Wear-resistant antifouling waterproof high-transmittance film and preparation method thereof

Abstract

The invention discloses a wear-resistant antifouling waterproof high-light-transmittance film and a preparation method thereof.The wear-resistant antifouling waterproof high-light-transmittance film comprises a base material and a wear-resistant antifouling waterproof high-light-transmittance layer, the wear-resistant antifouling waterproof high-light-transmittance layer comprises 60-80 parts of fluorinated polyether acrylate, 5-15 parts of nitrogen heterocyclic monomers, 0.1-1 part of an azo initiator, 0.01-1 part of graphene quantum dots, 1-5 parts of a photoinitiator and 1-5 parts of a cross-linking agent; and 20-40 parts of an organic solvent. According to the light-transmitting film, on the basis of fluorinated polyether acrylate, the nitrogen heterocyclic monomer, the graphene quantum dots, the cross-linking agent and other substances are introduced, N in the nitrogen heterocyclic ring can generate a compact cross-linked network in a conjugation mode, the hardness of a system is improved, meanwhile, through the synergistic effect with other substances, lower surface energy can be formed, and the light-transmitting film has the advantages that the light-transmitting film is more excellent in light-transmitting performance. And the diffuse reflection degree in the film is improved, so that the antifouling performance, the waterproof performance, the light transmission performance and the like are further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of permeable membrane, in particular to a wear-resistant, anti-fouling, waterproof and high-transmittance film and a preparation method thereof. BACKGROUND

[0002] With the development of economy and technology, electronic products have experienced explosive growth. People can form a better human-computer interaction with electronic products through touch screens. In the use process, fingerprints, dust and other pollutants tend to easily accumulate on the surface of electronic products, affecting people's operation of the human-computer interaction screen of the electronic product, thereby reducing people's experience of the electronic product. At the same time, touch screens are easily affected by external environmental factors such as scratching, water vapor, etc., thereby reducing the overall service life of the touch screen and the device. Generally, a wear-resistant, anti-fouling and light-transmitting film is pasted on the surface of the touch screen.

[0003] In the prior art, fluorocarbons (-CF) with low surface energy and oleophobic properties, such as perfluoropolyether, polytetrafluoroethylene and fluorosilane, are used. Although the comprehensive performance of fluorocarbons can meet most of the requirements of electronic product touch screens, there are the following defects: (1) It is difficult to simultaneously consider high wear resistance and high hydrophobicity in terms of light transmittance; (2) The wear resistance hardness is insufficient to meet the high-strength use scenarios of folding screens, AR / VR lenses, etc.; (3) Lack of antioxidant and free radical synergistic mechanism, prone to yellowing and loss of transparency during long-term use. Therefore, there is an urgent need for a protective film that takes into account high light transmittance, high wear resistance, high hydrophobicity and high stability. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, one of the purposes of the present application is to provide a wear-resistant, anti-fouling, waterproof and high-transmittance film to solve the above-mentioned traditional technical problems.

[0005] The second purpose of the present application is to provide a preparation method of the above-mentioned wear-resistant, anti-fouling, waterproof and high-transmittance film.

[0006] One of the purposes of the present application is achieved by the following technical scheme: A wear-resistant, anti-fouling, waterproof and high-transmittance film, comprising a substrate and a wear-resistant, anti-fouling, waterproof and high-transmittance layer coated on one side of the substrate, the wear-resistant, anti-fouling, waterproof and high-transmittance layer comprising the following components by weight: fluorinated polyether acrylate 60-80 parts, nitrogen heterocyclic monomer 5-15 parts, azo initiator 0.1-1 part, graphene quantum dot 0.01-1 part, photoinitiator 1-5 parts, crosslinking agent 1-5 parts, organic solvent 20-40 parts.

[0007] In the application, the light-transmitting film is prepared by introducing nitrogen heterocyclic monomers, graphene quantum dots, cross-linking agents and other substances on the basis of fluorinated polyether acrylate. The N in the nitrogen heterocyclic ring can form a dense cross-linking network through conjugation, thereby improving the hardness of the system. In addition, through the synergistic effect of other substances, a lower surface energy can be formed, and the antifouling, waterproof and light-transmitting properties of the light-transmitting film are further improved.

