Highly penetrating anti-fouling protective film

Abstract

This invention discloses a high-penetration anti-fouling protective film, comprising: a substrate layer; and a high-penetration pitting coating, which is laminated onto the upper surface of the substrate layer via a light-transmitting adhesive layer and consists of the following components in parts by weight: 4-5 parts fluorinated polyether acrylate, 3-4.5 parts titanium dioxide dispersion, 0.5-1 part nitrogen heterocyclic monomer, 0.05-0.1 part azo initiator, 0.01-0.1 part graphene quantum dots, 0.1-0.3 parts photoinitiator, 0.1-0.3 parts crosslinking agent, and 85-90 parts organic solvent. This invention exhibits excellent high-penetration performance, making it suitable for applications requiring extremely high light transmittance, such as electronic product screens and outdoor glass; it also demonstrates outstanding anti-fouling performance; and its overall performance is excellent, possessing not only high penetration and strong anti-fouling properties but also good wear resistance and anti-yellowing properties, with strong adhesion between the coating and the substrate; furthermore, its preparation process is simple and its production cost is low.

Description

Technical Field

[0001] This invention relates to the field of antifouling protective film technology, and specifically to a high-penetration antifouling protective film. Background Technology

[0002] Traditionally, fluorocarbon compounds with low surface energy and oleophobic properties (such as perfluoropolyethers, polytetrafluoroethylene, and fluorosilanes) are used to prepare antifouling protective films. While their overall performance can meet the needs of some scenarios, significant drawbacks remain: First, it is difficult to simultaneously achieve high light transmittance and high abrasion resistance; increasing coating thickness leads to decreased light transmittance, while insufficient thickness results in poor antifouling and abrasion resistance. Second, the abrasion resistance and hardness are insufficient for high-intensity applications such as foldable screens and AR / VR lenses. Third, the lack of synergistic mechanisms for anti-oxidation and free radical scavenging leads to yellowing and loss of transparency with long-term use, further affecting penetration performance. Furthermore, the preparation processes of some antifouling protective films are complex, resulting in high production costs, and the coating's adhesion to the substrate is weak, making it prone to peeling and curling, thus failing to meet the requirements of large-scale production and long-term use. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high-penetration anti-fouling protective film, which has high penetration, strong anti-fouling properties, and is easy to prepare.

[0004] The technical solution of the present invention is as follows: A high-penetration anti-fouling protective film, comprising: Substrate layer; A high-penetration pitting coating, which is laminated onto the upper surface of a substrate layer via a light-transmitting adhesive layer, is composed of the following components in parts by weight: 4-5 parts of fluorinated polyether acrylate, 3-4.5 parts of titanium dioxide dispersion, 0.5-1 parts of nitrogen heterocyclic monomer, 0.05-0.1 parts of azo initiator, 0.01-0.1 parts of graphene quantum dots, 0.1-0.3 parts of photoinitiator, 0.1-0.3 parts of crosslinking agent, and 85-90 parts of organic solvent.

[0005] Furthermore, the substrate layer is made of a high-transmittance polymer material selected from polyethylene terephthalate (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA).

[0006] Furthermore, the thickness of the substrate layer is 25-100 μm.

[0007] Furthermore, the substrate layer needs to be pretreated by placing the substrate in an ultrasonic cleaning device and ultrasonically cleaning it with deionized water for 10-15 minutes to remove surface impurities. Then, it is dried in an oven at 80-100℃ for 30-60 minutes and cooled to room temperature before use.

[0008] Furthermore, the particle size of the titanium dioxide dispersion is 20-30 nm.

[0009] Furthermore, the nitrogen-containing heterocyclic monomer is one or more of N-vinylimidazolium, N-vinylpyridine, 1-vinyl-1,2,4-triazole, and N-vinylpiperazine.

[0010] Furthermore, the azo initiator is azobisisobutyronitrile (AIBN).

[0011] Furthermore, the graphene quantum dots are carboxyl-type graphene quantum dots or hydroxyl-type graphene quantum dots, with a particle size of 2-5 nm, a thickness of 0.4-2.0 nm, and a planar size of less than 100 nm.

