Highly transparent scratch-resistant antistatic coating and method for its production

Abstract

The present application belongs to the field of advanced coating and preparation, and particularly relates to a high-transparent and scratch-resistant multifunctional antistatic coating and a preparation method thereof. The present application provides a high-transparent and scratch-resistant antistatic coating, raw materials of the antistatic coating comprising fluorion-containing silsesquioxane monomer, functional monomer and catalyst; wherein the functional monomer is a crosslinking agent or an anti-crystallization agent. The coating obtained by the present application has a light transmittance of >98% (550 nm); a surface pencil hardness of greater than 9H, no scratches after more than 1000 times of steel wool rubbing; a surface resistivity of about 10 8 ~10 9 Ω / sq, and a fast electrostatic discharge rate.

Description

Technical Field

[0001] This invention belongs to the field of advanced coatings and preparation, specifically relating to a highly transparent, scratch-resistant, multifunctional antistatic coating and its preparation method. Background Technology

[0002] With the advent of the Internet of Things (IoT) era, touchscreens, as a primary means of human-computer interaction, are finding increasingly wider applications. In the 3C (computer, communication, and consumer electronics) market, capacitive touchscreens have become mainstream due to their high sensitivity, multi-touch support, and excellent anti-interference capabilities. However, in actual use, frequent contact and friction between the human body, clothing, and the screen of electronic products can generate static electricity, potentially leading to issues such as accidental touches, lag, and crashes. Furthermore, excessive static charge, during rapid release, can damage critical electronic components, causing screen distortion or even permanent black spots. Therefore, applying a highly transparent, anti-static coating to the surface of touchscreen products is essential for their proper use. In addition, to prevent scratches from foreign objects, this coating also needs to possess high hardness. In specific application scenarios, the coating also needs to have functions such as fingerprint resistance, antibacterial properties, dynamic scratch repair, high refractive index, and flexibility to solve problems such as rough feel and unresponsive touch caused by fingerprints, dust, bacteria, scratches, and impacts during use, thereby improving the user experience.

[0003] Currently, most commercially available touchscreens use low-resistivity ITO (indium tin oxide) as the antistatic layer material. However, the chemical vapor deposition or sputtering deposition methods used in ITO layer processing are demanding and complex, and the inherent brittleness of ITO severely limits its practical applications, especially in future foldable and flexible wearable devices. Furthermore, traditional multifunctional coatings integrate single-function coating materials through accumulation. For example, in touchscreens, a multi-layer structure composed of an ITO layer, a hardening layer, an anti-fingerprint layer, and other functional layers can simultaneously achieve antistatic, scratch-resistant, anti-fingerprint, and other essential functions. This approach not only involves complex processes, increasing production difficulty and cost, but also makes it difficult to control the interface compatibility of the multi-layer structure and balance multiple functions, significantly increasing the complexity and difficulty of coating preparation. Additionally, although high transparency and antistatic properties (surface resistivity 1.2 × 10⁻⁶) are available in academic research... 12 While there have been reports on Ω / sq) coatings (ACS Appl. Mater. Interfaces 2021, 13, 10301-10312), achieving simultaneous integration of high transparency, scratch resistance, and antistatic properties remains challenging, and integrating even more functions is even more difficult. Therefore, applying a single coating to the substrate that simultaneously provides all these properties would simplify the manufacturing process and significantly reduce costs and complexity. Summary of the Invention

[0004] Current coating technologies struggle to overcome the limitation of integrating multiple functions into a small number of coatings, or even a single coating. This is primarily due to the lack of simple and efficient methods to balance the resistivity and hardness of transparent materials. Therefore, the key to achieving multifunctionality in highly transparent antistatic coatings lies in how to effectively combine resistivity and multi-functionality through rational structural design and specialized building blocks.

[0005] To address the aforementioned shortcomings, this invention provides a highly transparent, scratch-resistant, and antistatic coating. The resulting coating has a light transmittance >98% (550nm); a surface pencil hardness greater than 9H; and exhibits no scratches after over 1000 cycles of steel wool rubbing; its surface resistivity is approximately 10⁻⁶. 8 ~10 9 Ω / sq, fast electrostatic discharge rate.

[0006] The technical solution of this invention:

[0007] The first technical problem to be solved by the present invention is to provide a highly transparent and scratch-resistant antistatic coating, wherein the raw materials of the antistatic coating include silsesquioxane monomers containing fluoride ions, functional monomers and catalysts; wherein the functional monomers are crosslinking agents or anti-crystallization agents.

