Anti-fingerprint agent, and preparation method therefor and use thereof

Abstract

The present invention belongs to the technical field of materials, and provides an anti-fingerprint agent, and a preparation method therefor and the use thereof. The anti-fingerprint agent is prepared from compounds such as trichlorotriazine, fluorine-containing aromatic diamine, methyl acrylate, and chloroalkyl siloxane and by means of reactions including substitution, addition, and polymerization. The anti-fingerprint agent has a hyperbranched three-dimensional structure, along with a C-F bond and a silane terminal group, and has excellent hydrophobic properties, anti-fouling properties, anti-fingerprint properties, abrasion-resistant properties, etc. Moreover, the anti-fingerprint agent does not contain per- or poly-fluoroalkyl substances (PFASs), which are restricted by the European Union, making it environmentally friendly. After coating, the initial water droplet angle on the surface of a substrate is 111° or above, and the water droplet angle still remains about 105° after rubbing with rubber and steel wool is performed 5000 times, such that the film has excellent anti-fingerprint and abrasion-resistant properties.

Description

An anti-fingerprint agent, its preparation method and application Technical Field

[0001] This invention relates to an anti-fingerprint agent, particularly to an anti-fingerprint agent with a hyperbranched three-dimensional structure containing CF bonds and siloxane end caps, and also to a method for preparing the anti-fingerprint agent and an application of the anti-fingerprint agent, belonging to the field of new materials technology. Background Technology

[0002] In recent years, high-tech products such as mobile phones, laptops, digital bracelets, and wearable electronic products have become increasingly popular among consumers. However, during frequent use, the casings and screen surfaces of these electronic products are easily contaminated by fingerprints, skin oils, sweat, and cosmetics, leading to blurred images and reduced image quality and aesthetic appearance. Therefore, higher requirements have been placed on the anti-fingerprint performance of coatings applied to the casings and screen surfaces of electronic products.

[0003] Fluorocarbons possess excellent heat and chemical stability, water and oil repellency, and low surface energy, making them commonly used for hydrophobic and oleophobic modification of various materials. Therefore, fluorocarbons / polymers have become a common main component of anti-fingerprint coatings. For example, Chinese Patent (Publication No. CN104559761A) discloses a method for preparing an anti-fingerprint coating by reacting a silane coupling agent, water, co-solvent, and heptadecafluorodecyltriethoxysilane at 60–80°C for 2–4 hours, applying it to a substrate, and baking it at 180–220°C for 3–7 minutes to obtain a fluorinated anti-fingerprint coating. This coating exhibits good anti-fingerprint properties and good adhesion to the substrate. Chinese Patent (Publication No. CN113265199A) uses perfluorononane, perfluorooctyltriethoxysilane, dodecafluoroheptyl methacrylate, polyvinylidene fluoride, methyl methacrylate, and co-solvent to prepare a hydrophobic, light-release fluorinated material coating. This coating features aging resistance, good hydrophobicity, oil resistance, and light release properties, while achieving a hardness of 2H. However, the use of perfluorinated long-chain alkanes will inevitably have adverse effects on human health and the environment. Furthermore, with the EU's proposal to restrict perfluorinated or polyfluorinated hydrocarbons (PFASs), the use of long-chain perfluorinated and polyfluorinated alkanes is limited. Therefore, the development of environmentally friendly anti-fingerprint agents with relatively low fluorine content is urgently needed. Summary of the Invention

[0004] In view of the above-mentioned technical problems existing in the prior art, the first objective of the present invention is to provide an anti-fingerprint agent with a hyperbranched three-dimensional structure, which includes CF bonds and is end-capped with siloxane, giving the anti-fingerprint agent excellent hydrophobic, anti-fouling, and abrasion resistant properties, and it does not contain perfluorinated or polyfluorinated hydrocarbons (PFASs) restricted by the European Union, making it green and environmentally friendly.

[0005] The second objective of this invention is to provide a method for preparing an anti-fingerprint agent. This method mainly constructs the anti-fingerprint agent through well-established substitution and addition reactions. It is simple to operate, has a high reaction rate, and operates under mild conditions, which is beneficial for industrial production.

