Anti-fingerprint matte PET (Polyethylene Terephthalate) functional film and roll-to-roll magnetron sputtering production process thereof

Abstract

The invention discloses an anti-fingerprint matte PET (Polyethylene Terephthalate) functional film and a roll-to-roll magnetron sputtering production process thereof, and belongs to the field of high-molecular compound processing. The functional film comprises PET, porous SiO2, KH-570 and Si-CFx, the PET is polyethylene glycol terephthalate, the porous SiO2 is of a three-dimensional network structure formed by modulation of a magnetic field, the Si-CFx is of a comb-shaped structure formed by grafting of silane groups and fluorocarbon chain segments, and the main component of the KH-570 is gamma-methacryloxypropyltrimethoxysilane. The production process comprises the following steps: pretreating PET by plasma, periodically changing a magnetic field under Ar gas to deposit nano SiO2, CF4 and methyltrimethoxysilane steam treatment, and curing by a medium-pressure mercury lamp. The surface roughness of the film is 28 nm, the contact angle is 118 + / -3 degrees, the adhesive force is 5.5 N / cm, the wear resistance is larger than or equal to 12000 times, the haze is 8%, collaborative optimization of fingerprint resistance and matte property is achieved, and the material utilization rate reaches 95%.

Description

Technical Field

[0001] This invention belongs to the field of polymer compound processing, and particularly relates to anti-fingerprint matte PET functional film and its roll-to-roll magnetron sputtering production process. Background Technology

[0002] In terms of anti-fingerprint performance, the technical bottleneck of traditional PET functional films stems from the inherent defects in their coating systems and interface bonding mechanisms. Traditional anti-fingerprint coatings often rely on fluorosilicone-modified resins, whose polar groups in the molecular chain significantly increase surface energy, making them prone to fingerprint grease wetting. These greases have a surface tension of approximately 25–30 mN / m. When the coating surface energy is higher than the grease, the grease quickly spreads and fills surface micro-defects, forming difficult-to-remove marks. Experimental data shows that the contact angle of these coatings is generally below 105°, meaning that the roll-off angle of water droplets and grease on the film surface exceeds 30°, making it impossible to remove stains by natural rolling. Wiping requires significant pressure, which actually accelerates coating wear due to friction. More seriously, traditional processes often use fluorocarbon resin systems containing perfluorooctanoic acid (PFOA) to achieve anti-fingerprint effects. While PFOA acts as a surfactant to reduce coating surface energy, its strong hydrophobicity and chemical stability due to its fluorocarbon chains make it difficult to degrade in the environment, resulting in strong bioaccumulation and, as proven, interference with the human endocrine system. Meanwhile, the bonding between traditional coatings and PET substrates mainly relies on physical adsorption, lacking chemical bonding, resulting in adhesion generally below 4.5 N / cm. In daily use, even slight friction can cause localized peeling of the coating. The exposed substrate surface experiences a sudden increase in surface energy, completely negating its anti-fingerprint properties, and the rate of stain adhesion increases by 3 to 5 times compared to the initial state.

[0003] In terms of matte finish, traditional PET functional films face the dilemma of balancing light transmittance and low reflectivity. To meet the light transmittance requirements of displays, touch panels, and other applications, traditional processes often design the film surface as an ultra-smooth structure, with surface roughness strictly controlled below 5nm. At this level, light undergoes typical specular reflection on the film surface, with reflected light intensity reaching 20%–30% of the incident light. Under strong light conditions, the reflected light brightness of such films can exceed 300 cd / m², far exceeding the human visual comfort threshold, easily causing eye fatigue and even glare. Some processes attempt to improve the matte effect by adding inorganic particles, but these also have significant drawbacks. During particle dispersion, if the amount of dispersant is insufficient, the particles easily agglomerate, causing surface roughness to fluctuate to 15–50nm, resulting in uneven light scattering and localized bright spots. If the dispersion is excessive, the coating layer on the particle surface will be damaged, and the bonding force with the substrate will decrease. After friction and thermal cycling, the particles are easy to fall off from the coating, forming pits with a diameter of 1 to 5 μm. This not only causes the haze to rise abnormally to more than 15%, but also becomes a hiding place for stains, further deteriorating the anti-fingerprint performance.