[0008] Further, the nitrogen heterocyclic monomer is one or more of N-vinylimidazole, N-vinylpyridine, 1-vinyl-1,2,4-triazole and N-vinylpiperazine.

[0009] Further, the azo initiator is azobisisobutyronitrile.

[0010] Further, the graphene quantum dots are carboxyl-type graphene quantum dots or hydroxyl-type graphene quantum dots.

[0011] Compared with graphene, graphene quantum dots have the same thickness as graphene, which is single-layer or few-layer, usually 1-3 layers, and the thickness is about 0.4-2.0 nm. The difference lies in the size in the plane orientation, which is less than 100 nm for the former and above micron level for the latter. By introducing carboxyl (-COOH) functional groups or hydroxyl (-OH) functional groups on the basis of graphene quantum dots, they can react with other substances in the system through cross-linking or hydrogen bonding, etc. to improve the overall performance of the system.

[0012] Further preferably, the particle size of the graphene quantum dots is 2-5 nm.

[0013] Further, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0014] Further, the cross-linking agent is one or more of octavinyl cage-type silsesquioxane, octaallyl cage-type silsesquioxane and octaallyl cage-type silsesquioxane.

[0015] Further, the organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7: (2-4).

[0016] Further, the substrate is one of polyethylene terephthalate (PET), polycarbonate (PC) or polymethyl methacrylate (PMMA).

[0017] The second objective of the application is achieved by the following technical scheme: A preparation method of a wear-resistant, antifouling, waterproof and high-transmittance film, comprising the following preparation steps: S1: The substrate is cleaned by ultrasonic cleaning and then dried for standby; S2: under the condition of oxygen-free, the fluorinated polyether acrylate is mixed with the nitrogen heterocyclic monomer uniformly, then the azo initiator is added, and pre-polymerization is carried out at 55-65 DEG C to obtain a nitrogen heterocyclic grafted copolymer; S3: the organic solvent, graphene quantum dots, crosslinking agent and photoinitiator are sequentially added to the nitrogen heterocyclic grafted copolymer, mixed uniformly, ultrasonically treated at room temperature for 10-15 min, and vacuum degassed to obtain a coating glue; S4: the coating glue is coated on the substrate by using a coating device, and the coating glue is obtained.

[0018] Further, the coating device is a slot coating or a micro-concave roller coating, and the control parameters of the coating device are as follows: wet film thickness 8-12 mu m, UV curing: wavelength 365 nm, energy density 300-500 mJ / cm², line speed 5-15 m / min, and post-baking: drying at 80 DEG C for 2 min.

[0019] Compared with the prior art, the present application has the following advantages: The abrasion-resistant, antifouling and waterproof high-transmittance film of the present application introduces nitrogen heterocyclic monomers, graphene quantum dots, crosslinking agents and other substances on the basis of fluorinated polyether acrylate. The N in the nitrogen heterocyclic can form a dense crosslinking network through conjugation, thereby improving the hardness of the system. In addition, through the synergistic effect of other substances, a lower surface energy can be formed, and the antifouling, waterproof and light-transmitting properties of the film are further improved. DETAILED DESCRIPTION

[0020] The present application will be further described below in conjunction with specific embodiments. It should be noted that the embodiments described below or the technical features thereof can be combined in any manner to form new embodiments without conflict. In the following examples, all commercially available products are purchased unless otherwise specified. The substrate of the following examples and comparative examples is polycarbonate (PC).

[0021] The fluorinated polyether acrylate is purchased from Shanghai Daofu Industry Co., Ltd., and Mn=600-2000; N-vinylimidazole is purchased from Wuhan Kamik Technology Co., Ltd.; N-vinylpyridine is purchased from Hubei Jusheng Technology Co., Ltd.; 1-vinyl-1,2,4-triazole is purchased from Hubei Dahao Chemical Co., Ltd.; N-vinylpiperazine is purchased from Nanjing Kangmanlin Chemical Industry Co., Ltd.; Azo diisobutyronitrile is purchased from Hubei Taibang Chemical Co., Ltd.; Carboxyl-type graphene quantum dots are purchased from Shanghai Jizhisheng Chemical Technology Co., Ltd., and are 2-5 nm; Hydroxyl graphene quantum dots were purchased from Shanghai Jizhisheng Biotechnology Co., Ltd., 2-5 nm; 1-hydroxycyclohexyl benzophenone was purchased from Hubei Xinhongli Chemical Co., Ltd.; Octavinyl cage silsesquioxane was purchased from Hubei Chenghai Chemical Co., Ltd.; Octaallyl cage silsesquioxane was purchased from Hubei Jusheng Technology Co., Ltd.; Octaallyl cage silsesquioxane was purchased from Hubei Chenghai Chemical Co., Ltd.; Ethyl acetate was purchased from Hubei Xinhongli Chemical Co., Ltd.; Propylene glycol methyl ether acetate was purchased from Hubei Tuopeng Chemical Co., Ltd.