[0006] The third objective of this invention is to provide an application of an anti-fingerprint agent, which is used on the surface of a substrate material to prepare an anti-fingerprint coating, exhibiting excellent hydrophobic, anti-fouling, and abrasion-resistant properties.

[0007] To achieve the above-mentioned technical objectives, the present invention provides an anti-fingerprint agent having the following structural formula:

[0008] in,

[0009] Rf represents a fluorinated aromatic group unit:

[0010] The following structural units are used:

[0011] n is an integer between 1 and 3000;

[0012] It contains fluorinated siloxane groups.

[0013] The anti-fingerprint agent provided by this invention has a special molecular structure. On the one hand, it has a hyperbranched three-dimensional structure, which significantly improves the tensile strength and abrasion resistance of the polyurethane matrix polymer. On the other hand, an appropriate amount of CF bonds are introduced into the hyperbranched main chain through aryl units, and siloxanes are introduced as end-capping groups. The introduction of fluorine and silicon improves the polarity, stability and heat resistance of the polyurethane matrix, giving the anti-fingerprint agent excellent hydrophobic, antifouling, anti-fingerprint and abrasion resistance properties.

[0014] As a preferred embodiment, the fluorinated aromatic unit has the following structural formula:

[0015] By replacing existing perfluorinated or polyfluorinated hydrocarbon-based substances with fluorinated aromatic units, anti-fingerprint agents can achieve low toxicity and biodegradability, making them environmentally friendly.

[0016] As a preferred embodiment, the fluorosiloxane has the following structural formula:

[0017] Preferred siloxanes are used for end-capping hyperbranched fluorinated polyurethanes, thereby endowing the hyperbranched polymers with strong polarity, high stability, and high heat resistance.

[0018] The present invention also provides an anti-fingerprint agent, which includes the following preparation steps:

[0019] 1) 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine are reacted by substitution reaction I to give 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine;

[0020] or,

[0021] 2,4,6-trichloro-1,3,5-triazine and a fluorinated aromatic diamine were subjected to substitution reaction II to give 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine;

[0022] The 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula:

[0023] The 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula:

[0024] 2) 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine reacts with methyl acrylate via addition reaction I to obtain intermediate I;

[0025] The intermediate I has the following structural formula:

[0026] 3) 2-Chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine undergoes an addition reaction II with methyl acrylate to give intermediate II;

[0027] The intermediate II has the following structural formula:

[0028] 4) Intermediate II and a fluorinated aromatic diamine undergo substitution reaction III to obtain monomer I;

[0029] The monomer I has the following structural formula:

[0030] 5) Intermediate I and monomer I undergo a polymerization reaction to form hyperbranched fluorinated polyurethane;

[0031] The hyperbranched fluorinated polyurethane has the following structural formula:

[0032] 6) Chloroalkylsiloxanes and fluorinated aromatic diamines are subjected to substitution reaction IV to yield siloxane-based fluorinated aromatic diamines;

[0033] The fluorinated aromatic diamine has the following structural formula:

[0034] 7) The hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine undergo a substitution reaction V to obtain the target product.

[0035] As a preferred embodiment, the fluorinated aromatic diamine comprises: At least one of them.

[0036] As a preferred embodiment, the chloroalkylsiloxane comprises: At least one of them.

[0037] As a preferred embodiment, the reaction conditions for substitution reaction I, II, or III are as follows: in the presence of a base, in an ice-water bath, for 2–6 hours. Specifically, in substitution reaction I, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine is 1:(3–3.8); in substitution reaction II, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine is 1:(1.8–2.4); and in substitution reaction III, the molar ratio of intermediate II to the fluorinated aromatic diamine is 1:(0.7–1.2).

[0038] As a preferred embodiment, the reaction conditions for substitution reaction IV are as follows: reaction at room temperature for 2 to 4 hours, wherein the molar ratio of chloroalkylsiloxane to fluorinated aromatic diamine in substitution reaction IV is 1:(1 to 1.6).