[0008] Furthermore, the silsesquioxane monomers containing fluoride ions are classified into two categories based on whether they contain reactive groups, and their structures are at least one of the following structural formulas:

[0009]

[0010] in, or k + At least one of them; At least one of the reactive groups;

[0011] or At least one of the following non-reactive groups.

[0012] Preferably, R is a vinyl group. Styrene Phenyl or trifluoropropyl

[0013] Preferably, the X + Tetrabutylammonium

[0014] Furthermore, the functional monomer accounts for 5 to 20% of the molar amount of the sesquioxane monomer containing fluoride ions.

[0015] Furthermore, the catalyst accounts for 0.5 to 5% of the molar amount of the silsesquioxane monomer containing fluoride ions.

[0016] Furthermore, when the R group of the silsesquioxane monomer containing fluoride ions is a reactive group, the functional monomer is selected from a multifunctional crosslinking agent.

[0017] Furthermore, the multifunctional crosslinking agent includes at least one of the following: multifunctional olefin, multifunctional thiol, multifunctional epoxide, multifunctional silane, or multifunctional siloxane.

[0018] Preferably, the multifunctional olefin is selected from crosslinking agents in which the total number of vinyl / acrylate / methacrylate groups in a single molecule is greater than 1, such as neopentyl glycol diacrylate, trimethylolpropane triacrylate, etc.

[0019] The multifunctional thiols are selected from crosslinking agents with more than 1 thiol group per molecule, such as tris(3-mercaptopropionic acid)trimethylolpropane ester, pentaerythritol tetrakis(3-mercaptopropionic acid)tetraethylene ester, etc.

[0020] The multifunctional epoxides are selected from crosslinking agents with more than 1 number of epoxy groups per molecule, such as 1,2,5,6-diepoxyhexane, 4-vinyl-1-cyclohexene diepoxide, etc.

[0021] The multifunctional silanes or siloxanes include: linear, cyclic, random network, and ladder-shaped siloxanes, with the general structural formula being: Where R1 or Isoreactive groups, and One of the non-reactive groups, which may be the same or different, and cage-like silsesquioxanes T with peripheral groups of vinyl, styrene, mercaptopropyl, acrylate, and methacrylate. n (n = 8, 10, 12, etc.)

[0022] Furthermore, when the R group of the silsesquioxane monomer containing fluoride ions is a non-reactive group, the functional monomer is selected from anti-crystallization agents.

[0023] Furthermore, the anti-crystallization agent includes at least one of the following: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, trivinyltrimethylcyclotrisiloxane, tetravinyltetramethylcyclotetrasiloxane, etc.

[0024] Furthermore, the catalyst comprises:

[0025] The catalyst used in conjunction with the crosslinking agent is at least one of the following: azobisisobutyronitrile, azobisisobutyramidine hydrochloride, azobisisopropylimidazoline hydrochloride, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, or pyridine;

[0026] The catalyst used in conjunction with the anti-crystallization agent is at least one of the following: tetramethylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, etc.

[0027] Furthermore, when the R group of the fluoride-containing silsesquioxane monomer is a reactive group, the reactions that can occur with the crosslinking agent include: mercapto-olefin reaction, free radical polymerization reaction, ring-opening reaction, and hydrolysis-condensation reaction of siloxane.

[0028] Furthermore, when the R group of the silsesquioxane monomer containing fluoride ions is a non-reactive group, it can undergo a siloxane rearrangement reaction with the anti-crystallization agent.

[0029] Preferably, when R of the fluoride-containing silsesquioxane monomer is vinyl or styrene, the crosslinking agent is selected from: polyfunctional olefins or polyfunctional epoxides.

[0030] Preferably, when R in the silsesquioxane monomer containing fluoride ions is trifluoropropyl or phenyl, the anti-crystallization agent is octamethylcyclotetrasiloxane or tetramethyltetraphenylcyclotetrasiloxane.

[0031] Furthermore, the fluoride-containing silsesquioxane monomer is prepared by the following method: POSS precursor and anhydrous ion pair donor are added to solvent I at a molar ratio of 1:0.5 to 1.2, stirred for 16 to 24 hours, and the turbid suspension becomes translucent after standing. The suspension is concentrated and filtered, the solvent is removed under vacuum, and dried to obtain the fluoride-containing silsesquioxane monomer.

[0032] The POSS precursors are classified into two categories based on whether they contain reactive groups, and their structures are at least one of the following structural formulas:

[0033]

[0034] in

[0035] At least one of the reactive groups,

[0036] Or: At least one of the following non-reactive groups.

[0037] Furthermore, in the above-mentioned method for preparing silsesquioxane monomers containing fluoride ions, the ion pair donor includes any one of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, or potassium fluoride.

