintain vacuum level of 5×10 -4 The sputtering power was 300W, the substrate bias was -80V, and the working gas pressure was 1.0Pa. During deposition, the mixed gas included Ar, N2, and O2, with an Ar flow rate of 45 sccm and a ratio of Ar flow rate to total N2 and O2 flow rate of 8:2. The N2 and O2 flow rate ratio was adjusted sequentially from 1:2 to 1:4, 1:6, 1:8, and 1:10, with the N2 and O2 flow rate ratio adjusted every 5 nm of deposition. The deposition rate was 0.1 nm / s. TiO2 x N y The thickness of the transition film is 25 nm; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum level, place high-purity SiO2 (supplier: Tim (Beijing) New Material Technology Co., Ltd., 200 mesh) in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen (supplier: Qingdao Xin'en Gas Co., Ltd., 10L), adjust the ion beam energy and beam current density, deposit, anneal for 2 hours, cool with the furnace to form a SiO2 film layer, thus completing the AZP plastic evaporation coating surface process; maintain the vacuum level at 5×10 -4 Pa; preheating to evaporation temperature of 1750℃; evaporation rate of 0.1nm / s; pure oxygen flow rate of 12sccm; ion beam energy of 120eV and beam current density of 4mA / cm²; deposition rate of 0.15nm / s; annealing temperature of 85℃; SiO2 film thickness of 50nm.
[0015] Comparative Example 1 Compared with Example 3, the first film layer used in step (3) is replaced with a pre-treated base film layer, and the rest is exactly the same as in Example 3, to complete the AZP plastic evaporation coating surface process.
[0016] Comparative Example 2 Compared with Example 3, TiO x N y The transition film layer was replaced with TiO2 x N y Transition film layer-1, the rest are exactly the same as in Example 3, to complete the AZP plastic evaporation coating surface process; TiO x N y Preparation of transition film-1: Maintaining vacuum, the electron beam was turned off, and the RF power supply and gas flow controller were turned on. A high-purity titanium target (supplier: Baoji Yingzhibo Metal Materials Co., Ltd., circular target specification 60) was used as the target material. A mixed gas was introduced, and the sputtering power, substrate bias voltage, and working gas pressure were set to deposit TiO2. x N y Transition film layer-1; maintain vacuum level of 5×10 -4 The sputtering power was 300W, the substrate bias was -80V, and the working gas pressure was 1.0Pa. During deposition, the mixed gas included Ar, N2, and O2, with an Ar flow rate of 45 sccm and a ratio of Ar flow rate to total N2 and O2 flow rate of 8:2. The N2 and O2 flow rate ratio was adjusted sequentially from 1:1 to 1:3, 1:5, 1:7, and 1:9, with the N2 and O2 flow rate ratio adjusted every 5 nm of deposition. The deposition rate was 0.1 nm / s. TiO2 x N y The thickness of the transition film-1 is 25 nm.
[0017] Comparative Example 3 Compared with Example 3, TiO x N y The transition film layer was replaced with TiO2 x N y Transition film layer-2, the rest are exactly the same as in Example 3, to complete the AZP plastic evaporation coating surface process; TiO x N y Preparation of transition film-2: Maintaining vacuum, the electron beam was turned off, and the RF power supply and gas flow controller were turned on. A high-purity titanium target (supplier: Baoji Yingzhibo Metal Materials Co., Ltd., circular target specification 60) was used as the target material. A mixed gas was introduced, and the sputtering power, substrate bias voltage, and working gas pressure were set to deposit TiO2. x N y Transition film layer-2; maintain vacuum level of 5×10 -4 The sputtering power was 300W, the substrate bias was -80V, and the working gas pressure was 1.0Pa. During deposition, the mixed gas consisted of N2 and O2, with an N2 flow rate of 17 sccm. The N2 to O2 flow ratio was adjusted sequentially from 1:1 to 1:3, 1:5, 1:7, and 1:9, with the N2 to O2 flow ratio adjusted every 5 nm of deposition. The deposition rate was 0.1 nm / s. TiO2 x N y The thickness of the transition film-2 is 25 nm.
[0018] The following is a further performance test of the films obtained by the AZP plastic evaporation coating surface process provided in Examples 1-3 and Comparative Examples 1-3 of the present invention. The test results are shown below.
[0019] Adhesion test: Referring to GB / T 9286-2021, use a cross-cut adhesion tester to draw a 1mm×1mm grid (10 rows × 10 columns) on the film surface (i.e., 100 square grids with a side length of 1mm). Then, use 3M 600 tape to adhere to the grid area, and quickly peel off the tape at a 60° angle. Repeat 5 times, observe the area of film peeling off, and rate it according to 0B-5B; 5B grade: no peeling, the best adhesion; ≥4B grade: acceptable for industrial applications; <2B grade: adhesion unqualified.
[0020] The visible light transmittance of the film sample was tested using a UV-Vis spectrophotometer in the 400-700 nm range. The pretreated substrate film was used as a reference sample. Transmission spectra were collected under vertical incidence conditions. The transmittance difference between the film sample and the reference sample was calculated to obtain the transmittance enhancement of the film. The average transmittance in the 400-700 nm range was taken as the average visible light transmittance.
[0021] The results are recorded in Table 1; Table 1: Membrane Test Results According to the data in Table 1, the film layer obtained by the AZP plastic evaporation coating surface process used in this invention has strong adhesion, high repeatability and durability of adhesion, and high transparency of the film layer.