[0039] As a preferred embodiment, the reaction conditions for the substitution reaction V are: under the catalysis of ferric chloride, at room temperature, the reaction is carried out for 4 to 8 hours; wherein, in the substitution reaction V, the molar ratio of hyperbranched fluorinated polyurethane and siloxane-based fluorinated aromatic diamine is 1:(4 to 5)*(6+24n), where n is an integer between 0 and 3000.

[0040] As a preferred embodiment, the conditions for addition reaction I or addition reaction II are as follows: reflux at 80–120 °C for 4–10 h under the catalysis of copper chloride; wherein, in addition reaction I, the molar ratio of 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(6–8); and in addition reaction II, the molar ratio of 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(4–5).

[0041] As a preferred embodiment, the polymerization reaction conditions are: under the presence of alkali, reflux at 80-120°C for 8-12 hours; wherein, the molar ratio of intermediate I to monomer I in the polymerization reaction is 1:(1-1.2)*(6+24n), where n is an integer between 0 and 3000.

[0042] The present invention also provides an application of an anti-fingerprint agent for the preparation of an anti-fingerprint coating.

[0043] The anti-fingerprint agent provided by this invention is deposited on a substrate by vacuum evaporation. The initial water droplet angle on the substrate surface is above 111°, and it still maintains a water droplet angle of about 105° after 5000 rubs with rubber and steel wool. The adhesion test result shows 5B, which shows excellent anti-fingerprint and abrasion resistance.

[0044] The preparation method of the anti-fingerprint agent provided by the present invention includes the following specific preparation steps:

[0045] 1) Weigh 2,4,6-trichloro-1,3,5-triazine, fluorinated aromatic diamine, acetone, and sodium carbonate and add them to a reactor. React in an ice-water bath for 2–6 h. By controlling the ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine, substitution reaction I and substitution reaction II occur, respectively. The mixture is separated and purified by chromatographic column (hexane: ethyl acetate) to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, whose structural formulas are shown below:

[0046] The fluorinated aromatic diamine is a fluorinated substituent aromatic diamine or an aromatic diamine containing a short-chain fluorinated alkyl group. For example, the fluorinated aromatic diamine can be at least one of the following compounds:

[0047] Further preferably, the fluorinated aromatic diamine is 4,4'-diaminooctafluorobiphenyl. By selecting a suitable ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine, 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine or 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine can be obtained. For example, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine in the substitution reaction I is 1:(3-3.8); further preferably, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine is 1:3.4, in which case 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine is obtained. For example, in the substitution reaction II, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine is 1:(1.8–2.4); more preferably, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to the fluorinated aromatic diamine is 1:2.1. In this case, 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine is obtained.

[0048] 2) Weigh 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid, and copper chloride and add them to the reactor. Under a nitrogen atmosphere, reflux at 80–120 °C for 4–10 h to undergo addition reaction I. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate I, the structural formula of which is shown below:

[0049] In the addition reaction I, the molar ratio of 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(6-8); more preferably, the molar ratio of 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:7.2.

[0050] 3) Weigh 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid, and copper chloride and add them to the reactor. Under a nitrogen atmosphere, reflux at 80–120 °C for 4–10 h to undergo addition reaction II. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate II, the structural formula of which is shown below:

[0051] In the addition reaction II, the molar ratio of 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(4-5); more preferably, the molar ratio of 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine to methyl acrylate is 1:4.1.

[0052] 4) Weigh intermediate II, fluorinated aromatic diamine, acetone, and sodium carbonate and add them to the reactor. React in an ice-water bath for 2–6 hours to undergo substitution reaction III. After washing and vacuum distillation, monomer I is obtained, whose structural formula is shown below:

[0053] The molar ratio of intermediate II and fluorinated aromatic diamine in the substitution reaction III is 1:(0.7-1.2); more preferably, the molar ratio of intermediate II and fluorinated aromatic diamine is 1:1.1.

