Hardening liquid, preparation method thereof, coating and application

Abstract

The invention discloses hardening liquid as well as a preparation method, a coating and application thereof. The hardening liquid comprises an acidic hydrolysate of tetraalkoxysilane, siloxane containing reactive groups, a solvent and an auxiliary agent. The siloxane containing reactive groups in the hardening liquid can be used as a film-forming agent to prepare a subsequent coating, and more importantly, the siloxane containing reactive groups in the hardening liquid contributes to stable dispersion of a silicon-containing compound in an acidic hydrolysate of tetraalkoxysilane in the hardening liquid; the risk that the silicon-containing compound further reacts to generate silicon dioxide particles is reduced, and the stability of the hardening liquid is improved.

Description

Technical Field

[0001] This application relates to the field of hardening liquids, and more specifically to a hardening liquid, its preparation method, coating, and application. Background Technology

[0002] Traditional sunglasses lenses are mostly made of glass and resin. Glass lenses are gradually being phased out due to their weight and fragility. Compared to glass lenses, resin lenses are lightweight, impact-resistant, not easily broken, and have good light transmission, with a light transmittance of 84%-95%, making them more popular with consumers. Furthermore, the manufacturing process of resin lenses aspherical lenses is far less difficult than that of glass lenses, resulting in lower manufacturing costs.

[0003] However, resin lenses have a significant drawback: poor abrasion resistance, making the lens surface easily scratched. Therefore, a hardened film, formed by curing with a hardening solution, is typically applied to the surface of resin lenses to improve their abrasion and scratch resistance, enabling them to withstand damage from hard objects and extending their lifespan. Currently, silica particles are commonly added to the hardening solution for resin lenses to enhance the abrasion and scratch resistance and hardness of the hardened film. However, silica particles are inorganic and have compatibility issues with other organic components in the hardening solution, resulting in poor stability of hardening solutions containing silica particles, which does not meet market demands.

[0004] Therefore, in order to meet market demand, it is necessary to design a hardening fluid with excellent stability. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this application is to overcome the above-mentioned defects in the prior art. The purpose is to provide a curing liquid in which the siloxane containing reactive groups can not only be used as a film-forming agent to prepare subsequent coatings, but more importantly, the siloxane containing reactive groups in the curing liquid helps to stably disperse silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane in the curing liquid, reducing the risk of silicon-containing compounds further reacting to form silica particles and improving the stability of the curing liquid.

[0006] A first aspect of this application provides a curing liquid comprising an acidic hydrolysis product of a tetraalkoxysilane, a siloxane containing a reactive group, a solvent, and an additive.

[0007] This application reduces the risk of incompatibility between inorganic and organic systems and improves the stability of the curing solution by introducing the acidic hydrolysis product of tetraalkoxysilane into the curing solution, instead of directly introducing inorganic silica particles. Furthermore, the addition of siloxanes containing reactive groups not only serves as a film-forming material for subsequent curing film preparation, but more importantly, it further reduces the risk of tetraalkoxysilane continuing to undergo deep condensation at storage temperatures to form silica, significantly improving the stability of the curing solution. During the subsequent film formation process, the acidic hydrolysis product of tetraalkoxysilane can further condense to form silica, enhancing the wear resistance and hardness of the cured film.

[0008] In any embodiment, the tetraalkoxysilane comprises the structure shown in Formula I.

[0009]

[0010] Among them, R1, R2, R3, and R4 each independently include C. 1-4 At least one of the alkyl groups, optionally, the tetraalkoxysilane includes at least one of tetraethyl silicate, tetramethyl silicate, tetrapropyl silicate, and tetrabutyl silicate.

[0011] In any embodiment, the siloxane containing reactive groups includes at least one of the structures shown in Formula II-1, Formula II-2, Formula III, and Formula IV.