[0022] Comparing Example 3 with Comparative Example 1, it can be seen that replacing the first film layer used in step (3) with a pre-treated base film layer shows that the AZP plastic evaporation coating surface process using the first film layer in this invention results in a film layer with stronger adhesion and higher transparency.
[0023] A comparison of Example 3 and Comparative Example 2 shows that using TiO2... x N y Transition film layer-1 replaces TiO x N y Transition film layer, indicating that the present invention uses TiO2 x N y The transition film layer undergoes AZP plastic evaporation coating surface process, resulting in a film layer with strong adhesion and high transparency.
[0024] A comparison of Example 3 and Comparative Example 3 shows that using TiO2... x N y Transition film layer -2 replaces TiO x N y Transition film layer, indicating that the present invention uses TiO2 x N y The transition film layer undergoes AZP plastic evaporation coating surface process, resulting in a film layer with stronger adhesion and higher transparency.
[0025] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.
Claims
1. AZP plastic evaporation coating surface process, characterized by: Includes the following steps: Step (1): After hot pressing the AZP optical resin, cool it to room temperature to obtain a base film layer; immerse the base film layer in isopropanol, disperse it ultrasonically, dry it under vacuum, and then treat it with argon plasma to obtain a pretreated base film layer. Step (2): Place the pretreated substrate film in the evaporation coating machine, control the temperature and initial vacuum of the pretreated substrate film, place the film material s in the tungsten boat, close the baffle, turn on the power to heat and increase the evaporation current, remove the baffle, control the evaporation vacuum, deposit, anneal, and cool with the furnace to obtain the first film layer. Step (3): Reduce the evaporation current to zero, close the baffle, introduce argon gas, load Ti3O5 into the electron beam evaporation crucible, turn on the electron beam, preheat, start the ion source, apply bias voltage to bombard the first film layer, then adjust the electron beam power, turn on ion plating, deposit, anneal, cool with the furnace, and obtain the Ti3O5 film layer. Step (4): Maintain vacuum, turn off electron beam, turn on RF power supply and gas flow controller, use high-purity titanium as target material, introduce mixed gas, set sputtering power, substrate bias voltage and working gas pressure, and deposit TiO2. x N y Transition film layer; Step (5): Turn off the RF power supply and gas flow controller, maintain the vacuum, place the high-purity SiO2 in another electron beam evaporation crucible, preheat to the evaporation temperature, turn on the electron beam, control the evaporation rate, turn on the ion source power supply, introduce pure oxygen, adjust the ion beam energy and beam current density, deposit, anneal, cool with the furnace, form a SiO2 film layer, and complete the AZP plastic evaporation coating surface process.
2. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (1), the hot pressing is performed at a temperature of 130-135℃ and a pressure of 8-12MPa; the cooling rate is 0.5-0.7℃ / min; and the thickness of the base film is 0.8-1.2mm.
3. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (1), the ultrasonic dispersion power is 200-300W and the frequency is 20-30kHz; the vacuum drying temperature is 60-80℃; the argon plasma treatment pressure is 10-15Pa and the power is 150-200W.
4. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (2), the temperature of the pretreated substrate film is controlled at 35-40℃; the initial vacuum degree is ≤2.5×10⁻⁶. -3 Pa; membrane material S is SiO or MgF2; increase the evaporation current to 540-560 mA; evaporation vacuum degree is 1.8 × 10⁻⁶. -2 Pa-2.0×10 -2 Pa; deposition rate of 0.3-0.5 nm / s; annealing temperature of 70-75℃; thickness of the first film layer of 30-40 nm.
5. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (3), the rate at which the anti-evaporation current decreases to zero is 10-20 mA / min; the flow rate of argon gas is 5-10 sccm; the electron beam power during preheating is 1-2 kW; the volume ratio of argon to oxygen in the ion source is 95:5; the bias voltage is 300-310 V; and the power of the electron beam is adjusted to 4-6 kW.
6. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (3), the conditions for ion plating are: bias voltage of 100-150V and ion current density of 0.1-0.3mA / cm. 2 The deposition rate is 0.1-0.3 nm / s, and the vacuum degree during deposition is ≤5×10⁻⁶. -4 Pa; the annealing temperature is 75-80℃; the thickness of the Ti3O5 film is 40-50nm.
7. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (4), the vacuum level is maintained at ≤5×10 -4 Pa; sputtering power is 200-300W, substrate bias voltage is -120V to -80V, and working gas pressure is 0.5-1.0Pa.
8. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (4), during the deposition process, the mixed gas includes Ar, N2, and O2. The Ar flow rate is 35-45 sccm, and the ratio of Ar flow rate to the total flow rate of N2 and O2 is 7-8:2-3. The flow rate ratio of N2 and O2 is adjusted sequentially from 1:2 to 1:4, 1:6, 1:8, and 1:
10. The flow rate ratio of N2 and O2 is adjusted every 3-5 nm of deposition, and the deposition rate is 0.05-0.1 nm / s. TiO2 x N y The thickness of the transition film is 15-25 nm.
9. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (5), the vacuum level is maintained at ≤5×10⁻⁶. -4 Pa; preheat to evaporation temperature of 1650-1750℃; evaporation rate of 0.05-0.1nm / s; pure oxygen flow rate of 8-12sccm.
10. The AZP plastic evaporation coating surface process according to claim 1, characterized in that: In step (5), the ion beam energy is 80-120 eV, the beam current density is 2-4 mA / cm², the deposition rate is 0.08-0.15 nm / s, the annealing temperature is 80-85℃, and the thickness of the SiO2 film is 40-50 nm.