[0054] 5) Weigh intermediate I, monomer I, acetone, and sodium hydroxide (0.5 wt%) and add them to the reactor. Under reflux conditions at 80–120 °C, excess monomer I and intermediate I undergo a polymerization reaction to generate monomer III, a hyperbranched fluorinated polyurethane with a three-dimensional structure, as shown below:

[0055] The molar ratio of intermediate I to monomer I in the polymerization reaction is 1:(1~1.2)*(6+24n), where n is an integer between 0 and 3000; more preferably, the molar ratio of intermediate I to monomer I is 1:1.1*(6+24n), where n is an integer between 0 and 3000.

[0056] 6) Weigh out chloroalkylsiloxane, fluorinated aromatic diamine, and dichloromethane and add them to the reactor. React at room temperature for 2-4 hours to undergo substitution reaction IV. After washing and distillation, siloxane fluorinated aromatic diamine is obtained, and its structural formula is shown below:

[0057] The chloroalkylsiloxanes are specifically examples of:

[0058] At least one of the following. More preferably, chloromethyltriethoxysilane. The molar ratio of the chloroalkylsiloxane and the fluorinated aromatic diamine in the substitution reaction IV is 1:(1-1.6); more preferably, the molar ratio of the chloroalkylsiloxane and the fluorinated aromatic diamine is 1:1.1.

[0059] 7) Weigh out the three-dimensional hyperbranched fluorinated polyurethane, siloxane-based fluorinated aromatic diamine, ferric chloride, and dichloromethane and add them to the reactor. React at room temperature for 4-8 hours to undergo substitution reaction V. After washing and distillation, the final product is obtained. The molar ratio of the three-dimensional hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine in substitution reaction V is 1:(4-5)*(6+24n), where n is an integer between 0 and 3000. More preferably, the molar ratio of the three-dimensional hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine is 1:4.6*(6+24n), where n is an integer between 0 and 3000.

[0060] Compared with existing technical solutions, the beneficial effects of the technical solution of the present invention are as follows:

[0061] 1) The anti-fingerprint agent provided by this invention has a hyperbranched three-dimensional structure, which endows polyurethane with good tensile strength and abrasion resistance. At the same time, the CF bond and the siloxane used for end capping endow polyurethane with excellent properties such as strong polarity, high stability and high heat resistance. In summary, the fingerprint agent has excellent hydrophobic, anti-fouling, anti-fingerprint and abrasion resistance properties.

[0062] 2) The anti-fingerprint agent provided by the present invention avoids the use of perfluorinated or polyfluorinated hydrocarbons (PFASs) restricted by the EU proposal, and can achieve low toxicity and degradability of the anti-fingerprint agent, thus meeting the requirements of being friendly to human body and environment.

[0063] 3) The method for preparing the anti-fingerprint agent provided by this invention is synthesized through existing and very mature substitution and addition reactions. It is simple to operate, has a high reaction rate, and mild conditions, which is beneficial to industrial production.

[0064] 3) The anti-fingerprint agent provided by the present invention, after being coated by vacuum evaporation, has an initial water droplet angle of more than 111° on the substrate surface, and still maintains a water droplet angle of about 105° after 5000 rubs with rubber and steel wool. The adhesion test result shows 5B, which shows excellent anti-fingerprint and abrasion resistance. Attached Figure Description

[0065] Figure 1 shows the hydrogen nuclear magnetic resonance spectrum of the anti-fingerprint agent with a three-dimensional structure prepared in Example 1. Detailed Implementation

[0066] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0067] Example 1

[0068] The anti-fingerprint agent provided in this embodiment has the following structural formula:

[0069] Rf represents the main structure of 4,4'-diaminooctafluorobiphenyl, and its structural formula is shown below:

[0070] The polymer backbone structure is composed of 4,4'-diaminooctafluorobiphenyl, methyl acrylate, and trichlorotriazine, and its structural formula is as follows:

[0071] Where n = 10;

[0072] It is the product of the substitution reaction between chloromethyltriethoxysilane and 4,4'-diaminooctafluorobiphenyl, and its structural formula is as follows:

[0073] The specific preparation steps are as follows:

[0074] 1) 184.4 g (1 mol) of 2,4,6-trichloro-1,3,5-triazine and 4,4'-diaminooctafluorobiphenyl, with molar ratios of 1:3.4 and 1:2.1, respectively, were weighed and added to two reactors. Substitution reaction I and substitution reaction II were carried out in an ice-water bath for 2 h. The solutions were separated and purified by chromatographic column (hexane:ethyl acetate) to obtain 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine, respectively.