[0038] Furthermore, in the above-mentioned method for preparing silsesquioxane monomers containing fluoride ions, solvent I is at least one selected from tetrahydrofuran, chloroform, toluene, acetone, dichloromethane, xylene, methanol, ethanol, ethylene glycol, ethyl acetate, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0039] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned highly transparent and scratch-resistant antistatic coating. The preparation method is as follows: first, the raw materials are mixed evenly to obtain a coating composition, and then the coating composition is uniformly coated on the surface of the substrate to form the antistatic coating.

[0040] Furthermore, the method for preparing the coating composition from the raw materials is one of the following methods:

[0041] Method 1: A silsesquioxane monomer containing fluoride ions and a functional monomer are added to solvent II and stirred until dissolved. Then, a catalyst is added to prepare a coating composition; wherein, the functional monomer is a crosslinking agent.

[0042] Method 2: Add silsesquioxane monomers containing fluoride ions, functional monomers, and catalysts to solvent II and stir until dissolved. Wash and concentrate with solvent III to obtain a coating composition; wherein, the functional monomers are anti-crystallization agents.

[0043] Furthermore, solvent II is at least one of tetrahydrofuran, chloroform, toluene, acetone, dichloromethane, xylene, methanol, ethanol, ethylene glycol, ethyl acetate, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; and solvent III is at least one of methanol, ethanol, acetonitrile, toluene, xylene, acetone, dioxane, and deionized water.

[0044] Furthermore, the material of the substrate is selected from at least one of glass, polyethylene terephthalate, polyimide, polycarbonate, or polymethyl methacrylate.

[0045] Furthermore, the coating composition is uniformly coated on the substrate by any of the following methods: drip coating, spin coating, bar coating, scraping coating, or spraying.

[0046] Furthermore, the method for uniformly coating the coating composition onto the surface of the substrate to form the antistatic coating is as follows: the coating composition is uniformly applied to the substrate, and after the solvent evaporates, the antistatic coating is obtained by heat treatment and washing.

[0047] Furthermore, the heat treatment refers to curing at 50–200°C for 1 second to 120 minutes.

[0048] Furthermore, the thickness of the obtained antistatic coating is 5 nm to 500 μm, preferably 100 nm to 300 μm.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] Because this invention selects an ion pair donor that has a specific effect on siloxanes, it can efficiently solve the difficulties and conflicts brought about by the multi-layer structure used by traditional functional coatings to achieve multi-functional integration in terms of overall performance balance, and further endow it with more properties through the selection of appropriate functional monomers.

[0051] Because the coating provided by this invention uses a silsesquioxane monomer containing fluoride ions, combining the silsesquioxane with an ion-pair donor, the resistivity of this type of coating can be easily and efficiently adjusted. More importantly, under the action of the ion-pair donor, it can also be endowed with antibacterial, dynamic scratch repair and other functions.

[0052] Because the coating provided by this invention introduces special functional monomers, it not only imparts unique antistatic properties but also ensures high transparency. Furthermore, different types of functional monomers can be selected to achieve customized functions for the highly transparent and scratch-resistant antistatic coating, such as anti-oil, anti-fingerprint, flexibility, and high refractive index, thereby promoting the diversified development of the touch display field.

[0053] Because the coatings provided by this invention use a variety of functional monomers, such as silsesquioxane monomers containing fluoride ions, different types, structures, and functionalities of functional monomers can be selected to construct or rearrange crosslinking networks in various ways. Furthermore, by changing the relative content of functional monomers, the mechanical properties of the coating can be effectively controlled over a wide range to meet the application requirements in various scenarios.

[0054] Because the coating provided by this invention uses a fluoride-containing silsesquioxane monomer, the silsesquioxane is composed of an inorganic silicon-oxygen core and an outer organic group, which gives it the characteristics of nanoscale size and organic-inorganic hybrid structure. It can endow the coating with excellent optical and mechanical properties at the molecular scale through reasonable structural design.

[0055] Since the raw materials used in the functional coatings provided by this invention are all commercially available, the monomers are easy to prepare. They can be obtained simply by mixing various raw materials, coating and curing. This is simple, quick and easy to scale up.

[0056] At the same time, the present invention also has strong scalability. The coating can also be applied to the surface of optical products such as computer screens, optical lenses and precision optical components, so as to meet the protection and other functions while effectively preventing the dust attracted by surface electrostatics from affecting normal use. Attached Figure Description

[0057] Figure 1 The T8V8 (T8V8@F) prepared in Examples 1-3 of this invention using three different sizes of vinyl POSS as precursors - ), T 10 V 10 (T 10 V 10 @F - ) and T 12 V 12 (T 12 V 12 @F - Infrared spectrum of 3100-2800 cm⁻¹ -1 The alkyl peak and the peak appearing at 1120 cm⁻¹ -1 The nearby Si-O-Si peaks confirm the successful preparation of silsesquioxane monomers containing fluoride ions.