[0004] A deeper contradiction lies in the inherent structural conflict between fingerprint resistance and matte finish. Fingerprint resistance relies on a smooth, continuous structure of a low-surface-energy coating, requiring fluorocarbon segments to be orderly arranged on the film surface to form a dense hydrophobic layer. The smoother the surface and the more regular the arrangement of the hydrophobic segments, the lower the surface energy. On the other hand, matte finish relies on a porous, rough structure, requiring micro- and nano-scale unevenness to achieve diffuse light reflection. The more uniform the unevenness, the more stable the light scattering performance. This structural contradiction makes it difficult for traditional processes to achieve a performance balance—reducing roughness to below 5nm to improve fingerprint resistance results in haze below 3%, while increasing roughness to above 20nm to improve matte finish results in contact angles below 100°. These shortcomings make it difficult to meet the comprehensive requirements of high-end applications for low reflectivity, strong fingerprint resistance, high durability, and low cost. Summary of the Invention

[0005] To address the challenges of synergistic optimization of anti-fingerprint and matte finish properties, weak coating adhesion, and poor abrasion resistance.

[0006] To address the above problems, the present invention provides the following technical solution: Anti-fingerprint matte PET functional film, comprising the following components: 6900~20700 mg / m 2 PET, 3.85–7 mg / m³ 2 Porous SiO2, 0.1–0.5 mg / m 2 KH-570, 0.9~1.8 mg / m 2 Si-CFx; PET: The main component is polyethylene terephthalate; Porous SiO2: By periodically modulating argon plasma using a horizontal array magnetron target, sputtered SiO2 particles are deposited at specific energies and angles, and self-assemble to form a three-dimensional network porous structure. KH-570: Its main component is γ-methacryloyloxypropyltrimethoxysilane, and its structure is CH2=C(CH3)COO(CH2)3Si(OCH3)3; Si-CFx: is a comb-like structure formed by grafting silane groups and fluorocarbon segments.

[0007] Preferably, the main component of the PET is polyethylene terephthalate, with a molecular weight of 20,000 to 30,000 g / mol, a thickness of 50 to 150 μm, and a light transmittance of 85%.

[0008] Preferably, the porous SiO2 is a three-dimensional network structure formed by magnetic field modulation, and its SiO2 specific surface area is 200-300 m² / g. 2 / g, porosity 60-70%, its magnetic field modulation frequency is 10-50Hz, and magnetic field strength is 0.1-0.5T.

[0009] Preferably, the Si-CFx is composed of silane groups and fluorocarbon segments, with a surface energy ≤15mN / m, a contact angle between the Si-CFx graft layer and a water droplet of 155°±2°, and a contact angle of hexadecane of 135°±3°.

[0010] The roll-to-roll magnetron sputtering production process for anti-fingerprint matte PET functional films includes the following steps: S1: Use an ion bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in a hot air drying zone at 60-80℃ for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving PET roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the pretreatment cavity with a length of 1.0 to 1.5m. The radio frequency power of the plasma is set to 100 to 200W, the gas pressure in the pretreatment cavity is 0.5 to 1Pa, the gas used is Ar / O2, and the production line speed is set to 1 to 2m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300-500W, the gas pressure is set to 0.3-0.5Pa, and the deposition rate is set to 15-20nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-8 channel annular gas distribution port. Finally, the grafting precursor is passed through a 1-2m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80-100℃ for 10-30 seconds to achieve pre-relaxation of the grafted layer molecules and release of internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 2 to 5 minutes in a hot air circulating curing oven at 80 to 100°C with a nitrogen atmosphere.

[0011] Preferably, in step S2, the plasma treatment time for each step is 0.5 to 1 second, the production line speed is 1 to 2 m / min, and the surface energy of the prepared PET reaches 40 to 50 mN / m.

[0012] Preferably, the magnetron target in S3 is a Si target with a purity of 99.99%, wherein the thickness of the nano-SiO2 deposition layer is controlled between 50 and 100 nm.

[0013] Preferably, in S4, CF4 and methyltrimethoxysilane vapor are mixed at a volume flow rate ratio of 1:2, so that the graft layer thickness reaches 5-10 nm.

[0014] Preferably, the working sputtering power in the deposition chamber in S4 is set to 100-150 W and the gas pressure through which the steam passes is 0.1-0.2 Pa.

[0015] Preferably, in step S6, the high-pressure mercury lamp has a wavelength of 254nm, and the ultraviolet curing time is controlled to be 5-8s.

[0016] The anti-fingerprint matte PET functional film of this invention and its roll-to-roll magnetron sputtering production process have the following effects and advantages: 1. This invention uses a biaxial stretching process to improve flatness, and the surface is pretreated with plasma to form nanoscale micro-pits to enhance coating adhesion. Based on the magnetron sputtering production line, it is modified to achieve a balance between high performance, high capacity and low cost by precisely controlling process parameters, thus solving the problem of difficulty in achieving both high performance and high-speed continuous production.

[0017] 2. In this invention, the KH-570 is deposited after plasma pretreatment to form a gradient transition interface with the underlying layer. It forms -Si-O-Si- chemical bonds on the silicon surface through hydrolysis and condensation reaction, with an interfacial bonding force >5N / cm. Then, the Si-CFx cross-linked coating is deposited with the assistance of radio frequency bias, so that the wear resistance can be ≥12000 times.