[0012]

[0013]

[0014] Among them, R 11 R 12 R 13 R 15 R 16 R 17 R 21 R 23 R 24 R 25 R 31 R 33 R 34 R 35 Each independently includes C 1-4 Alkyl, C 1-4 At least one of the alkoxy groups, R 14 R 18 R 22 R 32 Including C 1-8 Alkyl, C 1-8 Alkoxy, C 1-8At least one of cycloalkyl and aromatic groups, and R 11 R 12 R 13 At least one of them includes C 1-4 At least one of the alkoxy groups, R 15 R 16 R 17 At least one of them includes C 1-4 At least one of the alkoxy groups, R 23 R 24 R 25 At least one of them includes C 1-4 At least one of the alkoxy groups, R 33 R 34 R 35 At least one of them includes C 1-4 At least one of the alkoxy groups, optionally, the siloxane containing the reactive group includes at least one of γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxypropyl)triethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane.

[0015] In any embodiment, the solvent includes water, and the hardening liquid does not include organic solvents other than the alcohol produced by the acidic hydrolysis of the tetraalkoxysilane.

[0016] Reducing the use of organic solvents can not only effectively improve the environmental friendliness of the hardening liquid, but also greatly reduce its flammability, thereby improving the safety of the hardening liquid during production, storage, transportation and use. At the same time, water, as a solvent for the hardening liquid, can be stored and transported under conventional cold chain conditions (0-5℃), which greatly reduces storage and transportation costs.

[0017] In any embodiment, the auxiliary agent includes at least one of a catalyst and a surfactant. The catalyst includes at least one of aluminum, zinc, iron, or cobalt metal acetylacetonate, diamide, imidazole, amine, organic sulfonic acid and its amine salt, alkali metal salt of carboxylic acid, and cyclic azide compound. The surfactant includes at least one of BYK347, BYK3455, BYK348, BYK3410, BYK307, Borchi Gol LA50, Capstone FS35, and Megaface F477.

[0018] In any embodiment, the acrylate monomer includes at least one of monofunctional acrylate monomers and polyfunctional acrylate monomers.

[0019] In any embodiment, the monofunctional acrylate monomer includes at least one of 2-phenoxyethyl acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 2-acrylate-[[1,1-binaphthyl]-2,2-di(oxy-2,1-ethide)] ester, ethoxybisphenol A diacrylate, 4-acryloylmorpholine, N-vinylpyrrolidone, tri(2-hydroxyethyl)isocyanurate triacrylate, and their modified forms.

[0020] In any embodiment, the multifunctional acrylate monomer includes at least one of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, bisphenol fluorene diacrylate, 2-acrylate-[[1,1-binaphthyl]-2,2-di(oxy-2,1-ethideyl)] ester, bisphenol A diacrylate ethoxylated, bisphenol A dimethacrylate ethoxylated, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, bis-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, bis-pentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, and their modified forms.

[0021] In any embodiment, the molar ratio of the tetraalkoxysilane to the siloxane containing the reactive group is 1:(1 / 4 to 4), and optionally 1:(0.5 to 3).

[0022] Controlling the molar ratio of tetraalkoxysilane to siloxane containing reactive groups to 1:(1 / 4–4) ensures sufficient interaction between the siloxane containing reactive groups and the silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane, while effectively reducing the impact of excessive siloxane containing reactive groups on the stability of the curing solution. Further controlling the molar ratio of tetraalkoxysilane to siloxane containing reactive groups to 1:(0.5–3) further balances the stability of the curing solution and the wear resistance of the cured film.

[0023] In any embodiment, the molar ratio of the tetraalkoxysilane to the solvent is 1:(2-50), optionally 1:(8-25), and the molar ratio of the sum of the moles of the tetraalkoxysilane and the siloxane containing the reactive group to the moles of the solvent is 1:(1-30), optionally 1:(5-20).

[0024] By controlling the molar ratio of tetraalkoxysilane to solvent, and the molar ratio of the sum of the moles of tetraalkoxysilane and siloxane containing reactive groups to solvent within a suitable range, the above substances can form a stable miscible system, so that the properties of the hardening solution remain stable after long-term storage.

[0025] In any embodiment, the mass content of the tetraalkoxysilane is 5% to 55% based on the total mass of the hardening liquid, and optionally 15% to 55%.