[0058] Figure 2 This is a schematic diagram illustrating the preparation of a highly transparent and scratch-resistant customized antistatic coating according to an embodiment of the present invention. First, a silsesquioxane monomer containing fluoride ions, a crosslinking agent or anti-crystallization agent, a catalyst, and a solvent are mixed to prepare a coating. The target coating can be obtained by coating and curing.

[0059] Figure 3 For ordinary glass cover ( Figure 3 A) and the highly transparent and scratch-resistant customized antistatic coating prepared in this invention ( Figure 3 In the electrostatic dissipation experiment (taking Example 8 as an example), the surface static charge generated by the electrostatic gun was not completely dissipated after 30 minutes, while the coating prepared by the present invention can dissipate the static charge in a very short time, proving that the coating has excellent antistatic effect.

[0060] Figure 4 The UV-Vis transmittance of the highly transparent and scratch-resistant customized antistatic coatings prepared in Examples 8-13 of this invention; Figure 4 It can be seen that the light transmittance of the coatings in Examples 8 to 13 of the present invention is greater than 98% (wavelength of 550nm), which proves that the coatings prepared by the present invention have high light transmittance.

[0061] Figure 5 A is the scratch resistance test device, using #0000 grade steel wool, and the calculated average vertical pressure is approximately 27.9 kPa; Figure 5B and 5D are SEM and optical microscope images of the PET after only one abrasion. Figure 5 C and 5E are SEM electron microscope images and optical microscope images of Example 8 of the present invention after 1000 scratches.

[0062] Figure 6 The antibacterial experimental effect of the highly transparent and scratch-resistant customized antistatic coating prepared in Example 8 of this invention is shown in the figure. It indicates that *Escherichia coli* and *Staphylococcus aureus* can grow normally on the surface of the glass cover, while almost no bacteria grow on the surface of the coating in Example 8. Figure 6 It can be seen that the functionalized coating prepared in Example 8 of the present invention has excellent antibacterial effect.

[0063] Figure 7 This invention demonstrates the dynamic repair effect of the highly transparent and scratch-resistant customized antistatic coating prepared in Example 8 of this invention. The figure shows the scratch condition of the coating surface before and after water vapor treatment at 50°C and 90% humidity. Figure 7 It can be seen that the scratches on the coating disappeared after the water vapor treatment, proving that this type of coating has excellent dynamic scratch repair performance.

[0064] Figure 8 The bending test of the double-layer composite material of the highly transparent and scratch-resistant customized antistatic coating and PET film prepared in Example 10 of the present invention showed that the coating prepared in Example 10 did not show any cracks when the bending radius was 1 mm, indicating that the customized coating material in Example 10 of the present invention has excellent flexibility.

[0065] Figure 9 The refractive index of the highly transparent and scratch-resistant customized antistatic coating prepared in Example 12 of this invention; by Figure 9 It can be seen that the refractive index of the coating prepared in Example 12 is greater than 1.68 (589nm), indicating that the coating material customized in Example 12 of the present invention has a high refractive index.

[0066] Figure 10 A represents the water contact angle of the highly transparent and scratch-resistant customized antistatic coating prepared in Example 13 of this invention. Figure 10 B demonstrates the anti-oil stain effect; by Figure 10 It can be seen that the water contact angle of the coating is >105°; the marker marks on the glass cover are not easy to remove, while the pen marks on the coating surface are easy to clean, indicating that the coating customized in Example 13 of this invention has excellent hydrophobic and oil-resistant properties. Detailed Implementation

[0067] This invention uses silsesquioxane monomers containing fluoride ions, where the silsesquioxane structure brings excellent characteristics of nanoscale size and organic-inorganic hybrid structure; combining silsesquioxane with ionic pair donors adjusts the resistivity of the coating and can also endow it with antibacterial, dynamic scratch repair and other functions; the introduction of functional monomers breaks the regularity of the overall network, avoids its crystallization, achieves high transparency, creates conditions for the practical application of the coating, and provides the coating with more selectable properties. The combination of multiple functional components finally produces a highly transparent, scratch-resistant, antistatic multifunctional coating.