[0018] 3. In this invention, a three-dimensional network porous SiO2 layer formed by dynamic magnetic field modulation and a comb-structured Si-CFx coating form a stable composite structure with porous support and low-energy surface. The 2-5nm pores of the porous SiO2 can enhance the bonding with the PET substrate through mechanical interlocking effect, while the fluorocarbon segments in Si-CFx are firmly anchored through grafting reaction. The three-dimensional network structure of the porous SiO2 imparts matte properties to the film, and the fluorocarbon segments in Si-CFx impart anti-fingerprint properties.

[0019] 4. This invention achieves a highly efficient combination of anti-fingerprint and matte performance through the synergistic effect of Si-CFx comb-like molecular structure and nanoporous SiO2 three-dimensional network structure. At the same time, the 8% haze formed by porous SiO2 gives it an excellent matte effect, and the microstructure with a surface roughness of 28nm ensures a matte texture.

[0020] 5. In this invention, polyethylene terephthalate is suitable as a functional membrane substrate due to its molecular structure and mechanical properties, and plasma pretreatment specifically alters its surface chemical properties.

[0021] 6. In this invention, the bottom layer is plasma-modified PET providing a stable substrate, KH-570 acts as a bridge connecting PET and porous SiO2, the middle layer is a three-dimensional network structure of porous SiO2 providing matte finish and mechanical support, and the surface layer is a comb-like structure of Si-CFx reducing surface energy. At the same time, silane groups combine with the hydroxyl groups of porous SiO2, and through the synergistic effect of the low surface energy coating and the porous structure, the composite properties of anti-fingerprint, matte finish, high adhesion, and high wear resistance are finally achieved.

[0022] 7. The PET functional film of this invention is suitable for electronic device scenarios, which can reduce reflection, resist fingerprints, and resist scratches. It is suitable for high-frequency touch operation scenarios. In automotive interiors, the matte texture can reduce the glare of sunlight reflection and has the characteristics of fingerprint resistance, easy cleaning and high temperature resistance. In furniture panels, it provides a soft matte finish to enhance visual comfort. It is highly wear-resistant, suitable for long-term use, and environmentally friendly.

[0023] 8. In this invention, the KH-570 coupling layer enables the adhesion of the functional film to reach level 5B, and the weather resistance test does not show delamination. The γ-methacryloyloxypropyltrimethoxysilane contained therein can form chemical bonds with the free radicals on the surface of the PET substrate and the hydroxyl groups of the porous SiO2 layer. Attached Figure Description

[0024] Figure 1 This is a flowchart illustrating the preparation process of the anti-fingerprint matte PET functional film in this invention. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0026] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. Example 1

[0027] This embodiment provides a roll-to-roll magnetron sputtering production process for anti-fingerprint matte PET functional films, utilizing metal material plating, coating, and surface treatment methods. The implementation details are as follows: Experimental objective: PET functional films are prepared using a roll-to-roll magnetron sputtering process for coating metal materials.

[0028] Experimental materials: Ar / O2, PET, high-purity silicon target, CF4, methyltrimethoxysilane vapor.

[0029] Experimental steps: S1: Use an ion bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in hot air at 60°C for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving PET roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the 1.0m long pretreatment cavity. The plasma radio frequency power is set to 100W, the gas pressure in the pretreatment cavity is 0.5Pa, the gas used is Ar / O2, and the production line speed is set to 1m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300W, the gas pressure is 0.3Pa, and the deposition rate is 15nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-channel annular gas distribution port. Finally, the grafting precursor is passed through a 1m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80°C for 10 seconds to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 2 minutes in a hot air circulation curing oven at 80°C with a nitrogen atmosphere.

[0030] Experimental results: See Table 1 for details.

[0031] Table 1: Test Results of Example 1

[0032] Also refer to Figure 1 The preparation process described in Example 1 involves the fabrication of an anti-fingerprint matte PET functional film with excellent comprehensive performance via roll-to-roll magnetron sputtering. This process achieves precise multilayer construction of the functional film through key steps such as plasma pretreatment, magnetic field-modulated deposition of nanoporous SiO2, CF4 and methyltrimethoxysilane vapor grafting reaction, and ultraviolet curing. The final product exhibits a surface roughness of 28 nm, a water contact angle of 118°±3°, an adhesion of 5.5 N / cm, a wear resistance exceeding 12,000 cycles, and a haze of 8%, significantly improving the synergistic performance of anti-fingerprint properties and matte finish. Furthermore, this process offers advantages such as high-speed continuous production, high material utilization, and environmental friendliness, making it suitable for high-end applications such as electronic devices, automotive interiors, and furniture panels, and demonstrating promising industrialization prospects. Example 2

[0033] This embodiment provides a roll-to-roll magnetron sputtering production process for anti-fingerprint matte PET functional films. It utilizes metal material plating, coating, and surface treatment methods, employing different operating parameters. The implementation details are as follows: Experimental objective: PET functional films are prepared using a roll-to-roll magnetron sputtering process for coating metal materials.