[0075] 2) Weigh 1 mol of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2 wt%) in a molar ratio of 1:7.2 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 5 h to undergo addition reaction I. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate I.

[0076] 3) Weigh 1 mol of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2 wt%) in a molar ratio of 1:4.1 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 5 h to carry out addition reaction II. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate II.

[0077] 4) Weigh intermediate II (1 mol) and 4,4'-diaminooctafluorobiphenyl, acetone (5 mol), and sodium carbonate (2 wt%) in a molar ratio of 1:1.1 and add them to the reactor. React in an ice-water bath for 3 h to undergo substitution reaction III. After washing and vacuum distillation, monomer I is obtained.

[0078] 5) Weigh 1 mol of intermediate I and monomer I with a molar ratio of 1:1.1*(6+24n)(n=10), 5 mol of acetone, and 0.5 wt% of sodium hydroxide and add them to the reactor. Under the condition of heating and reflux at 110℃, the excess monomer I and intermediate I undergo a polymerization reaction for 9 h to generate monomer III of hyperbranched fluorinated polyurethane with a three-dimensional structure.

[0079] 6) Weigh 1 mol of chloromethyltriethoxysilane, 4,4'-diaminooctafluorobiphenyl and 2 mol of dichloromethane in a molar ratio of 1:1.1 and add them to the reactor. React at room temperature for 2 h to undergo substitution reaction IV. After washing and distillation, siloxane-based fluorinated aromatic diamine is obtained.

[0080] 7) Weigh 1 mol of monomer III (1:4.6*(6+24n)(n=10), siloxane-containing fluorinated aromatic diamine, ferric chloride (3wt%), and dichloromethane (10 mol) into a reactor. React at room temperature for 6 h to induce substitution reaction V. After washing and distillation, the final product is obtained. Its structural schematic diagram is shown in Figure 1.

[0081] The novel environmentally friendly anti-fingerprint agent prepared in Example 1 was used for substrate coating (plasma treatment for 3 min, voltage 65-68V, current 2.5-3A; electron gun preheating power 10%-15%, silicon deposition 12nm, turntable rotation 99.9%, and the voltage ratio of the three stages of evaporation A:B:C was 20.5%:22.1%:22.1%). After completion, the adhesion, initial water droplet angle, resistance to rubber friction, resistance to steel wool friction, and resistance to oil-based pens on the substrate surface were tested, and the results are shown in Table 1.

[0082] Example 2

[0083] This embodiment provides an anti-fingerprint agent with the following structural formula:

[0084] Wherein, Rf represents the main structure of tetrafluorop-phenylenediamine, and its structural formula is shown below:

[0085] The polymer backbone of tetrafluorop-phenylenediamine, methyl acrylate, and trichlorotriazine is shown in the following structural formula:

[0086] Where n = 10;

[0087] It is the product of the substitution reaction between chloroethyltrimethoxysilane and tetrafluorop-phenylenediamine, and its structural formula is as follows:

[0088] The specific preparation steps are as follows:

[0089] 1) 184.4 g (1 mol) of 2,4,6-trichloro-1,3,5-triazine and tetrafluoro-p-phenylenediamine in molar ratios of 1:3.5 and 1:2.2, respectively, were weighed and added to two reactors. Substitution reaction I and substitution reaction II were carried out in an ice-water bath for 3 h. The solutions were separated and purified by chromatographic column (hexane:ethyl acetate) to obtain 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine, respectively.

[0090] 2) Weigh 1 mol of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2 wt%) in a molar ratio of 1:7 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 6 h to undergo addition reaction I. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate I.

[0091] 3) Weigh 1 mol of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2 wt%) in a molar ratio of 1:4.3 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 6 h to undergo addition reaction II. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate II.