[0068] The present invention will be further illustrated by the following embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0069] This invention provides a method for preparing a highly transparent and scratch-resistant customized antistatic coating. The preparation process steps and conditions of this method are as follows:

[0070] (1) Preparation of silsesquioxane monomers containing fluoride ions:

[0071] The POSS precursor and anhydrous ion pair donor were added to solvent I at a molar ratio of 1:0.5 to 1.2 and stirred for 16-24 hours. The turbid suspension became translucent after standing. The suspension was concentrated and filtered, and the solvent was removed under vacuum. After drying, silsesquioxane monomers containing fluoride ions were obtained.

[0072] (2) Preparation of coating composition:

[0073] Method 1: Add fluoride-containing silsesquioxane monomers and crosslinking agents accounting for 5-20% of the molar amount of fluoride-containing silsesquioxane monomers to solvent II and stir until dissolved. Then add catalysts accounting for 0.5-5% of the molar amount of fluoride-containing silsesquioxane monomers to obtain a coating composition.

[0074] Method 2: Add fluoride-containing silsesquioxane monomer, 5-20% of the molar amount of anti-crystallization agent and 0.5-5% of the molar amount of catalyst to solvent II and stir until dissolved. Wash and concentrate with solvent III to obtain the coating composition.

[0075] (3) The obtained coating composition is uniformly coated on the surface of the substrate by any one of the following methods: drop coating, spin coating, bar coating, scraping coating and spraying; the coating thickness is 5nm to 500μm, preferably 100nm to 300μm; after heat treatment (50 to 200℃), the surface is cleaned with solvent IV to obtain the highly transparent and scratch-resistant customized antistatic coating.

[0076] It is worth noting that: 1) In the following examples, the ratio of the precursor and ion pair donor of the fluoride-containing silsesquioxane monomer, the ratio of the fluoride-containing silsesquioxane monomer, the functional monomer, and the catalyst are all molar ratios; 2) The UV-Vis transmittance of the highly transparent and scratch-resistant customized antistatic coatings obtained in the following examples was tested using a Shimadzu UV-3600; the pencil hardness was tested using an Elecometer H501 pencil hardness tester; the surface resistivity was tested using an RTS-8 four-probe tester; the flexibility was tested using a micrometer; and the refractive index was tested using a Metricon MODEL 2010 / M prism coupler.

[0077] Example 1: Preparation of silsesquioxane monomers containing fluoride ions

[0078] Octadecyl cage-like silsesquioxane (T8V8, 5 mmol) was added to anhydrous tetrahydrofuran and stirred at room temperature until the monomer was completely dissolved. Then, tetrabutylammonium fluoride trihydrate (TBAF, 5 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran. The two solutions were then mixed and stirred at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension became translucent. The solvent was removed under vacuum, and the suspension was dried to obtain the final product—T8V8 containing fluoride ions (T8V8@F). - (Molecules, yield 79%)

[0079] Example 2: Preparation of silsesquioxane monomers containing fluoride ions

[0080] Decylvinyl cage-like silsesquioxane (T) 10 V 10 Add 5 mmol of tetrabutylammonium fluoride trihydrate (TBAF) to anhydrous tetrahydrofuran and stir at room temperature until the monomer is completely dissolved. Then, dissolve 5 mmol of tetrabutylammonium fluoride trihydrate (TBAF) in 50 mL of anhydrous tetrahydrofuran. Mix the two solutions and stir at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension becomes translucent. Remove the solvent under vacuum and dry to obtain the final product—T containing fluoride ions. 10 V 10 (T 10 V 10 @F - (molecule, yield 72%)

[0081] Example 3: Preparation of silsesquioxane monomers containing fluoride ions

[0082] Dodecylvinyl cage silsesquioxane (T) 12 V 12Add 5 mmol of tetrabutylammonium fluoride trihydrate (TBAF) to anhydrous tetrahydrofuran and stir at room temperature until the monomer is completely dissolved. Then, dissolve 5 mmol of tetrabutylammonium fluoride trihydrate (TBAF) in 50 mL of anhydrous tetrahydrofuran. Mix the two solutions and stir at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension becomes translucent. Remove the solvent under vacuum and dry to obtain the final product—T containing fluoride ions. 12 V 12 (T 12 V 12 @F - ( ) molecules, yield 64%.

[0083] Example 4: Preparation of silsesquioxane monomers containing fluoride ions

[0084] Octadecyl cage-like silsesquioxane (T8V8, 5 mmol) was added to anhydrous tetrahydrofuran and stirred at room temperature until the monomer was completely dissolved. Then, tetrabutylammonium fluoride trihydrate (TBAF, 4 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran. The two solutions were then mixed and stirred at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension became translucent. The solvent was removed under vacuum, and the suspension was dried to obtain the final product—T8V8 containing fluoride ions (T8V8@F). - ( ) molecules, yield 66%.