[0034] Experimental materials: Ar / O2, PET, high-purity silicon target, CF4, methyltrimethoxysilane vapor.

[0035] Experimental steps: S1: Use an ion air bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in hot air at 80°C for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving PET roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the 1.5m long pretreatment cavity. The radio frequency power of the plasma is set to 200W, the gas pressure in the pretreatment cavity is 1Pa, the gas used is Ar / O2, and the production line speed is set to 2m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 500W, the gas pressure is 0.5Pa, and the deposition rate is 20nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through an 8-channel annular gas distribution port. Finally, the grafting precursor is passed through a 2m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 100°C for 30 seconds to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 5 minutes in a hot air circulation curing oven at 100°C with a nitrogen atmosphere.

[0036] Experimental results: See Table 2 for details.

[0037] Table 2: Test Results of Example 2

[0038] Compared to Example 1, Example 2 uses higher power, longer treatment time, higher gas pressure, and thicker deposition; the thicker SiO2 deposition and more intense plasma pretreatment form a more significant three-dimensional network structure, resulting in increased roughness; while the thicker Si-CFx graft layer can provide more sufficient low surface energy fluorocarbon segments, thus improving hydrophobicity; the stronger plasma pretreatment and the thicker KH-570 coupling layer work together to form stronger interfacial chemical bonds. Example 3

[0039] This embodiment provides a roll-to-roll magnetron sputtering production process for anti-fingerprint matte PET functional films. It utilizes metal plating, coating, and surface treatment methods, eliminating the need for UV curing. The implementation details are as follows: Experimental objective: PET functional films are prepared using a roll-to-roll magnetron sputtering process for coating metal materials.

[0040] Experimental materials: Ar / O2, PET, high-purity silicon target, CF4, methyltrimethoxysilane vapor.

[0041] Experimental steps: S1: Use an ion bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in hot air at 60°C for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving PET roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the 1.0m long pretreatment cavity. The plasma radio frequency power is set to 100W, the gas pressure in the pretreatment cavity is 0.5Pa, the gas used is Ar / O2, and the production line speed is set to 1m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300W, the gas pressure is 0.3Pa, and the deposition rate is 15nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-channel annular gas distribution port. Finally, the grafting precursor is passed through a 1m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80°C for 2 minutes to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress.

[0042] Experimental results: See Table 3 for details.

[0043] Table 3: Test Results of Example 3

[0044] Because the UV curing process was omitted from the experimental design, the Si-CFx comb-like structure failed to fully cross-link and cure, resulting in a decrease in the roughness of the SiO2 layer. At the same time, the lack of curing caused the low surface energy CFx segments to be arranged in an disordered and dense manner, leading to a significant decrease in hydrophobicity. Furthermore, the lack of curing resulted in a poorer adhesion between the entire coating system and the substrate. Example 4

[0045] This embodiment provides a roll-to-roll magnetron sputtering production process for anti-fingerprint matte PET functional films. It utilizes metal plating, coating, and surface treatment methods, and adjusts the plasma RF power and cavity gas pressure. The implementation details are as follows: Experimental objective: PET functional films are prepared using a roll-to-roll magnetron sputtering process for coating metal materials.

[0046] Experimental materials: Ar / O2, PET, high-purity silicon target, CF4, methyltrimethoxysilane vapor.

[0047] Experimental steps: S1: Use an ion bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in hot air at 60°C for 1 hour to improve the anti-oil interference effect. S2: Plasma is used to modify and pretreat the surface of continuously moving PET rolls. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the 1.0m long pretreatment cavity. The plasma radio frequency power is set to 250W, the gas pressure in the pretreatment cavity is 1.5Pa, the gas used is Ar / O2, the production line speed is set to 1m / min, and the plasma treatment time is set to 0.5s. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300W, the gas pressure is 0.3Pa, and the deposition rate is 15nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-channel annular gas distribution port. Finally, the grafting precursor is passed through a 1m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80°C for 10 seconds to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 2 minutes in a hot air circulation curing oven at 80°C with a nitrogen atmosphere.

[0048] Experimental results: See Table 4 for details.