[0092] 4) Weigh intermediate II (1 mol) with a molar ratio of 1:1.1, tetrafluorop-phenylenediamine, acetone (5 mol), and sodium carbonate (2.5 wt%) and add them to the reactor. React in an ice-water bath for 4 h to undergo substitution reaction III. After washing and vacuum distillation, monomer I is obtained.

[0093] 5) Weigh 1 mol of intermediate I and monomer I with a molar ratio of 1:1.1*(6+24n)(n=10), 5 mol of acetone, and 0.5 wt% of sodium hydroxide and add them to the reactor. Under the condition of heating and reflux at 120℃, the excess monomer I and intermediate I undergo a polymerization reaction (10 h) to generate monomer III of hyperbranched fluorinated polyurethane with a three-dimensional structure.

[0094] 6) Weigh out 1 mol of chloroethyltrimethoxysilane, 2 mol of tetrafluorop-phenylenediamine and dichloromethane in a molar ratio of 1:1.3 and add them to the reactor. React at room temperature for 2 h to undergo substitution reaction IV. After washing and distillation, siloxane-containing fluorinated aromatic diamine is obtained.

[0095] 7) Weigh 1 mol of monomer III with a molar ratio of 1:4.6*(6+24n)(n=10), 1 mol of siloxane-containing fluorinated aromatic diamine, 3 wt% of ferric chloride, and 10 mol of dichloromethane and add them to the reactor. React at room temperature for 7 h to undergo substitution reaction V. After washing and distillation, the final product is obtained.

[0096] The same procedure as in Example 1 was followed. After completion, tests were conducted on the substrate surface for properties such as adhesion, initial water droplet angle, resistance to rubber abrasion, resistance to steel wool abrasion, and resistance to oil-based pens. The results are shown in Table 1.

[0097] Example 3

[0098] The anti-fingerprint agent provided in this embodiment has the following structural formula:

[0099] Wherein, Rf is the main structure of tetrafluoro-1,3-phenylenediamine, and its structural formula is shown below:

[0100] The polymer backbone structure is composed of tetrafluoro-1,3-phenylenediamine, methyl acrylate, and trichlorotriazine, and its structural formula is as follows:

[0101] Where n = 10;

[0102] It is the product of the substitution reaction between chloromethyltrimethoxysilane and tetrafluoro-1,3-phenylenediamine, and its structural formula is as follows:

[0103] The specific preparation steps are as follows:

[0104] 1) 184.4 g (1 mol) of 2,4,6-trichloro-1,3,5-triazine and tetrafluoro-1,3-phenylenediamine in molar ratios of 1:3.6 and 1:2.1, respectively, were weighed and added to two reactors. Substitution reaction I and substitution reaction II were carried out in an ice-water bath for 2 h. The solutions were separated and purified by chromatographic column (hexane:ethyl acetate) to obtain 2,4,6-tris(fluoroaromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluoroaromatic diamine)-1,3,5-triazine, respectively.

[0105] 2) Weigh 1 mol of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2.5 wt%) in a molar ratio of 1:6.8 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 8 h to undergo addition reaction I. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate I.

[0106] 3) Weigh 1 mol of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid (5 mol), and copper chloride (2.5 wt%) in a molar ratio of 1:4.2 and add them to the reactor. Under a nitrogen atmosphere, reflux at 120 °C for 8 h to undergo addition reaction II. After washing and vacuum distillation, the product is purified by silica column chromatography to obtain intermediate II.

[0107] 4) Weigh intermediate II (1 mol) and tetrafluoro-1,3-phenylenediamine, acetone (5 mol), and sodium carbonate (2 wt%) in a molar ratio of 1:0.9 and add them to the reactor. React in an ice-water bath for 2 h to undergo substitution reaction III. After washing and vacuum distillation, monomer I is obtained.

[0108] 5) Weigh 1 mol of intermediate I and monomer I with a molar ratio of 1:1.2*(6+24n)(n=10), 5 mol of acetone, and 0.5 wt% of sodium hydroxide and add them to the reactor. React at 110℃ under reflux for 10 h. Excess monomer I and intermediate I undergo polymerization reaction to generate monomer III of hyperbranched fluorinated polyurethane with a three-dimensional structure.

