A perfluoropolyether-based anti-blue light silane compound, a synthetic method thereof, and use thereof

Abstract

The application provides a perfluoropolyether-based silane compound and a preparation method. A perfluoropolyether carboxylic acid is subjected to an acyl chloride reaction, an amide reaction is performed between the obtained acyl chloride product and an aminohydroxybenzoic acid to obtain an intermediate 1 containing a carboxyl group; the intermediate 1 is subjected to an acyl chloride reaction, an amide reaction is performed between the obtained acyl chloride product and a diallylamine to obtain an intermediate 2 containing a double allyl group; an esterification reaction is performed between the intermediate 2 and 2-cyano-3-[4-(dimethylamino)phenyl]propenoic acid to obtain a chromophore intermediate 3 containing a double allyl group; and a hydrosilylation reaction is performed between the intermediate 3 and trimethoxysilane in the presence of a catalyst to obtain the perfluoropolyether-based anti-blue light silane compound. The perfluoropolyether-based anti-blue light silane compound designed and synthesized in the application has a good blocking effect on high-energy blue light of a 380-445 wave band, and has excellent anti-fouling and wear-resistant properties.

Description

Technical Field

[0001] This invention belongs to the field of surface treatment agents, specifically relating to a hydroxyl-terminated perfluoropolyether compound, its preparation method, and its application. Background Technology

[0002] With the widespread use of electronic display devices, people are exposed to blue light for a significantly longer period of time. Short-wavelength high-energy blue light in the range of 380–445 nm can easily penetrate the human eye, causing eye fatigue, dry eyes, and even retinal damage. Therefore, there is an urgent need for a functional coating that combines blue light protection with stain resistance and wear resistance.

[0003] Existing blue light blocking coatings mostly use organic absorbing dyes or multi-layer optical film structures, which have defects such as poor photostability, easy aging and fading, low light transmittance, and insufficient wear and stain resistance. Conventional perfluoropolyether silane coatings have excellent hydrophobic and antifouling properties, wear and weather resistance and low surface energy properties, and are widely used for surface modification of optical devices, but they only have protective functions and no ability to selectively block blue light.

[0004] Currently, there are no products that combine blue light blocking functionality with perfluoropolyether silanes, making it difficult to simultaneously meet the integrated requirements of precise blue light filtering, high light transmittance, stain and wear resistance, and long-term stability. Therefore, developing a perfluoropolyether blue light blocking silane compound has significant practical value. Summary of the Invention

[0005] The purpose of this invention is to develop a perfluoropolyether blue light blocking silane material. By adopting the solution in this invention, a perfluoropolyether silane compound that simultaneously possesses blue light blocking, stain resistance, and wear resistance functions can be obtained.

[0006] To achieve the above objectives, the first aspect of the present invention provides a perfluoropolyether blue light blocking silane compound.

[0007] A second aspect of the present invention provides a method for preparing a perfluoropolyether blue light blocking silane compound.

[0008] The third aspect of the present invention provides a perfluoropolyether blue light blocking silane compound obtained by the second aspect of the present invention.

[0009] A fourth aspect of the present invention provides a surface treatment agent containing the perfluoropolyether blue light blocking silane compound described in the first aspect of the present invention; or, the perfluoropolyether blue light blocking silane compound described in the third aspect of the present invention.

[0010] Through the above technical solution, the excellent effects of the present invention are as follows: the thin film formed on the substrate by the perfluoropolyether blue light blocking silane compound designed and synthesized by the present invention has a good blocking effect on high-energy blue light in the 380-445 wavelength band, and at the same time has excellent anti-fouling and wear-resistant properties. Attached Figure Description

[0011] Figure 1 The nuclear magnetic resonance spectrum of compound (1a) in Example 1 is shown.

[0012] Figure 2 The nuclear magnetic resonance spectrum of compound (2a) in Example 1 is shown.

[0013] Figure 3 The image shows the nuclear magnetic resonance spectrum of compound (3a) in Example 1.