[0085] Example 5: Preparation of silsesquioxane monomers containing fluoride ions

[0086] Octadecyl cage-like silsesquioxane (T8V8, 5 mmol) was added to anhydrous tetrahydrofuran and stirred at room temperature until the monomer was completely dissolved. Then, tetrabutylammonium fluoride trihydrate (TBAF, 6 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran. The two solutions were then mixed and stirred at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension became translucent. The solvent was removed under vacuum, and the suspension was dried to obtain the final product—T8V8 containing fluoride ions (T8V8@F). - (Molecules, yield 70%)

[0087] Example 6: Preparation of silsesquioxane monomers containing fluoride ions

[0088] Octaptyryl cage-like silsesquioxane (SPOSS, 5 mmol) was added to anhydrous tetrahydrofuran and stirred at room temperature until the monomer was completely dissolved. Then, tetrabutylammonium fluoride trihydrate (TBAF, 5 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran. The two solutions were then mixed and stirred at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension became translucent. The solvent was removed under vacuum, and the suspension was dried to obtain the final product—SPOSS (SPOSS@F) with tetrabutylammonium as the outer cation and fluoride ions as the inner cation. - The yield was 82%.

[0089] Example 7: Preparation of silsesquioxane monomers containing fluoride ions

[0090] 8-trifluoropropyl cage-like silsesquioxane (FPOSS, 5 mmol) was added to anhydrous tetrahydrofuran and stirred at room temperature until the monomer was completely dissolved. Then, an equimolar amount of tetrabutylammonium fluoride trihydrate (TBAF, 5 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran. The two solutions were then mixed and stirred at room temperature for 16 hours to obtain a turbid suspension. After standing for a period of time, the suspension became translucent. The solvent was removed under vacuum, and the suspension was dried to obtain the final product—FPOSS (FPOSS@F) with tetrabutylammonium as the outer cation and fluoride ions as the inner cation. - (Molecules, yield 71%)

[0091] Example 8: Preparation of Coating

[0092] The T8V8@F in Example 1 - 0.6 mmol of trimethylolpropane triacrylate (0.1 mmol) was added to 20 mL of tetrahydrofuran and stirred at room temperature to dissolve. AIBN (0.03 mmol) was added as a free radical catalyst and stirred for five minutes. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 70 °C for 6 hours. The coating material was obtained by rinsing with ethanol.

[0093] Example 9

[0094] T in Example 2 10 V 10 @F - 0.6 mmol of trimethylolpropane triacrylate (0.1 mmol) was added to 20 mL of tetrahydrofuran and stirred at room temperature to dissolve. AIBN (0.03 mmol) was added as a free radical catalyst and stirred for five minutes. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 70 °C for 6 hours. The coating material was obtained by rinsing with ethanol.

[0095] Example 10

[0096] The T8V8@F in Example 1 - 0.6 mmol of neopentyl glycol diacrylate and 0.12 mmol of neopentyl glycol diacrylate were added to 20 mL of tetrahydrofuran and stirred at room temperature to dissolve. AIBN (0.03 mmol) free radical catalyst was added and stirred for five minutes. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 70 °C for 6 hours. The coating material was obtained by rinsing with ethanol.

[0097] Example 11

[0098] SPOSS@F in Example 6 -0.6 mmol of tetrahydrofuran and 0.1 mmol of octamethylcyclotetrasiloxane were added to 20 mL of tetrahydrofuran and stirred at room temperature to dissolve. Then, tetrabutylammonium fluoride catalyst (0.03 mmol) was added and stirred for five minutes. The solution was then washed and concentrated in acetonitrile. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 70 °C for 6 hours. The coating material was obtained by rinsing with ethanol.

[0099] Example 12

[0100] SPOSS@F in Example 6 - (0.6 mmol) and tetramethyltetraphenylcyclotetrasiloxane (0.1 mmol) were dissolved in 20 mL of tetrahydrofuran under stirring at room temperature, and then the catalyst tetrabutylammonium fluoride (0.03 mmol) was added. The mixture was stirred for five minutes and then washed and concentrated in acetonitrile. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 50 °C for 5 h. The coating material was obtained by rinsing with ethanol.

[0101] Example 13

[0102] FPOSS@F in Example 7 - (0.6 mmol) and trifluoropropylmethylcyclotrisiloxane (0.1 mmol) were dissolved in 20 mL of tetrahydrofuran under stirring at room temperature, and then the catalyst tetrabutylammonium fluoride (0.03 mmol) was added. The mixture was stirred for five minutes and then washed and concentrated in acetonitrile. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 50 °C for 5 h. The coating material was obtained by rinsing with ethanol.