[0022] Example 1 A film comprising a substrate and a wear-resistant, stain-resistant, waterproof, and high-transmittance layer, the wear-resistant, stain-resistant, waterproof, and high-transmittance layer comprising the following components by weight: fluorinated polyether acrylate 60 parts, nitrogen heterocyclic monomer 15 parts, azo initiator 0.1 part, graphene quantum dots 0.01 part, photoinitiator 2 parts, crosslinking agent 2 parts, organic solvent 40 parts.

[0023] The nitrogen heterocyclic monomer is N-vinylimidazole, the azo initiator is azobisisobutyronitrile, the graphene quantum dots are carboxyl graphene quantum dots, the photoinitiator is 1-hydroxycyclohexyl benzophenone, the crosslinking agent is octavinyl cage silsesquioxane, and the organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7:3.

[0024] Example 2 A film comprising a substrate and a wear-resistant, stain-resistant, waterproof, and high-transmittance layer, the wear-resistant, stain-resistant, waterproof, and high-transmittance layer comprising the following components by weight: fluorinated polyether acrylate 70 parts, nitrogen heterocyclic monomer 12 parts, azo initiator 0.2 part, graphene quantum dots 0.01 part, photoinitiator 2 parts, crosslinking agent 2 parts, organic solvent 40 parts.

[0025] The nitrogen heterocyclic monomer is N-vinylimidazole, the azo initiator is azobisisobutyronitrile, the photoinitiator is 1-hydroxycyclohexyl benzophenone, the crosslinking agent is octaallyl cage silsesquioxane, and the organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7:3.

[0026] Example 3 A film comprising a substrate and a wear-resistant, stain-resistant, waterproof, and high-transmittance layer, the wear-resistant, stain-resistant, waterproof, and high-transmittance layer comprising the following components by weight: fluorinated polyether acrylate 80 parts, nitrogen heterocyclic monomer 15 parts, azo initiator 0.5 part, graphene quantum dots 0.01 part, photoinitiator 2 parts, crosslinking agent 2 parts, organic solvent 40 parts.

[0027] wherein the azaheterocyclic monomer is 1-vinyl-1,2,4-triazole, the azo initiator is azobisisobutyronitrile, the graphene quantum dots are hydroxyl type graphene quantum dots, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, the crosslinking agent is octapropargyl cage silsesquioxane, and the organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7:3.

[0028] Example 4 A film comprising a substrate and an abrasion-resistant, stain-resistant, waterproof, and high-transmittance layer, the abrasion-resistant, stain-resistant, waterproof, and high-transmittance layer comprising the following components by weight: fluorinated polyether acrylate 80 parts, azaheterocyclic monomer 15 parts, azo initiator 1 part, graphene quantum dots 1 part, photoinitiator 4 parts, crosslinking agent 2 parts, and organic solvent 40 parts.

[0029] wherein the azaheterocyclic monomer is N-vinylpiperazine, the azo initiator is azobisisobutyronitrile, the graphene quantum dots are carboxyl type graphene quantum dots, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, the crosslinking agent is octavinyl cage silsesquioxane, and the organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7:3.