[0014] Figure 4 The nuclear magnetic resonance spectrum of compound (4a) in Example 1 is shown.

[0015] Figure 5 The image shows the UV-Vis absorption spectrum of compound (4a). Detailed Implementation

[0016] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0017] To achieve the above objectives, a first aspect of the present invention provides a perfluoropolyether-based silane compound having the structure shown in formula (A). Formula (A), Wherein, A is a benzene ring, and B is Rf or RfCH2OCH2; Perfluoropolyethers are special perfluorinated polymers containing only three elements: carbon (C), phosphorus (F), and oxygen (O). Depending on the monomers used and the polymerization method, perfluoropolyethers mainly have the following four molecular structures: Type K, Type Y, Type Z, and Type D, the perfluoropolyether groups in this application, can be selected by those skilled in the art according to their needs. For example, the perfluoropolyether groups have the structure shown in formula (B), F - (CF2). d1 - (OC4F8) d2 -(OC3F6) d3 - (OC2F4) d4 - (OCF2) d5 - O(CF2) d6- Equation (B), wherein the order of the repeating units enclosed in parentheses with d1, d2, d3, d4 and d5 and whether each repeating unit has branches are arbitrary in the equation; d2, d3, d4 and d5 are greater than or equal to 0 and less than or equal to 100 respectively; the sum of d2, d3, d4 and d5 is greater than or equal to 1; d1 and d6 are integers greater than 0 and less than or equal to 20 respectively.

[0018] In the structure shown in equation (B), each repeating unit contains cases where there are branches, for example: -OC3F6- includes the following three structural formulas.

[0019] .

[0020] In some embodiments of this application, the perfluoropolyether group has a structure shown in any of formulas (C-1), (C-2), (C-3), and (C-4). Equation (C-1): CF3-(OC2F4) d4 -(OCF2) d5 -O-CF2-; where the sum of d4 and d5 is an integer greater than or equal to 5 and less than or equal to 200; Formula (C-2): F-(CF2)3-(OCF(CF3)CF2) d3 -O-(CF2)2-; where d3 is an integer greater than or equal to 5 and less than or equal to 100; Formula (C-3): CF3-(OCF(CF3)CF2) d3 -(OCF2) d5 -(OCF(CF3)) d4 -O-CF2-; where the sum of d3, d4, and d5 is an integer greater than or equal to 5 and less than or equal to 200; Equation (C-4): F-(CF2)3-(OCF2CF2CF2) d3 -O-(CF2)2-; where d3 is an integer greater than or equal to 5 and less than or equal to 100.

[0021] In this invention, in formula C-2 (OCF(CF3)CF2) d3 In the sum C-4 (OCF2CF2CF2) d3 These represent (OC3F6) respectively. d3 The branched and straight-chain structures. The number-average molecular weight of the groups shown in formula (C-1) is 500 to 23,000, preferably 1,500 to 23,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 6,000.

[0022] The number-average molecular weight of the groups shown in formula (C-2) is 1,000 to 16,000, preferably 1,500 to 23,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 6,000.

[0023] The number-average molecular weight of the groups shown in formula (C-3) is 200 to 33,000, preferably 1,500 to 23,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 6,000.

[0024] The number-average molecular weight of the groups shown in formula (C-4) is 1,000 to 16,000, preferably 1,500 to 23,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 6,000. The above number-average molecular weight is derived from... 19 F-NMR determination.

[0025] A second aspect of the present invention provides a method for preparing a perfluoropolyether-based silane compound, the method comprising the following steps: (1) The perfluoropolyether carboxylic acid was subjected to acyl chloride reaction, and the resulting acyl chloride product was subjected to amidation reaction with aminohydroxybenzoic acid to obtain compound 1 containing a carboxyl group; (2) Compound 1 was subjected to acyl chloride reaction, and the resulting acyl chloride product was subjected to amidation reaction with diallylamine to obtain compound 2 containing diallyl group; (3) Compound 2 was esterified with 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid to obtain compound 3 containing a dielyl chromophore; (4) Compound 3 was subjected to a hydrosilylation reaction with trimethoxysilane in the presence of a catalyst to obtain the perfluoropolyether-based blue light blocking silane compound.