[0103] Comparative Example 1

[0104] The T8V8@F in Example 1 - Add 20 mL of tetrahydrofuran (0.6 mmol) and stir to dissolve at room temperature. Add the free radical catalyst AIBN (0.03 mmol) and stir for five minutes. Then, drop the solution onto the substrate. After the solvent evaporates, cure at 70°C for 6 hours. Rinse with ethanol to obtain the coating material.

[0105] Comparative Example 2

[0106] SPOSS@F in Example 6 - (0.6 mmol) was dissolved in 20 mL of tetrahydrofuran at room temperature with stirring, and then the catalyst tetrabutylammonium fluoride (0.03 mmol) was added. The mixture was stirred for five minutes and then washed and concentrated in acetonitrile. The solution was then drop-coated onto the substrate. After the solvent evaporated, the solution was cured at 50 °C for 5 h. The coating material was obtained by rinsing with ethanol.

[0107] Table 2 summarizes the effective modulus, hardness, and H / E of Examples 8-13 of the present invention. *The study included measurements of pencil hardness, light transmittance, surface resistivity, triboelectric voltage, scratch repair capability, antibacterial capability, oil resistance, fingerprint resistance, bending radius, and 1000 steel wool scratch tests. Among these, the effective modulus and hardness obtained from the nanoindentation experiment showed that Examples 8-13 of this invention exhibited high hardness, while Example 10 showed a low effective modulus and H / E ratio. * The value is 0.17, indicating excellent flexibility; in the pencil hardness test, the coatings of Examples 8-12 of this invention all have a hardness greater than 9H, and Example 13 has a hardness of 8H, all of which exhibit excellent scratch resistance; in the light transmittance test, the coatings of Examples 8-13 of this invention all have a light transmittance greater than 98% at a wavelength of 550nm, indicating high light transmittance; the surface resistivity of the coatings of Examples 10-13 of this invention is all below 10. 8 ~10 9 Within the Ω / sq range, it exhibits excellent antistatic properties. The surface static voltage, measured by rubbing the coating surface with a copper rod 200 times, shows that the absolute values ​​of the instantaneous surface static voltage of the coatings in Examples 9-13 of this invention are all less than 50V, indicating that Examples 9-13 all have excellent antistatic effects. Specifically, the static voltage of Example 8 is greater than 50V, while the static voltage of Example 13 is negative. In Comparative Examples 1 and 2, the resulting coatings precipitate white crystals during curing, exhibiting poor transparency, which is unsuitable for practical applications.

[0108] Table 1 Raw materials for Examples 8-13

[0109]

[0110] Table 2 shows the performance results of the coatings obtained in Examples 8-13.

[0111]

Claims

1. A highly transparent, scratch-resistant, antistatic coating, characterized in that, The raw materials for the antistatic coating include: silsesquioxane monomers containing fluoride ions, functional monomers, and catalysts; wherein, the functional monomers are crosslinking agents or anti-crystallization agents; the functional monomers account for 5-20% of the molar amount of the silsesquioxane monomers containing fluoride ions; when R of the silsesquioxane monomers containing fluoride ions is a reactive group, the functional monomers are crosslinking agents; the reactions that can occur between the functional monomers and the crosslinking agents include: mercapto-olefin reactions, ring-opening reactions, and hydrolysis-condensation reactions of siloxanes; Alternatively: When R in a silsesquioxane monomer containing fluoride ions is a non-reactive group, the functional monomer is an anti-crystallization agent; it can undergo a siloxane rearrangement reaction with the anti-crystallization agent; Furthermore, the fluoride-containing silsesquioxane monomer is prepared by the following method: a POSS precursor and an ion pair donor are added to solvent I at a molar ratio of 1:0.5~1.2, and stirred for 16~24 hours to obtain a suspension. The turbid suspension becomes translucent after standing. The suspension is then concentrated, filtered, and the solvent is removed under vacuum. Finally, the suspension is dried to obtain the fluoride-containing silsesquioxane monomer. The POSS precursor is selected from at least one substance shown in the following structural formula: , or ; Where R= , , , , , , , , , , , or At least one of the reactive groups, Or: , , , , or At least one of the non-reactive groups; the solvent I is at least one of tetrahydrofuran, chloroform, toluene, acetone, dichloromethane, xylene, methanol, ethanol, ethylene glycol, ethyl acetate, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, or N,N-dimethylacetamide.

2. The highly transparent, scratch-resistant, antistatic coating according to claim 1, characterized in that, The R is , , or .