[0109] 6) Weigh 1 mol of chloromethyltrimethoxysilane, 2 mol of tetrafluoro-1,3-phenylenediamine and dichloromethane in a molar ratio of 1:1.2 and add them to the reactor. React at room temperature for 2 h to undergo substitution reaction IV. After washing and distillation, siloxane-based fluorinated aromatic diamine is obtained.

[0110] 7) Weigh 1 mol of monomer III with a molar ratio of 1:4.3*(6+24n)(n=10), siloxane-containing fluorinated aromatic diamine, ferric chloride (3wt%), and dichloromethane (10 mol) and add them to the reactor. React at room temperature for 7 h to undergo substitution reaction V. After washing and distillation, the final product is obtained.

[0111] The same procedure as in Example 1 was followed. After completion, tests were conducted on the substrate surface for properties such as adhesion, initial water droplet angle, resistance to rubber abrasion, resistance to steel wool abrasion, and resistance to oil-based pens. The results are shown in Table 1.

[0112] Comparative Example 1

[0113] The difference between this comparative example and Example 1 is that 4,4'-diaminooctafluorobiphenyl is replaced with 4,4'-diaminobiphenyl, while the rest of the preparation steps and conditions are the same.

[0114] The same procedure as in Example 1 was followed. After completion, tests were conducted on the substrate surface for properties such as adhesion, initial water droplet angle, resistance to rubber abrasion, resistance to steel wool abrasion, and resistance to oil-based pens. The results are shown in Table 1.

[0115] Comparative Example 2

[0116] The difference between this comparative example and Example 1 is that chloromethyltriethoxysilane is no longer added for end-capping treatment, while the other preparation steps and conditions are the same.

[0117] The same procedure as in Example 1 was followed. After completion, tests were conducted on the adhesion, initial water droplet angle, resistance to rubber abrasion, resistance to steel wool abrasion, and resistance to oil-based pens on the substrate surface (tempered glass screen protector for mobile phones). The results are shown in Table 1.

[0118] Table 1. Performance test results of different embodiments and comparative products

[0119] Adhesion: Test with 3M 600 tape 3 times by drawing a 100-grid cross.

[0120] Hydrophobic angle test method: The static contact angle of the coating was measured using a JGW-360a contact angle meter. The test liquid volume was 2 μL, and the test environment was 24±1℃ with a relative humidity of 45±1%. Five points were measured for the water droplet contact angle, and the average value was taken.

[0121] Rubber abrasion resistance test method: The rubber abrasion resistance test is conducted by a ZJ-339-GSR abrasion tester. The coated substrate is fixed on the tester, the pressure is set to 1000g, the stroke is set to 40mm, and the speed is 40 cycles / min. After the test, the water droplet angle test result of the substrate is recorded.

[0122] Steel Wool Abrasion Resistance Test Method: The steel wool abrasion resistance test is conducted using a ZJ-339-GSR abrasion tester. The coated substrate is fixed on the tester, the rubber type is MUNBANGSAWOO, the pressure is set to 1000g, the stroke is set to 40mm, and the speed is 40 cycles / min. After the test, the water droplet angle test results of the substrate are recorded.

[0123] Oil-resistant pen test: Mark two points symmetrically in the middle of the sample board, with a distance of 5 cm between the two points; draw a straight line between the two points with an oil-based pen, wipe it with a lint-free cloth, and record it as 1 time; then draw a straight line in the same position with an oil-based pen and wipe it with a lint-free cloth, repeating this process until the oil-based pen marks cannot be wiped clean with a lint-free cloth, and record the number of times as N times. The number of times the oil-resistant pen is used is (N-1) times. The more times the oil-resistant pen is used, the better the oil resistance of the surface.

[0124] As can be seen from the data in Examples 1-3, the anti-fingerprint agent, after being adhered to the substrate surface as a film material, exhibits excellent adhesion, hydrophobicity, anti-fouling properties, abrasion resistance, and oil-based pen resistance. In Comparative Examples 1 and 2, since CF functional groups and end-capping siloxanes were not added, respectively, the resulting substrate surfaces did not show significant differences in adhesion, but their hydrophobicity, abrasion resistance, and oil-based pen resistance were significantly reduced. Figure 1 shows the 1H NMR spectrum of the anti-fingerprint agent prepared in Example 1, indicating the successful preparation of the anti-fingerprint agent.