[0026] In this invention, a perfluoropolyether-based silane compound with both blue light protection and anti-fouling functions is obtained by using the above-described preparation method.

[0027] According to the present invention, the purified material can be used for subsequent reactions. The specific purification steps can be selected by those skilled in the art based on production needs. For example, the purified substance can be obtained by washing the reactants with water, solvent extraction, and vacuum distillation.

[0028] In this invention, the amount of various reactants added can be appropriately adjusted as needed. For ease of implementation, a range of reactant amounts is provided. The equivalents in this application are calculated in molar amounts, for example: In step (1), the amount of carboxyl groups in perfluoropolyether carboxylic acid is 1 equivalent, the amount of acyl chloride reagent is 1-5 equivalents, the amount of N,N-dimethylformamide is 0.1-1.0 equivalents, the amount of aminohydroxybenzoic acid is 1-5 equivalents, the amount of alkaline substance is 1-5 equivalents, and the amount of solvent is (1-10 ml) / 1g perfluoropolyether carboxylic acid; In step (2), the amount of carboxyl group in compound 1 is 1 equivalent, the amount of acyl chloride reagent is 1-5 equivalents, the amount of N,N-dimethylformamide is 0.1-1.0 equivalents, the amount of diallylamine is 1-5 equivalents, the amount of alkaline substance is 1-5 equivalents, and the amount of solvent is (1-10 ml) / 1g of compound 1; In step (3), the amount of carboxyl group in compound 2 is 1 equivalent, the amount of 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid is 1-5 equivalent, the amount of condensing agent is 1-5 equivalent, the amount of activator is 0.1-1.0 equivalent, and the amount of solvent is (1-10 ml) / 1g of compound 2; In step (4), the molar number of double bonds in compound 3 is 1 equivalent, the amount of alkoxysilane is 1-5 equivalents, and the amount of catalyst is 1×10⁻⁶. -5 -5×10 -3 The equivalent amount and solvent volume are (1-10 ml) / 1g of compound 3.

[0029] To facilitate understanding of the technical solution of this application, some of the substances used in this application will be illustrated below. It should be noted that the raw materials used in the preparation method of this application are not limited to the substances listed below. Those skilled in the art can also choose other substitutes for preparation under the inspiration of the substances listed below.

[0030] The perfluoropolyether carboxylic acid is at least one of Rf-COOH or Rf-CH2OCH2COOH; The aminohydroxybenzoic acid is selected from the following structures:

[0031] The alkaline substance is selected from at least one of LiOH, NaOH, KOH, K2CO3, Na2CO3, NaHCO3, t-BuOK, pyridine, triethylamine, diisopropylethylamine, and 1,4-diazabicyclo[2.2.2]octane; The acyl chloride reagent is selected from oxalyl chloride or dimethyl sulfoxide; the condensing agent is selected from at least one of CDI, DCC, EDCI, DIC, HATU, HBTU, HCTU, TBTU, PyBOP, and BOP. The activator is selected from at least one of HOBt, HOAt, DMAP, and 4-PPY; The solvent is selected from at least one of m-difluorotoluene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, trifluorotrichloroethane, perfluorohexane, polyhexafluoropropylene, methanol, ethanol, tert-butanol, isopropanol, ethyl acetate, methyl acetate, acetone, dichloromethane, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

[0032] In some preferred embodiments, the technical solution of the present invention includes the following steps: (1) A mixture of perfluoropolyether carboxylic acid, N,N-dimethylformamide and solvent was prepared. An acyl chloride reagent was added dropwise to the mixture at 0-10°C. After the acyl chloride reagent was added, the mixture was reacted at room temperature for 1-5 h to obtain perfluoropolyether acyl chloride. In another reaction flask, aminohydroxybenzoic acid, an alkaline substance and a solvent were added. The perfluoropolyether acyl chloride was added dropwise to the mixture of compound 1, the alkaline substance and the solvent at 0-10°C. After the perfluoropolyether acyl chloride was added dropwise, the mixture was reacted at room temperature for 1-10 h to obtain compound 1.