[0049] Table 4: Test Results of Example 4

[0050] Excessive plasma sputtering power within the cavity can cause plasma to penetrate PET, damaging the production machinery. Increasing the power and gas pressure of plasma pretreatment in S1 results in stronger plasma etching of the PET surface, creating deeper nano-micropits, which leads to a slight decrease in overall roughness. Furthermore, the increased surface roughness, activity, and high power cause excessive degradation of the molecular chains on the PET surface, weakening the strength of the material itself. Example 5

[0051] This embodiment provides a roll-to-roll magnetron sputtering production process for an anti-fingerprint matte LDPE functional film, utilizing a polyimide film to prepare the anti-fingerprint matte film. The implementation details are as follows: Experimental objective: Anti-fingerprint matte functional film was prepared by modifying LDPE as a substrate.

[0052] Experimental materials: Ar / O2, LDPE, high-purity silicon target, CF4, methyltrimethoxysilane vapor.

[0053] Experimental steps: S1: Use an ion bar to remove dust and static electricity from the LDPE roll, then spray the LDPE roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the LDPE roll in hot air at 60°C for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving LDPE roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the LDPE through the 1.0m long pretreatment cavity. The plasma radio frequency power is set to 100W, the gas pressure in the pretreatment cavity is 0.5Pa, the gas used is Ar / O2, and the production line speed is set to 1m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300W, the gas pressure is 0.3Pa, and the deposition rate is 15nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-channel annular gas distribution port. Finally, the grafting precursor is passed through a 1m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80°C for 10 seconds to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 2 minutes in a hot air circulation curing oven at 80°C with a nitrogen atmosphere.

[0054] Experimental results: See Table 5 for details.

[0055] Table 5: Test Results of Example 5

[0056] Example 5 replaced the substrate with low-density polyethylene, and the results confirmed the crucial role of the high-performance PET substrate in the process and the final performance. The inherent low heat resistance of LDPE caused significant thermal shrinkage and deformation during the process, resulting in damage to the surface smoothness of the substrate. The physical deformation introduced huge internal stress between the substrate and the coating and weakened the mechanical interlocking effect, resulting in loss of bonding force. At the same time, the surface of LDPE is extremely chemically inert, making it difficult to form sufficient active sites through plasma treatment, so that the KH-570 coupling agent cannot establish effective chemical bonds with the substrate, further deteriorating the interfacial bonding. Finally, the uneven and chemically inactive substrate prevented the subsequent deposition of porous SiO2 and Si-CFx layers from forming densely and uniformly, resulting in uncontrolled surface roughness, large fluctuations in hydrophobic properties, and a sharp decline in wear resistance. Comparative Example 1

[0057] This embodiment provides a method for preparing a conventional PET functional film, as detailed below: Experimental objective: Preparation of traditional PET functional films.

[0058] Experimental materials: PET base layer, fluorosilicone modified resin, acrylic pressure-sensitive adhesive.

[0059] Experimental steps: S1: Use a three-stage ultrasonic cleaning process of deionized water, anhydrous ethanol, and deionized water to clean the substrate for 15 minutes each time to remove surface oil and weak boundary layer, followed by drying at 60°C for 30 minutes. S2: Subsequently, the surface is subjected to 5-10 kW at a speed of 5-10 m / min to increase the surface tension of PET from 42 mN / m to 50 mN / m, thereby enhancing the coating adhesion; S3: Then, tetraethyl orthosilicate is mixed with anhydrous ethanol at a ratio of 1:10 to 1:12, deionized water and ammonia are added to adjust the pH to 10, and stirred at room temperature for 2 to 6 hours before aging in a 30°C water bath for 5 days. S4: Using a 200-mesh micro-grooved roller, apply the sol at a speed of 15-20 m / min, and UV cure to form the initial AR layer; S5: Mix fluorosiloxane, anhydrous ethanol, and deionized water in a ratio of 3:50:100, apply twice, and UV cure to form a hydrophobic surface; S6: Use a slot extrusion coating machine to apply the acrylic adhesive at a speed of 20m / min, cure with hot air at 90-110℃ for 10 minutes, and then cure at 40℃ for 72 hours to ensure that the cohesive strength of the adhesive is >5N / cm.

[0060] Experimental results: See Table 6 for details.

[0061] Table 6: Test Results of Comparative Example 1

[0062] In terms of process, a three-stage ultrasonic cleaning process involving deionized water, anhydrous ethanol, and deionized water effectively removes oil stains and weak boundary layers from the PET substrate surface. Combined with a ~10kW corona treatment, the surface tension is increased from 42mN / m to 50mN / m, laying the foundation for subsequent coating adhesion. A fluorosilicone modified resin coating is prepared using the sol-gel method. After microgravure coating and UV curing, an initial AR layer is formed. Then, a secondary coating with fluorosiloxane is used to enhance the hydrophobic properties. Finally, an acrylic pressure-sensitive adhesive is applied by slot extrusion to complete the construction of the functional layer. The surface roughness of this traditional PET functional film is only 3.2nm, and the haze is 1.8%, demonstrating excellent transparency and making it suitable for high light transmittance applications. The fluorosilicone modified coating gives it a contact angle of 105°±2°, providing basic anti-fouling capabilities. Combined with an adhesion of 4.2N / cm and a wear resistance of ≥4000 cycles, it can meet the scratch resistance and anti-fouling requirements of normal use. Comparative Example 2

[0063] A PET functional film with dual functions of antistatic and wear resistance is provided, as described below: Experimental materials: Biaxially oriented PET film, waterborne polyurethane, quaternary ammonium salt antistatic agent, nano-alumina, ethyl acetate.