[0026] In any embodiment, based on the total mass of the hardening liquid, the mass content of the siloxane containing the reactive group is 5% to 55%, optionally 15% to 55%.

[0027] In any embodiment, the solvent content is 10% to 70% by mass, and optionally 10% to 60%, based on the total mass of the hardening liquid.

[0028] A second aspect of this application provides a method for preparing a hardening liquid, the method comprising:

[0029] At 15℃~20℃, tetraalkoxysilane and acid solution are mixed and hydrolyzed to prepare acidic hydrolysis products, wherein the molar ratio of tetraalkoxysilane to water in hydrochloric acid solution is 1:(2~4).

[0030] At a temperature not exceeding 35°C, the acidic hydrolysis product is mixed with a siloxane containing a reactive group and stirred until homogeneous to obtain a mixed solution.

[0031] The mixed solution, additives, and solvent are mixed and stirred evenly at a temperature not exceeding 40°C to prepare a hardening liquid.

[0032] In any embodiment, the molar ratio of the tetraalkoxysilane to the siloxane containing the reactive group is 1:(1 / 4 to 4), and optionally 1:(0.5 to 3).

[0033] A third aspect of this application provides a coating comprising a substrate and a hardened film layer located on at least one side of the substrate, the hardened film layer being prepared by a hardening liquid provided in the first aspect of this application or a hardening liquid prepared by a preparation method provided in the second aspect of this application.

[0034] The fourth aspect of this application provides the application of the coating provided in the third aspect of this application in the field of lenses. Detailed Implementation

[0035] The following detailed description discloses the hardening liquid of this application, its preparation method, and its application embodiments. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of actually identical structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Any product identical or similar to this application, derived by anyone based on the teachings of this application or by combining features of this application with other prior art, falls within the protection scope of this application.

[0036] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "ab" represents a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. Similarly, the numerical range "0-7" indicates that all real numbers between "0" and "7" have been listed in this document; "0-7" is simply a shortened representation of these numerical combinations. Furthermore, when describing an integer with a parameter ≥ 3, it is equivalent to disclosing that the parameter is, for example, an integer such as 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0037] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0038] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0039] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), indicating that the method may include steps (1) and (2) performed sequentially, or it may include steps (2) and (1) performed sequentially. For example, the mention that the method may also include step (3) indicates that step (3) may be added to the method in any order. For example, the method may include steps (1), (2) and (3), or it may include steps (1), (3) and (2), or it may include steps (3), (1) and (2), etc.

[0040] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0041] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0042] This application discloses a curing liquid comprising an acidic hydrolysis product of a tetraalkoxysilane, a siloxane containing a reactive group, a solvent, and an additive.

[0043] In this paper, the term "tetraalkoxysilane" refers to a substance in which the hydrogen atoms in the four Si-H bonds of a silane are replaced by alkoxy groups.

[0044] In this document, the term "acidic hydrolysis product of tetraalkoxysilane" refers to the product obtained by preliminary hydrolysis of tetraalkoxysilane under acidic conditions; the structure of the acidic hydrolysis product of tetraalkoxysilane includes, but is not limited to, the following: Or R x -OH (x is 1, 2, 3 or 4); the acidic hydrolysis products of tetraalkoxysilanes include silicon-containing compounds and alcohols, including but not limited to silicon-containing compounds. Furthermore, substances containing two or more silicon atoms in the acidic hydrolysis products of tetraalkoxysilanes can be called silicon-oxygen crosslinkers, which include, but are not limited to, those containing silicon atoms.

[0045] In this document, the term "siloxane containing a reactive group" refers to a siloxane that can react under high energy (heating or UV light irradiation), and the reactive group includes, but is not limited to, amino, methacryloyloxy, acryloyloxy, epoxy, or carbon-carbon double bond.

[0046] In some embodiments, the tetraalkoxysilane comprises the structure shown in Formula I.

[0047]

[0048] Among them, R1, R2, R3, and R4 each independently include C. 1-4 At least one of alkyl groups. In some embodiments, the tetraalkoxysilane includes at least one of tetraethyl silicate, tetramethyl silicate, tetrapropyl silicate, and tetrabutyl silicate.