3. A highly transparent, scratch-resistant, antistatic coating according to any one of claims 1 to 2, characterized in that, The catalyst accounts for 0.5 to 5% of the molar amount of the sesquioxane monomer containing fluoride ions.

4. A highly transparent, scratch-resistant, antistatic coating according to any one of claims 1 to 2, characterized in that, When the functional monomer is a crosslinking agent, the catalyst is at least one of the following: azobisisobutyronitrile, azobisisobutyramidine hydrochloride, azobisisopropylimidazoline hydrochloride, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, or pyridine. When the functional monomer is an anti-crystallization agent, the catalyst is at least one of tetramethylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.

5. The highly transparent, scratch-resistant, antistatic coating according to claim 4, characterized in that, The crosslinking agent includes at least one of the following: a polyfunctional olefin, a polyfunctional thiol, a polyfunctional epoxide, a polyfunctional silane, or a siloxane; Alternatively: the anti-crystallization agent includes at least one of the following: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, trivinyltrimethylcyclotrisiloxane, and tetravinyltetramethylcyclotetrasiloxane.

6. The highly transparent, scratch-resistant, antistatic coating according to claim 5, characterized in that, The polyfunctional olefin is selected from: neopentyl glycol diacrylate or trimethylolpropane triacrylate; The polyfunctional thiols are selected from: tris(3-mercaptopropionic acid)trimethylolpropane ester or tetra(3-mercaptopropionic acid)pentaerythritol ester; The multifunctional epoxide is selected from: 1,2,5,6-dicyclohexane or 4-vinyl-1-cyclohexene diepoxide; The multifunctional silanes or siloxanes include: linear, cyclic, random network, and ladder-shaped siloxanes, with the general structural formula being: Where R1 or R2 = , reactive groups, or , , , , , One of the non-reactive groups, and cage-like silsesquioxanes T with peripheral groups of vinyl, styrene, mercaptopropyl, acrylate, and methacrylate. n n = 8, 10, or 12.

7. The highly transparent, scratch-resistant, antistatic coating according to claim 5, characterized in that, When R of the fluoride-containing silsesquioxane monomer is vinyl or styrene, the crosslinking agent is selected from: polyfunctional olefins and polyfunctional epoxides. When the R of the silsesquioxane monomer containing fluoride ions is trifluoropropyl or phenyl, the anti-crystallization agent is octamethylcyclotetrasiloxane or tetramethyltetraphenylcyclotetrasiloxane.

8. The highly transparent, scratch-resistant, antistatic coating according to claim 1, characterized in that, The ion pair donor is selected from any one of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, or potassium fluoride.

9. A method for preparing the highly transparent, scratch-resistant, antistatic coating according to any one of claims 1 to 8, characterized in that, The preparation method is as follows: first, the raw materials are mixed evenly to obtain a coating composition, and then the coating composition is uniformly coated on the surface of the substrate to form the antistatic coating.

10. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 9, characterized in that, The method for mixing the raw materials to obtain the coating composition is one of the following methods: Method 1: A silsesquioxane monomer containing fluoride ions and a functional monomer are added to solvent II and stirred until dissolved. Then, a catalyst is added to prepare a coating composition; wherein, the functional monomer is a crosslinking agent. Method 2: Add the silsesquioxane monomer containing fluoride ions, the functional monomer, and the catalyst to solvent II and stir until dissolved. Wash and concentrate with solvent III to obtain the coating composition; wherein, the functional monomer is an anti-crystallization agent. Solvent II is at least one of tetrahydrofuran, chloroform, toluene, acetone, dichloromethane, xylene, methanol, ethanol, ethylene glycol, ethyl acetate, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; solvent III is at least one of methanol, ethanol, acetonitrile, toluene, xylene, acetone, dioxane, and deionized water.

11. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 9, characterized in that, The substrate material is selected from at least one of glass, polyethylene terephthalate, polyimide, polycarbonate, or polymethyl methacrylate.

12. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 9, characterized in that, The coating composition is uniformly applied to the substrate by any of the following methods: drip coating, spin coating, rod coating, squeegee coating, or spray coating.

13. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 9, characterized in that, The method for uniformly coating the coating composition onto the surface of the substrate to form the antistatic coating is as follows: the coating composition is uniformly coated onto the substrate, and after the solvent evaporates, the antistatic coating is obtained by heat treatment and washing.

14. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 13, characterized in that, The heat treatment refers to heating and curing at 50–200 °C for 1 s–120 min.

15. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 13, characterized in that, The thickness of the antistatic coating is 5 nm to 500 μm.

16. The method for preparing the highly transparent, scratch-resistant, antistatic coating according to claim 15, characterized in that, The thickness of the antistatic coating is 100 nm to 300 μm.

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