[0033] (2) Compound 1, N,N-dimethylformamide and solvent were mixed. An acyl chloride reagent was added dropwise to the mixture at 0-10°C. After the addition of the acyl chloride reagent, the mixture was reacted at room temperature for 1-5 h. Then, the mixture was concentrated under reduced pressure to remove unreacted acyl chloride reagent, yielding an acyl chloride intermediate. Diallylamine, a basic substance and solvent were added to another reaction flask. The acyl chloride intermediate was added dropwise to the mixture of intermediate 1, the basic substance and solvent at 0-10°C. After the addition of the acyl chloride intermediate, the mixture was reacted at room temperature for 1-10 h to obtain compound 2.

[0034] (3) Compound 2, 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid (synthesized according to the literature Head-to-TailAssemblies of Dipolar, Piperazine-Linked Chromophores: Synthesis, X-ray Structure, and Dielectric Characterization) and solvent were mixed, and then condensing agent and activator were added in sequence. The mixture was reacted at room temperature for 1-5 h to obtain compound 3.

[0035] (4) Compound 3, trimethoxysilane, catalyst and solvent are mixed and reacted at 60~100℃ for 1~10 h to obtain blue light blocking perfluoropolyether silane compound 4.

[0036] The present invention also provides a perfluoropolyether-based blue light blocking silane compound prepared by the method, which achieves excellent blocking of high-energy blue light in the 380-445nm wavelength band.

[0037] The first aspect of the present invention provides a surface treatment agent containing the aforementioned perfluoropolyether-based blue light blocking silane compound.

[0038] A second aspect of the present invention provides a substrate having a cured film formed by the surface treatment agent attached to its surface.

[0039] The third aspect of the present invention provides a blue light blocking perfluoropolyether-based silane compound prepared according to the second aspect of the present invention.

[0040] A fourth aspect of the present invention provides a surface treatment agent containing the blue light blocking perfluoropolyether-based silane compound described in the first aspect of the present invention; or, the blue light blocking perfluoropolyether-based silane compound described in the third aspect of the present invention.

[0041] The following are the test methods for performance parameters involved in this invention: 1. Hydrophobicity test The contact angle of the treated layer (hereinafter referred to as the surface treatment layer) formed on the surface of a glass substrate after treatment with a surface treatment agent was measured with respect to water using a contact angle measuring device (HAKE-DWA).

[0042] 2. Steel wool abrasion durability test At 25°C, a 4 μL water droplet was deposited onto a glass slide using an injection needle. The angle between the water droplet and the surface was defined as the "static contact angle with water." The angle was measured using droplet shape analysis technology and equipment software of a DSA100 (droplet shape analyzer). The measurement uncertainty was + / - 1.3°.

[0043] Steel wool model: #0000 (manufactured by Bon Star) Weight: 1kg Stroke: 40 mm Movement speed: 60 rpm.

[0044] 3. Visible light transmittance test Testing instrument: Perkin Elmer Lambda 1050+ UV / Vis / NIR spectrometer.

[0045] Test parameters: wavelength range 300-780nm, data interval 5nm, data were collected and analyzed using UV-WinLab software, with a focus on examining the transmission curve characteristics in the 380-445nm band.

[0046] All tests were conducted at room temperature (23±2℃) and humidity (50±5%RH). Each sample was tested three times and the average value was taken to ensure the accuracy and reproducibility of the data.

[0047] In the following embodiments, unless otherwise specified, all raw materials used are commercially available.