[0064] Experimental objective: A PET with both antistatic and wear-resistant properties was prepared.

[0065] Experimental steps: S1: Immerse the PET film in 5% NaOH solution and sonicate for 10 minutes to remove surface grease. Then rinse with deionized water until neutral and dry at 60℃ for 20 minutes. S2: Atmospheric pressure plasma treatment was employed, with a nitrogen atmosphere of 800W power and a velocity of 8m / min, to increase the surface hydrocarbon content to 3.2 nm. 2 Enhance coating adhesion; S3: Mix waterborne polyurethane and ethyl acetate at a mass ratio of 1:1 and stir for 30 minutes until uniform. Then add quaternary ammonium salt antistatic agent and nano alumina, disperse at high speed for 30 minutes to form a uniform suspension. Finally, add defoamer and leveling agent, stir at low speed for 10 minutes, and control the viscosity of the coating liquid to 25-30 cps. S4: Apply the coating with a doctor blade at a speed of 12m / min to form a wet film on the PET surface. Perform segmented heat curing: pre-bake at 60℃ for 1 minute → cross-link and cure at 120℃ for 3 minutes. Cool and set the shape, then allow it to cool naturally to room temperature. Control the winding tension at 8N to avoid stretching and deformation of the film.

[0066] Experimental results: See Table 7 for details.

[0067] Table 7: Test Results of Comparative Example 2

[0068] Comparative Example 2 prepared a PET functional film with dual functions of antistatic and wear resistance through a substrate pretreatment-coating composite-curing and shaping process. First, the PET surface hydroxyl content was increased by ultrasonic cleaning with 5% NaOH solution and plasma treatment with 800W power and 8m / min nitrogen atmosphere. Then, waterborne polyurethane and ethyl acetate were mixed at a ratio of 1:1, and quaternary ammonium salt antistatic agent and nano alumina were added and dispersed at high speed before coating. After pre-baking at 60℃ and cross-linking and curing at 120℃, the film was shaped and shaped. Its performance was as follows: surface roughness 5.8nm, contact angle 65°±3°, adhesion 4.8N / cm, wear resistance ≥5500 times, and haze 2.5%. It is suitable for industrial scenarios that are sensitive to static electricity and focus on wear resistance. Its performance positioning is significantly different from that of the anti-fingerprint matte ET functional film.

[0069] Example 1 serves as a benchmark case, demonstrating the best overall performance achievable with optimized process parameters: surface roughness 28 nm, contact angle 118°±3°, adhesion 5.5 N / cm, abrasion resistance ≥12000 cycles, and haze 8%. It successfully proves that the technical path of plasma pretreatment, magnetic field-modulated sputtering of SiO2, CF4 / methyltrimethoxysilane vapor grafting, and UV curing can synergistically optimize fingerprint resistance and matte finish, and achieve extremely high adhesion and abrasion resistance, providing a reliable solution for industrialization.

[0070] Example 3, by eliminating the UV curing step, resulted in a contact angle of 95°±5°, an adhesion of 3.0 N / cm, and a wear resistance of only ≥500 cycles. This, in turn, confirms that UV curing is an indispensable key step for the full cross-linking, anchoring, and ultimately excellent wear resistance and hydrophobicity of the Si-CFx low surface energy coating. Without this step, the entire functional layer system cannot establish a strong chemical bond, and its performance is completely ineffective.

[0071] Example 4 attempted to enhance the effect by increasing the power and gas pressure of plasma pretreatment, but the results showed that the adhesion and abrasion resistance were actually lower than in Example 1. This indicates that plasma treatment needs to be precisely optimized rather than being as strong as possible. Excessive treatment damages the molecular structure of the PET substrate surface, forming a weak interface layer, which becomes the weak link in the final coating adhesion.

[0072] Example 5 replaced the substrate from PET with low-performance LDPE. The results showed a large fluctuation in the contact angle (105°±10°), adhesion ≤1.5N / cm, abrasion resistance ≥500 cycles, and haze ≥15%. This clearly illustrates that a high-performance substrate is the foundation for supporting the entire high-performance coating system. The inherent defects of LDPE, such as poor heat resistance, strong surface inertness, and low mechanical strength, make it completely unable to withstand the harsh conditions of subsequent processes, resulting in ineffective coating adhesion and the inability to achieve the desired process. This case highlights the paramount importance of substrate selection.