[0012] Furthermore, the photoinitiator is 1-hydroxycyclohexylbenzophenone.

[0013] Furthermore, the thickness of the high-penetration anti-fouling coating is 70-150 nm.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) Excellent high penetration performance: By rationally selecting the substrate material and pre-treating the substrate, and optimizing the composition and thickness of the light-transmitting adhesive layer and the high-penetration anti-fouling coating, the present invention makes the light transmittance of the entire protective film ≥93%, haze ≤0.3%, and light refraction and scattering loss extremely low, which can perfectly preserve the optical performance of the protected object. It is suitable for scenarios with extremely high light transmittance requirements such as electronic product screens and outdoor glass. (2) Outstanding anti-fouling performance: The high-penetration anti-fouling coating uses fluorinated polyether acrylate as the base component, introduces nitrogen heterocyclic monomers and graphene quantum dots, and forms a dense cross-linked network through conjugation. At the same time, it is modified with low surface energy, with a surface contact angle ≥110° and a roll-off angle ≤10°, which can effectively resist the adhesion of contaminants such as fingerprints, oil stains, and dust. The contaminants are easy to wipe off and leave no residue, solving the problem of existing protective films being easy to get dirty and difficult to clean. (3) Excellent comprehensive performance: Through the synergistic effect of each component, the protective film not only has high penetration and strong anti-fouling performance, but also has good anti-yellowing performance (after 1000h aging test, the yellowing index is ≤0.2), and the coating has strong adhesion to the substrate, is not easy to peel off or lift, and has a long service life. (4) Simple preparation process: The preparation method of the present invention adopts conventional coating and UV curing process, and the parameters of each step are easy to control. The solvents, photoinitiators and crosslinking agents used in the light-transmitting adhesive layer and the high-penetration anti-fouling coating are the same, which can simplify the process flow, reduce production costs, and is suitable for large-scale production. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0016] This invention provides a high-penetration anti-fouling protective film, which is composed of a high-penetration pitting coating and a substrate layer layer sequentially laminated from top to bottom. The layers work synergistically to achieve both high penetration and strong anti-fouling effects, as detailed below: The substrate layer is made of a high-transmittance polymer material, selected from polyethylene terephthalate (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA), with a preferred thickness of 25-100 μm. Preferably, the substrate layer is pretreated by ultrasonically cleaning it with deionized water for 10-15 minutes to remove surface impurities, followed by drying in an oven at 80-100°C for 30-60 minutes, and then cooling to room temperature for later use. The pretreated substrate layer has a transmittance ≥92% and a haze ≤0.5% to ensure the basic penetration performance of the protective film.

[0017] A high-penetration pitting coating is adhered to the upper surface of the substrate layer, with a thickness of 70-150 μm. This high-penetration pitting coating is the core layer that achieves high-penetration anti-fouling function, and it is composed of the following components in parts by weight: 4-5 parts of fluorinated polyether acrylate, 3-4.5 parts of titanium dioxide dispersion with a particle size of 20-30 nm, 0.5-1 parts of nitrogen heterocyclic monomer, 0.05-0.1 parts of azo initiator, 0.01-0.1 parts of graphene quantum dots, 0.1-0.3 parts of photoinitiator, 0.1-0.3 parts of crosslinking agent, and 85-90 parts of organic solvent.

[0018] in: The titanium dioxide dispersion has a particle size of 20-30 nm and a refractive index of 1.74 to improve the light transmittance of the coating. Under specific conditions, it can act as a photocatalyst to participate in the degradation of grease and improve the anti-fouling ability of the coating.

[0019] The nitrogen heterocyclic monomer is one or more of N-vinylimidazolium, N-vinylpyridine, 1-vinyl-1,2,4-triazole, and N-vinylpiperazine. The N in its molecule can form a dense cross-linked network with other components through conjugation to improve the coating hardness and wear resistance.

[0020] The azo initiator is azobisisobutyronitrile (AIBN), which can promote the smooth progress of the component polymerization reaction.