[0048] Example 1 The blue light blocking perfluoropolyether-based silane compound (4a) was synthesized according to the following steps. Step 1: In a 100 ml round-bottom flask, add 10.0 g of CF3 (OCF2CF2) with an average composition. p (OCF2) q Perfluoropolyether carboxylic acid (MW=5000) of OCF2COOH, 0.03 g DMF, and 10 ml m-difluorotoluene (HFX) were reacted under N2 protection. 0.38 g of oxaloyl chloride was added in an ice bath. After the addition of oxaloyl chloride, the reaction was carried out at room temperature for 2 h. Unreacted oxaloyl chloride was then removed by pressure distillation to obtain a m-difluorotoluene solution of the acyl chloride intermediate. In another round-bottom flask, 20 ml of a mixed solvent (m-difluorotoluene:THF=1:1), 0.46 g of 5-amino-2-hydroxybenzoic acid, and 0.39 g of N,N-diisopropylethylamine (DIPEA) were added. The m-difluorotoluene solution of the acyl chloride intermediate was added dropwise to the above reaction mixture under an ice bath and nitrogen atmosphere. After the addition of the acyl chloride intermediate, the reaction was carried out at room temperature for 5 h.

[0049] After the reaction was complete, 20 mL of perfluorohexane was added, and then the mixture was extracted three times with methanol. The lower layer was collected and distilled under reduced pressure to obtain 9.0 g of red product, which was compound (1a).

[0050] 1 H NMR (600 MHz, CDCl3): δ 10.83 (s, 1H), 9.86 (s, 1H), 9.34 (s, 1H), 8.09 (s, 1H), 7.57 (s, 1H), 6.83 (s, 1H). The structural formula of (1a) is as follows: .

[0051] The reaction formula is as follows:

[0052] Step 2: In a 100 ml round-bottom flask, 10.0 g of compound (1a), 0.03 g of DMF, and 10 ml of m-difluorotoluene were added. Under N2 protection, 0.25 g of oxalyl chloride was added in an ice bath. After the addition of oxalyl chloride, the reaction was allowed to proceed at room temperature for 1.5 h to obtain a solution of m-difluorotoluene containing the acyl chloride intermediate. In another round-bottom flask, 20 ml of m-difluorotoluene, 0.28 g of diallylamine, and 0.37 g of N,N-diisopropylethylamine were added. Under an ice bath and nitrogen atmosphere, the m-difluorotoluene solution of the acyl chloride intermediate was added dropwise to the above reaction mixture. After the addition of the acyl chloride intermediate, the reaction was allowed to proceed at room temperature for 5 h.

[0053] After the reaction was complete, 20 mL of perfluorohexane was added, and then the mixture was extracted three times with methanol. The lower layer was collected and distilled under reduced pressure to obtain 9.5 g of yellow product, which was compound (2a).

[0054] 1 H NMR (600 MHz, CDCl3): δ 9.51 (s, 1H), 8.95 (s, 1H), 7.53 (d, J = 9.4Hz, 1H), 7.11 (s, 1H), 6.74 (s, 1H), 5.96–5.81 (m, 2H), 5.26 (t, J = 12.3 Hz, 4H), 4.07 (s, 4H). The structural formula of compound (2a) is as follows:

[0055] The reaction formula is as follows:

[0056] Step 3: 10 g of compound (2a), 0.6 g of 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid, 10 mL of m-difluorotoluene, and 10 mL of THF were added to a reaction flask and stirred until homogeneous. Then, 0.55 g of DCC and 0.12 g of DMAP were added sequentially, and the mixture was stirred overnight at room temperature. After the reaction was complete, 20 mL of perfluorohexane was added, followed by extraction three times with methanol. The lower layer was collected and distilled under reduced pressure to obtain 9.5 g of a pale red product, which was compound (3a).

[0057] 1 H NMR (600 MHz, CDCl3) δ 9.05 (s, 1H), 8.22 (s, 1H), 8.07 (d, J = 8.7Hz, 2H), 7.60 (d, J= 9.1 Hz, 1H), 7.57 (s, 1H), 7.24 (d, J = 8.9 Hz, 1H), 6.78 (d, J = 8.9 Hz, 2H), 5.91 (td, J = 10.4, 5.0 Hz, 1H), 5.82 (td, J = 10.5, 5.1 Hz,1H), 5.26 - 5.16 (m, 4H), 3.96 - 3.90 (m, 3H), 3.51 (s, 1H), 3.17 (s, 6H), 3.14 (s, 1H). The structural formula of compound (3a) is as follows:

[0058] The reaction formula is as follows:

[0059] Step 4: 10.0 g of compound (3a), 15 ml of m-difluorotoluene, 0.6 g of trimethoxysilane, 0.1 g of a 2% (w / w) platinum(O)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane-toluene solution, and 0.1 g of methyltriacetoxysilane were added to a reaction flask under nitrogen protection and incubated at 80 °C. o Heating at C for 3 hours, then cooling to room temperature, adding 20 mL of perfluorohexane, extracting three times with methanol, and finally distilling under reduced pressure to obtain 9.0 g of reddish-brown product, namely the perfluoropolyether blue light blocking silane compound (4a).

[0060] 1 H NMR (600 MHz, CDCl3): δ 9.48 (s, 1H), 8.23 ​​(d, J = 4.7 Hz, 1H), 8.06(d, J = 8.4 Hz, 2H), 7.56 (d, J = 9.4 Hz, 1H), 7.50 (d, J = 13.4 Hz, 1H), 7.43(s, 1H), 6.77 (d, J = 8.6 Hz, 2H), 3.71-3.45 (m, 18H), 3.17 (s, 6H), 1.81 -1.69 (m, 4H), 1.41 (s, 4H), 1.02 - 0.94 (m, 4H). The structural formula of compound (4a) is as follows:

[0061] The reaction formula is as follows:

[0062] The catalyst in the reaction is a platinum(0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane toluene solution with a solute mass percentage of 2%.

[0063] Example 2 The difference between Example 2 and Example 1 is that in Example 2, the average composition of the perfluoropolyether carboxylic acid is F-(CF2)3-(OCF(CF3)CF2). m O(CF2)2COOH (MW=5000). With the stoichiometric amounts of the corresponding reactants unchanged and the remaining steps unchanged, a perfluoropolyether blue light blocking silane compound (4b) was obtained.

[0064] Example 3 The difference between Example 3 and Example 1 is that in Example 3, the average composition of the perfluoropolyether carboxylic acid is CF3-(OCF(CF3)CF2). m -(OCF2) q -(OCF(CF3)) p -O-CF2COOH (MW=5000). The stoichiometric amounts of the corresponding reactants remain unchanged, and the remaining steps are kept constant to obtain a perfluoropolyether blue light blocking silane compound (4c).

[0065] Example 4 The difference between Example 4 and Example 1 is that in Example 4, the average composition of the perfluoropolyether carboxylic acid is F-(CF2)3-(OCF2CF2CF2). m -O-(CF2)2-COOH (MW=5000). With the stoichiometric amounts of the corresponding reactants unchanged and the remaining steps unchanged, a perfluoropolyether blue light blocking silane compound (4d) was obtained.

[0066] Example 5 The difference between Example 5 and Example 1 is that in Example 5, the average composition of the perfluoropolyether carboxylic acid is CF3(OCF2CF2). p (OCF2) q OCF2COOH (MW=2500), with the equivalent amount of the corresponding reactants remaining unchanged and the other steps unchanged, yields a perfluoropolyether blue light blocking silane compound (4e).

[0067] Example 6 The difference between Example 6 and Example 1 is that in Example 6, the average composition of the perfluoropolyether carboxylic acid is CF3(OCF2CF2). p(OCF2) q OCF2COOH (MW=3000). With the stoichiometric amounts of the corresponding reactants unchanged and the remaining steps unchanged, a perfluoropolyether blue light blocking silane compound (4f) is obtained.

[0068] Example 7 The difference between Example 7 and Example 1 is that in Example 7, the average composition of the perfluoropolyether carboxylic acid is CF3(OCF2CF2). p (OCF2) q OCF2COOH (MW=4000). With the equivalent amounts of the corresponding reactants unchanged and the remaining steps unchanged, a perfluoropolyether blue light blocking silane compound (4g) was obtained.