[0073] Example 2 represents the performance limit achievable within the process window of this invention by comprehensively enhancing various process parameters; this scheme uses the highest parameters for all steps: stronger plasma pretreatment, thicker nano-SiO2 deposition layer, thicker Si-CFx graft layer, and longer UV curing time; as a result, the prepared functional film surpasses Example 1 in both mechanical and hydrophobic properties, reaching a higher level; this is due to more intense surface activation, a more significant three-dimensional network structure, and more abundant hydrophobic segments.

[0074] Comparative Example 1 describes the preparation of a traditional PET functional film. Using PET substrate, fluorosilicone modified resin, and acrylic pressure-sensitive adhesive as raw materials, the film undergoes a three-stage ultrasonic cleaning process (deionized water, anhydrous ethanol, and deionized water), corona treatment at 5-10 kW, initial AR layer formation via sol-gel coating of tetraethyl orthosilicate and anhydrous ethanol, secondary coating with a fluorosiloxane mixture and UV curing, and final coating and thermal curing with acrylic adhesive. The resulting product exhibits a surface roughness of 3.2 nm, a contact angle of 105°±2°, adhesion of 4.2 N / cm, abrasion resistance ≥4000 cycles, and haze of 1.8%. While possessing basic anti-fouling and scratch resistance, making it suitable for high-transmittance applications, its fingerprint resistance and matte finish are relatively weak. Furthermore, its production efficiency and material utilization are inferior to the anti-fingerprint matte PET functional film prepared by the roll-to-roll magnetron sputtering process in Example 1.

[0075] Comparative Example 2 focuses on the preparation of a PET functional film with dual functions of antistatic and wear resistance. Its raw materials include biaxially oriented PET film, waterborne polyurethane, quaternary ammonium salt antistatic agent, nano-alumina, ethyl acetate, etc. In the preparation process, the PET film is first immersed in 5% NaOH solution and ultrasonically treated for 10 minutes to remove surface grease. It is then rinsed with deionized water until neutral and dried at 60°C for 20 minutes. Next, it is treated with atmospheric pressure plasma under a nitrogen atmosphere at 800W power and 8m / min speed to increase the surface hydroxyl content. Then, waterborne polyurethane and ethyl acetate are mixed at a ratio of 1:1, and quaternary ammonium salt antistatic agent and nano-alumina are added and dispersed at high speed before coating. It is then produced by segmented thermosetting steps, including pre-baking at 60°C for 1 minute and cross-linking and curing at 120°C for 3 minutes. The product has a surface roughness of 5.8nm, a contact angle of 65°±3°, an adhesion of 4.8N / cm, a wear resistance of ≥5500 cycles, and a haze of 2.5%. It is suitable for static-sensitive scenarios, but its performance positioning is significantly different from the requirements for anti-fingerprint and matte finishes.

[0076] This invention, through rigorous comparative experiments, comprehensively verifies the superiority and reliability of the described anti-fingerprint matte functional film and its roll-to-roll magnetron sputtering production process. A comprehensive evaluation of the performance data from each embodiment shows that the process scheme represented by Example 2 exhibits the best overall performance: its contact angle, adhesion, and abrasion resistance are all superior to Example 1. This scheme, by employing comprehensively enhanced process parameters, successfully prepared a functional film product with extreme performance. Its test results comprehensively surpass Example 1, which serves as the benchmark, in the three core performance indicators of hydrophobicity, adhesion, and abrasion resistance, demonstrating the peak performance achievable with this combination of process parameters. Furthermore, although its haze slightly increases due to the more significant micro / nano structure, this is due to its superior matte effect and ultra-high performance. The source of strong mechanical properties lies in the reasonable and controllable trade-offs during performance optimization. In contrast, Example 3 failed due to the lack of a key curing step, Example 4 suffered substrate damage due to over-processing, and Example 5 failed completely due to improper substrate selection. These examples all demonstrate the precision and necessity of the process parameters in Example 2. In summary, Example 2 not only successfully achieved the ultimate synergy between anti-fingerprint and matte performance, but also made breakthrough progress in adhesion and abrasion resistance, perfectly solving the industry pain points mentioned in the background art. This solution represents the optimal process parameter configuration under the technical route of this invention, possessing high performance, high durability, and good industrialization potential. It is an excellent solution with the most promising application prospects and technical representativeness.

[0077] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims.

[0078] In conclusion, 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, improvements, etc., made within the spirit and principles of the present invention should be included in the protection of the present invention.