[0030] In the above examples, the preparation steps are as follows: S1: the substrate is cleaned by ultrasonic and dried, and is ready for use; S2: under anaerobic conditions, the fluorinated polyether acrylate and the azaheterocyclic monomer are mixed uniformly, and then the azo initiator is added, and pre-polymerization is carried out at 55-65°C to obtain an azaheterocyclic grafted copolymer; S3: the azaheterocyclic grafted copolymer is added with the organic solvent, the graphene quantum dots, the crosslinking agent, and the photoinitiator in sequence, mixed uniformly, ultrasonically treated at room temperature for 15 min, and vacuum degassed to obtain a coating glue; S4: the coating glue is coated on the substrate using a slot coating device to obtain the product. wherein the control parameters of the coating device are as follows: wet film thickness 10 μm, UV curing: wavelength 365 nm, energy density 350 mJ / cm², line speed 12 m / min, and post-baking: drying at 80°C for 2 min.

[0031] The comparative examples are as follows: Comparative Example 1 Comparative Example 1 is a commercially available perfluoropolyether.

[0032] Comparative Example 2 Comparative Example 2 is the same as Example 1 except that no azaheterocyclic monomer is added, and the preparation method is the same, which is not described here.

[0033] Comparative Example 3 Comparative Example 3 does not add graphene quantum dots, and other and preparation method is same, here no longer repeat.

[0034] Comparative Example 4 Comparative Example 4 does not add crosslinking agent, and other and preparation method is same, here no longer repeat.

[0035] Performance test 1, the test method is shown in Table 1 as follows: Table 1

[0036] 2, the test results are shown in Table 2 as follows: Table 2

[0037] From the above table, relative to the comparative example, the comprehensive performance of the membrane of the embodiment of the application is the best.

[0038] The above embodiment is only a preferred embodiment of the application, and cannot be used to limit the scope of protection of the application, and any non-substantial changes and replacements made by those skilled in the art on the basis of the application all belong to the scope of protection claimed by the application.

Claims

1. A wear-resistant, stain-resistant, waterproof, and high-transmittance film, characterized in that, The material includes a substrate and a wear-resistant, stain-resistant, waterproof, and high-transmittance layer coated on one side of the substrate. The wear-resistant, stain-resistant, waterproof, and high-transmittance layer comprises the following components in parts by weight: Fluorinated polyether acrylate 60-80 parts, nitrogen heterocyclic monomer 5-15 parts, azo initiator 0.1-1 parts, graphene quantum dots 0.01-1 parts, photoinitiator 1-5 parts, crosslinking agent 1-5 parts, organic solvent 20-40 parts.

2. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane 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.

3. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 1, characterized in that, The azo initiator is azobisisobutyronitrile.

4. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 1, characterized in that, The graphene quantum dots are carboxyl-type graphene quantum dots or hydroxyl-type graphene quantum dots.

5. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 4, characterized in that, The graphene quantum dots have a particle size of 2-5 nm.

6. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 1, characterized in that, The photoinitiator is 1-hydroxycyclohexylbenzophenone.

7. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 1, characterized in that, The crosslinking agent is one or more of octavinyl cage silsesquioxane, octaallyl cage silsesquioxane, and octapropynyl cage silsesquioxane.

8. The wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 1, characterized in that, The organic solvent is composed of ethyl acetate and propylene glycol methyl ether acetate in a mass ratio of 7:(2-4).

9. A method for preparing a wear-resistant, stain-resistant, waterproof, and high-transmittance film as described in any one of claims 1-8, characterized in that, The preparation steps include the following: S1: The substrate is ultrasonically cleaned and then dried for later use; S2: Fluorinated polyether acrylate and nitrogen heterocyclic monomers are mixed evenly under anaerobic conditions, and then an azo initiator is added. Prepolymerization is carried out at 55–65°C to obtain nitrogen heterocyclic graft copolymers. S3: Add organic solvent, graphene quantum dots, crosslinking agent and photoinitiator to the nitrogen heterocyclic graft copolymer in sequence, mix evenly, sonicate at room temperature for 10-15 min, and degas under vacuum to obtain coating adhesive; S4: Apply the coating adhesive to the substrate using coating equipment to obtain the final product.

10. The method for preparing the wear-resistant, stain-resistant, waterproof, and high-transmittance membrane according to claim 9, characterized in that, The coating equipment is a slot coating or a micro-grooved roller coating. The control parameters of the coating equipment are: wet film thickness 8–12 μm, UV curing: wavelength 365 nm, energy density 300–500 mJ / cm², linear speed 5–15 m / min, and post-baking: drying at 80°C for 2 min.

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