[0069] Application Example 1 The compound (4a) prepared in Example 1 was mixed with hydrofluoroether (3M, Novec HFE 7200) to a concentration of 20% by mass. The resulting 20% ​​solids content surface treatment agent was diluted with Novec HFE 7200 to obtain a diluted solution with a solids content of 0.1%. This diluted solution was then wet-sprayed onto chemically strengthened glass (Corning Gorilla 3) that had undergone plasma surface treatment, with a spraying amount set at 60 g / m². 2 The coated substrate is then baked at 150°C for 30 minutes and then cooled to room temperature to obtain a glass substrate treated with a surface treatment agent.

[0070] Application Example 2 The difference between this application example and application example 1 is that the compound (4b) prepared in example 2 is used instead of the compound (4a) in example 1.

[0071] Application Example 3 The difference between this application example and application example 1 is that the compound (4c) prepared in example 3 is used instead of the compound (4a) in example 1.

[0072] Application Example 4 The difference between this application example and application example 1 is that the compound (4d) prepared in example 4 is used instead of the compound (4a) in example 1.

[0073] Application Example 5 The difference between this application example and application example 1 is that the compound (4e) prepared in example 5 is used instead of the compound (4a) in example 1.

[0074] Application Example 6 The difference between this application example and application example 1 is that the compound (4f) prepared in example 6 is used instead of the compound (4a) in example 1.

[0075] Application Example 7 The difference between this application example and application example 1 is that the compound (4g) prepared in example 7 is used instead of the compound (4a) in example 1.

[0076] Application Example 8 The difference between this application example and application example 1 is that the compound (2a) prepared in example 1 is used instead of the compound (4a) in example 1.

[0077] Table 1 Hydrophobicity and Slip Properties

[0078] Table 2 Visible light transmittance and abrasion resistance

[0079] As can be seen from the above application examples and comparative examples, the surface treatment agent prepared using the perfluoropolyether blue light blocking silane compound of the present invention enables the glass substrate treated with it to have excellent blue light blocking and wear resistance properties. The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A perfluoropolyether-based blue light blocking silane compound, characterized in that, The compound has the structure shown in formula (A). Formula (A), Where A is a benzene ring and B is Rf or RfCH2OCH2.

2. The compound according to claim 1, characterized in that, The perfluoropolyether group Rf has the structure shown in formula (B). F-(CF2) d1 -(OC4F8) d2 -(OC3F6) d3 -(OC2F4) d4 -(OCF2) d5 -O(CF2 ) d6 - Formula (B), The order in which the repeating units d1, d2, d3, d4, and d5 enclosed in parentheses exist is arbitrary. And / or, each repeating unit with d1, d2, d3, d4 and d5 enclosed in parentheses may selectively contain branches; d2, d3, d4 and d5 are greater than or equal to 0 and less than or equal to 100 respectively; the sum of d2, d3, d4 and d5 is greater than or equal to 1; d1 and d6 are integers greater than 0 and less than or equal to 20 respectively.

3. The compound according to claim 1, characterized in that, The perfluoropolyether group Rf has a structure shown in any of the formulas (C-1), (C-2), (C-3), and (C-4). Equation (C-1): CF3-(OC2F4) d4 -(OCF2) d5 -O-CF2-; where the sum of d4 and d5 is an integer greater than or equal to 5 and less than or equal to 200; Formula (C-2): F-(CF2)3-(OCF(CF3)CF2) d3 -O-(CF2)2-; where d3 is an integer greater than or equal to 5 and less than or equal to 100; Formula (C-3): CF3-(OCF(CF3)CF2) d3 -(OCF2) d5 -(OCF(CF3)) d4 -O-CF2-; where the sum of d3, d4, and d5 is an integer greater than or equal to 5 and less than or equal to 200; Equation (C-4): F-(CF2)3-(OCF2CF2CF2) d3 -O-(CF2)2-; where d3 is an integer greater than or equal to 5 and less than or equal to 100.