[0125] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anti-fingerprint agent characterized in that: having the following structural formula: in, Rf represents a fluorinated aromatic group unit: for the following structural units: n is an integer between 1 and 3000; It contains fluorinated siloxane groups.

2. The anti-fingerprint agent according to claim 1, characterized in that: The fluorine-containing aromatic group unit has the following structural formula: The fluorine-containing siloxane has the following structural formula:

3. An anti-fingerprint agent according to claim 1 or 2, characterized in that: The preparation steps include the following: 1) 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine are reacted by substitution reaction I to give 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine; or, 2,4,6-trichloro-1,3,5-triazine and a fluorinated aromatic diamine were subjected to substitution reaction II to give 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine; The 2,4,6-tris(fluorine-containing aromatic diamine)-1,3,5-triazine has the following structural formula: The 2-chloro-4,6-bis(fluorine-containing aromatic diamine)-1,3,5-triazine has the following structural formula: 2) 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine reacts with methyl acrylate via addition reaction I to obtain intermediate I; The intermediate I has the following structural formula: 3) 2-Chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine undergoes an addition reaction II with methyl acrylate to give intermediate II; The intermediate II has the following structural formula: 4) Intermediate II and a fluorinated aromatic diamine undergo substitution reaction III to obtain monomer I; The monomer I has the following structural formula: 5) Intermediate I and monomer I undergo a polymerization reaction to form hyperbranched fluorinated polyurethane; The hyperbranched fluorine-containing polyurethane has the following structural formula: 6) Chloroalkylsiloxanes and fluorinated aromatic diamines are subjected to substitution reaction IV to yield siloxane-based fluorinated aromatic diamines; The fluorine-containing aromatic diamine has the following structural formula: 7) The hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine undergo a substitution reaction V to obtain the target product.

4. The method for preparing an anti-fingerprint agent according to claim 3, characterized in that: The fluorine-containing aromatic diamine includes: at least one of the group consisting of 5. The method for preparing an anti-fingerprint agent according to claim 3, characterized in that: The chloroalkylsiloxane comprises: at least one of the group consisting of 6. The method for preparing an anti-fingerprint agent according to claim 3, characterized in that: The reaction conditions for substitution reaction I, II, or III are as follows: in the presence of a base, in an ice-water bath, for 2–6 hours. The reaction conditions for the substitution reaction IV are: 2-4 hours at room temperature; The reaction conditions for the substitution reaction V are: under the catalysis of ferric chloride, at room temperature, for 4 to 8 hours; in, In substitution reaction I, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine is 1:(3-3.8); In substitution reaction II, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine is 1:(1.8–2.4). In substitution reaction III, the molar ratio of intermediate II to the fluorinated aromatic diamine is 1:(0.7–1.2). In substitution reaction IV, the molar ratio of chloroalkylsiloxane to fluorinated aromatic diamine is 1:(1–1.6). In substitution reaction V, the molar ratio of hyperbranched fluorinated polyurethane and siloxane-based fluorinated aromatic diamine is 1:(4~5)*(6+24n), where n is an integer between 0 and 3000.

7. The method for preparing an anti-fingerprint agent according to claim 3, characterized in that: The conditions for addition reaction I or addition reaction II are: reflux at 80–120°C for 4–10 h under the catalysis of copper chloride; wherein, In addition reaction I, the molar ratio of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(6-8). In addition reaction II, the molar ratio of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(4-5).

8. The method for preparing the anti-fingerprint agent according to claim 3, characterized in that: The polymerization reaction condition is: in the presence of alkali, at a temperature of 80-120℃, refluxing for 8-12h; Wherein, the molar ratio of intermediate I and monomer I in the polymerization reaction is 1:(1-1.2)﹡(6+24n), n is an integer between 0 and 3000.

9. Use of an anti-fingerprint agent according to claim 1 or 2, characterized in that: for preparing an anti-fingerprint coating.

Images