[0021] The graphene quantum dots are carboxyl-type or hydroxyl-type graphene quantum dots with a particle size of 2-5 nm, a thickness of 1-3 layers (approximately 0.4-2.0 nm), and a planar size of less than 100 nm. The carboxyl (-COOH) or hydroxyl (-OH) functional groups on the surface can combine with other substances in the system through cross-linking or hydrogen bonding, further improving the light transmittance, wear resistance, and anti-yellowing properties of the coating.

[0022] The photoinitiator is 1-hydroxycyclohexylbenzophenone, which is the same as the photoinitiator used in the transparent adhesive layer, thus simplifying the preparation process.

[0023] The crosslinking agent used is the same as that used in the light-transmitting adhesive layer, ensuring the adhesion between the coating and the substrate layer.

[0024] The organic solvent is the same as the solvent used in the light-transmitting adhesive layer, which improves the compatibility of each component and adjusts the effective thickness of the coating during application.

[0025] The surface of the high-penetration anti-fouling coating is modified to form a low surface energy structure with a surface contact angle ≥110° and a roll-off angle ≤10°. It can effectively prevent the adhesion of contaminants such as fingerprints, oil, and dust. The adhered contaminants can be completely removed by simple wiping without leaving any residue.

[0026] To illustrate the technical solution described in this invention, specific embodiments are described below.

[0027] Example 1 This embodiment provides a high-penetration anti-fouling protective film, including a substrate layer and a high-penetration anti-fouling coating. The substrate layer has a thickness of 50 μm, and the high-penetration anti-fouling coating has a thickness of 70 nm.

[0028] (1) Substrate layer: PET material is used, which is pretreated (deionized water ultrasonic cleaning for 12 min, drying at 85℃ for 45 min). After pretreatment, the light transmittance is 91.7% and the haze is 0.4%. (2) A high-penetration anti-fouling coating, composed of the following components by weight: 4 parts of fluorinated polyether acrylate, 1 part of N-vinyl imidazole, 0.1 part of azobisisobutyronitrile, 0.1 part of carboxyl graphene quantum dots, 0.3 parts of 1-hydroxycyclohexyl benzophenone, 3-4.5 parts of titanium dioxide dispersion, 0.3 parts of octavinyl cage-type silsesquioxane, and 100 parts of butanone and propylene glycol methyl ether acetate (mass ratio 6:4); (3) Preparation method: Coated with a micro-grooved roller, with a wet adhesive content of 9-11 g / m². UV curing parameters are: wavelength 365 nm, energy density 1500 mj / cm², and linear speed 10 m / min.

[0029] The high-penetration anti-fouling protective film prepared in this embodiment has a light transmittance of 92.7%, a haze of 0.25%, a surface contact angle of 115°, a roll-off angle of 8°, and a yellowing index of 0.2 after 1000h aging test. The coating has strong adhesion to the substrate and no peeling or lifting. Fingerprints and oil stains can be easily wiped clean without residue.

[0030] Example 1 This embodiment provides a high-penetration anti-fouling protective film, including a substrate layer and a high-penetration anti-fouling coating, with the following thicknesses: substrate layer 50μm, high-penetration anti-fouling coating 110nm.

[0031] (1) Substrate layer: PET material is used, which is pretreated (deionized water ultrasonic cleaning for 12 min, drying at 85℃ for 45 min). After pretreatment, the light transmittance is 91.4% and the haze is 0.5%. (2) A high-penetration anti-fouling coating, composed of the following components by weight: 4 parts of fluorinated polyether acrylate, 1 part of N-vinyl imidazole, 0.1 part of azobisisobutyronitrile, 0.1 part of carboxyl graphene quantum dots, 0.3 parts of 1-hydroxycyclohexyl benzophenone, 3-4.5 parts of titanium dioxide dispersion, 0.3 parts of octavinyl cage-type silsesquioxane, and 90 parts of butanone and propylene glycol methyl ether acetate (mass ratio 6:4); (3) Preparation method: Coated with a micro-grooved roller, with a wet adhesive content of 9-11 g / m². UV curing parameters are: wavelength 365 nm, energy density 1500 mj / cm², and linear speed 10 m / min.