4. A method for preparing perfluoropolyether-based silane compounds, characterized in that, The method includes the following steps: (1) The perfluoropolyether carboxylic acid was subjected to acyl chloride reaction, and the resulting acyl chloride product was subjected to amidation reaction with aminohydroxybenzoic acid to obtain compound 1 containing a carboxyl group; (2) Compound 1 was subjected to acyl chloride reaction, and the resulting acyl chloride product was subjected to amidation reaction with diallylamine to obtain compound 2 containing diallyl group; (3) Compound 2 was esterified with 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid to obtain compound 3 containing a dielyl chromophore; (4) Compound 3 was subjected to a hydrosilylation reaction with trimethoxysilane in the presence of a catalyst to obtain the perfluoropolyether-based blue light blocking silane compound.

5. The method according to claim 4, characterized in that, In step (1), The perfluoropolyether carboxylic acid is Rf-COOH or Rf-CH2OCH2COOH; The aminohydroxybenzoic acid is selected from any one of the following structural formulas: ； The alkaline substance is selected from at least one of LiOH, NaOH, KOH, K2CO3, Na2CO3, NaHCO3, t-BuOK, pyridine, triethylamine, diisopropylethylamine, and 1,4-diazabicyclo[2.2.2]octane; The acyl chloride reagent is selected from oxalyl chloride or dimethyl sulfoxide; The condensing agent is selected from at least one of CDI, DCC, EDCI, DIC, HATU, HBTU, HCTU, TBTU, PyBOP, and BOP; The activator is selected from at least one of HOBt, HOAt, DMAP, and 4-PPY; The solvent is selected from at least one of m-difluorotoluene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, trifluorotrichloroethane, perfluorohexane, polyhexafluoropropylene, methanol, ethanol, tert-butanol, isopropanol, ethyl acetate, methyl acetate, acetone, dichloromethane, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. The catalyst for the hydrosilylation reaction is a platinum catalyst.

6. The method according to claim 4, characterized in that, In step (1), the amount of carboxyl groups in perfluoropolyether carboxylic acid is 1 equivalent, the amount of acyl chloride reagent is 1-5 equivalents, the amount of N,N-dimethylformamide is 0.1-1.0 equivalents, the amount of aminohydroxybenzoic acid is 1-5 equivalents, the amount of alkaline substance is 1-5 equivalents, and the amount of solvent is (1-10 ml) / 1g perfluoropolyether carboxylic acid; In step (2), the amount of carboxyl group in compound 1 is 1 equivalent, the amount of acyl chloride reagent is 1-5 equivalents, the amount of N,N-dimethylformamide is 0.1-1.0 equivalents, the amount of diallylamine is 1-5 equivalents, the amount of alkaline substance is 1-5 equivalents, and the amount of solvent is (1-10 ml) / 1g of compound 1; In step (3), the amount of carboxyl group in compound 2 is 1 equivalent, the amount of 2-cyano-3-[4-(dimethylamino)phenyl]acrylic acid is 1-5 equivalent, the amount of condensing agent is 1-5 equivalent, the amount of activator is 0.1-1.0 equivalent, and the amount of solvent is (1-10 ml) / 1g of compound 2; In step (4), the molar number of double bonds in compound 3 is 1 equivalent, the amount of alkoxysilane is 1-5 equivalents, and the amount of catalyst is 1×10⁻⁶. -5 -5×10 -3 The equivalent amount and solvent volume are (1-10 ml) / 1g of compound 3.

7. The method according to claim 4, characterized in that, The reaction temperature in steps (1)-(2) is 0-10℃; the reaction temperature in step (3) is room temperature; and the reaction temperature in step (4) is 60-100℃.

8. A perfluoropolyether-based blue light blocking silane compound prepared by any one of claims 4-7, which achieves excellent blocking of high-energy blue light in the 380-445 nm wavelength band.

9. A surface treatment agent, characterized in that, Contains a perfluoropolyether-based blue light blocking silane compound as described in any one of claims 1-3 or 8.

10. A substrate, characterized in that, The surface of the substrate is coated with a cured film formed by the surface treatment agent of claim 9.

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