Claims

1. An anti-fingerprint matte PET functional film, characterized in that, Includes the following components: 6900~20700 mg / m 2 PET, 3.85~7 mg / m 2 Porous SiO2, 0.1~0.5 mg / m 2 KH-570, 0.9~1.8mg / m 2 Si-CFx; PET: The main component is polyethylene terephthalate; Porous SiO2: By periodically modulating argon plasma using a horizontal array magnetron target, sputtered SiO2 particles are deposited at specific energies and angles, and self-assemble to form a three-dimensional network porous structure. KH-570: Its main component is γ-methacryloyloxypropyltrimethoxysilane, and its structure is CH2=C(CH3)COO(CH2)3Si(OCH3)3; Si-CFx: is a comb-like structure formed by grafting silane groups and fluorocarbon segments.

2. The anti-fingerprint matte PET functional film as described in claim 1, characterized in that, The main component of the PET is polyethylene terephthalate, with a molecular weight of 20,000 to 30,000 g / mol, a thickness of 50 to 150 μm, and a light transmittance of 85%.

3. The anti-fingerprint matte PET functional film as described in claim 1, characterized in that, The porous SiO2 has a three-dimensional network structure formed by magnetic field modulation, and the specific surface area of ​​SiO2 is 200-300 m² / g. 2 / g, porosity 60-70%, its magnetic field modulation frequency is 10-50Hz, and magnetic field strength is 0.1-0.5T.

4. The anti-fingerprint matte PET functional film as described in claim 1, characterized in that, The Si-CFx is composed of silane groups and fluorocarbon segments, with a surface energy ≤15mN / m. The contact angle between the Si-CFx graft layer and the water droplet is 155°±2°, and the contact angle of the hexadecane is 135°±3°.

5. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in any one of claims 1-4, characterized in that, Includes the following steps: S1: Use an ion air bar to remove dust and static electricity from the PET roll, then spray the PET roll with an isopropanol aqueous solution with a concentration of less than 5%, and then place the PET roll in hot air at 60-80℃ for 1 hour to improve the anti-oil interference effect. S2: The surface of the continuously moving PET roll is modified and pretreated using plasma. Then, KH-570 is introduced into the cavity in the form of steam to pass the PET through the pretreatment cavity with a length of 1.0 to 1.5m. The radio frequency power of the plasma is set to 100 to 200W, the gas pressure in the pretreatment cavity is 0.5 to 1Pa, the gas used is Ar / O2, and the production line speed is set to 1 to 2m / min. S3: Ar gas with a purity of 99.99% is introduced into the sputtering chamber along the direction of roll material movement. The magnetic field of the roll material movement direction is periodically changed by a horizontally arrayed magnetron target. The sputtering power in the sputtering chamber is set to 300-500W, the gas pressure is set to 0.3-0.5Pa, and the deposition rate is set to 15-20nm / min. S4: Then, CF4 with a purity of 99.99% and methyltrimethoxysilane vapor are thoroughly mixed in a 1:2 ratio in the mixing chamber. The mixed gas is then heated to 80°C and the vapor is applied to the silane-containing grafting precursor through a 6-8 channel annular gas distribution port. Finally, the grafting precursor is passed through a 1-2m long deposition chamber to complete the grafting reaction. S5: Place the roll material obtained after the grafting reaction in a hot air circulation system at 80-100℃ for 10-30 seconds to allow the molecular chain segments of the grafted layer to initially relax and arrange themselves and reduce internal stress. S6: UV intensity set to 800±20mW / cm 2 The mercury lamp power was stabilized at 150±5W. Then, a 1cm long tension buffer section was set at the outlet of the functional film curing chamber to avoid fluctuations in the winding tension affecting the curing effect. S7: The functional film obtained by UV curing is continuously treated for 2 to 5 minutes in a hot air circulating curing oven at 80 to 100°C with a nitrogen atmosphere.

6. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in claim 5, characterized in that, In S2, the plasma treatment time for each step is 0.5 to 1 second, the production line speed is 1 to 2 m / min, and the surface energy of the prepared PET reaches 40 to 50 mN / m.

7. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in claim 5, characterized in that, The magnetron target in S3 is a Si target with a purity of 99.99%, and the thickness of the nano-SiO2 deposition layer is controlled between 50 and 100 nm.

8. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in claim 5, characterized in that, In S4, CF4 and methyltrimethoxysilane vapors are mixed at a volume flow rate ratio of 1:2, resulting in a graft layer thickness of 5–10 nm.

9. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in claim 5, characterized in that, The working sputtering power in the deposition chamber of S4 is set to 100-150 W, and the gas pressure through which the steam passes is 0.1-0.2 Pa.

10. The roll-to-roll magnetron sputtering production process of the anti-fingerprint matte PET functional film as described in claim 5, characterized in that, The S6 uses a high-pressure mercury lamp with a wavelength of 254nm, and the ultraviolet curing time is 5-8s.

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