[0032] The high-penetration anti-fouling protective film prepared in this embodiment has a light transmittance of 93.7%, a haze of 0.31%, a surface contact angle of 117°, a roll-off angle of 10°, and a yellowing index of 0.2 after 1000h aging test. The coating has strong adhesion to the substrate and no peeling or lifting. Fingerprints and oil stains can be easily wiped clean without residue.

[0033] Example 3 This embodiment provides a high-penetration anti-fouling protective film, including a substrate layer and a high-penetration anti-fouling coating, with the following thicknesses: substrate layer 50μm, high-penetration anti-fouling coating 150nm.

[0034] (1) Substrate layer: PET material is used, which is pretreated (deionized water ultrasonic cleaning for 12 min, drying at 85℃ for 45 min). After pretreatment, the light transmittance is 91.5% and the haze is 0.3%. (2) A high-penetration anti-fouling coating, composed of the following components by weight: 4 parts of fluorinated polyether acrylate, 1 part of N-vinyl imidazole, 0.1 part of azobisisobutyronitrile, 0.1 part of carboxyl graphene quantum dots, 0.3 parts of 1-hydroxycyclohexyl benzophenone, 3-4.5 parts of titanium dioxide dispersion, 0.3 parts of octavinyl cage-type silsesquioxane, and 60 parts of butanone and propylene glycol methyl ether acetate (mass ratio 6:4); (3) Preparation method: Coated with a micro-grooved roller, with a wet adhesive content of 9-11 g / m². UV curing parameters are: wavelength 365 nm, energy density 1500 mj / cm², and linear speed 10 m / min.

[0035] The high-penetration anti-fouling protective film prepared in this embodiment has a light transmittance of 92.1%, a haze of 0.54%, a surface contact angle of 113°, a roll-off angle of 8°, and a yellowing index of 0.2 after 1000h aging test. The coating has strong adhesion to the substrate and no peeling or lifting. Fingerprints and oil stains can be easily wiped clean without residue.

[0036] The test data for Examples 1-3 are shown in the table below: The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-penetration, anti-fouling protective film, characterized in that, include: Substrate layer; A high-penetration pitting coating, which is laminated onto the upper surface of a substrate layer via a light-transmitting adhesive layer, is composed of the following components in parts by weight: 4-5 parts of fluorinated polyether acrylate, 3-4.5 parts of titanium dioxide dispersion, 0.5-1 parts of nitrogen heterocyclic monomer, 0.05-0.1 parts of azo initiator, 0.01-0.1 parts of graphene quantum dots, 0.1-0.3 parts of photoinitiator, 0.1-0.3 parts of crosslinking agent, and 85-90 parts of organic solvent.

2. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The substrate layer is made of a high-transmittance polymer material, selected from polyethylene terephthalate (PET), polycarbonate (PC) or polymethyl methacrylate (PMMA).

3. The high-penetration anti-fouling protective film according to claim 2, characterized in that, The thickness of the substrate layer is 25-100 μm.

4. The high-penetration anti-fouling protective film according to claim 2, characterized in that, The substrate layer needs to be pretreated by placing it in an ultrasonic cleaning device and ultrasonically cleaning it with deionized water for 10-15 minutes to remove surface impurities. Then, it is dried in an oven at 80-100℃ for 30-60 minutes and cooled to room temperature before use.

5. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The particle size of the titanium dioxide dispersion is 20-30 nm.

6. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The nitrogen-containing heterocyclic monomer is one or more of N-vinylimidazolium, N-vinylpyridine, 1-vinyl-1,2,4-triazole, and N-vinylpiperazine.

7. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The azo initiator is azobisisobutyronitrile.

8. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The graphene quantum dots are carboxyl-type or hydroxyl-type graphene quantum dots with a particle size of 2-5 nm, a thickness of 0.4-2.0 nm, and a planar size of less than 100 nm.

9. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The photoinitiator is 1-hydroxycyclohexylbenzophenone.

10. The high-penetration anti-fouling protective film according to claim 1, characterized in that, The thickness of the high-penetration anti-fouling coating is 70-150 nm.

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