[0049] In some embodiments, the siloxane containing the reactive group includes at least one of the structures shown in Formula II-1, Formula II-2, Formula III, and Formula IV.

[0050]

[0051] Among them, R 11 R 12 R 13 R 15 R 16 R 17 R 21 R 23 R 24 R 25 R 31 R 33 R 34 R 35 Each independently includes C 1-4 Alkyl, C 1-4 At least one of the alkoxy groups, R 14 R 18 R 22 R 32 Including C 1-8 Alkyl, C 1-8 Alkoxy, C 1-8 At least one of cycloalkyl and aromatic groups, and R 11 R 12 R 13 At least one of them includes C 1-4 At least one of the alkoxy groups, R 15 R 16 R 17 At least one of them includes C 1-4 At least one of the alkoxy groups, R 23 R 24 R 25 At least one of them includes C 1-4 At least one of the alkoxy groups, R 33 R 34 R 35 At least one of them includes C 1-4 At least one of the alkoxy groups.

[0052] In some embodiments, the siloxane containing the reactive group includes at least one of γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxypropyl)triethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane.

[0053] In some embodiments, the additive includes at least one of a catalyst and a surfactant. The catalyst includes at least one of aluminum, zinc, iron or cobalt metal acetylacetonate, diamide, imidazole, amine, organic sulfonic acid and its amine salt, alkali metal salt of carboxylic acid, and cyclic azide compound. The surfactant includes at least one of BYK347, BYK3455, BYK348, BYK3410, BYK307, Borchi Gol LA50, Capstone FS35, and Megaface F477.

[0054] This application reduces the risk of incompatibility between inorganic and organic systems and improves the stability of the curing solution by introducing the acidic hydrolysis product of tetraalkoxysilane into the curing solution, instead of directly introducing inorganic silica particles. Furthermore, the addition of siloxanes containing reactive groups not only serves as a film-forming material for subsequent curing film preparation, but more importantly, the introduction of siloxanes with reactive groups allows them to form stable interactants with the silicon-containing compounds in the acidic hydrolysis product of tetraalkoxysilane. This further reduces the risk of the silicon-containing compounds in the acidic hydrolysis product of tetraalkoxysilane continuing to react deeply and form silica, greatly improving the stability of the curing solution. Simultaneously, the stable interaction between the siloxanes with reactive groups and the silicon-containing compounds in the acidic hydrolysis product of tetraalkoxysilane allows for stable dispersion in the curing solution, which also helps improve the light transmittance of the curing solution, resulting in a curing film with excellent optical properties. During the subsequent film formation process, the silicon-containing compounds in the acidic hydrolysis product of tetraalkoxysilane can further react to form silica particles, improving the wear resistance and hardness of the curing film.

[0055] In some embodiments, the solvent includes water, and the curing liquid does not contain any organic solvents other than the alcohol produced by the hydrolysis of tetraalkoxysilane.

[0056] Currently, almost all solvents used in industrial curing solutions are organic solvents. For example, EP0614957 discloses the use of a mixture of methanol and 2-ethoxyethanol as a solvent for the curing solution, while US9957398 uses a mixture of 2-propanol and 1-methoxy-prop-2-ol as a solvent. The use of organic solvents not only causes carbon emissions and potential biosafety risks during the curing process, but also poses safety hazards due to their volatility and flammability. In addition, curing solutions using organic solvents typically require low-temperature storage and transportation, such as at -18°C, which significantly increases storage and transportation costs.

[0057] The solvent of the curing liquid in this application is water, and the curing liquid does not contain any organic solvents other than the alcohol produced by the hydrolysis of tetraalkoxysilane, which greatly reduces the use of organic solvents. This not only effectively improves the environmental friendliness of the curing liquid, but also greatly reduces its flammability, thereby improving the safety of the curing liquid during production, storage, transportation and use. At the same time, water as the solvent of the curing liquid can enable the curing liquid to be stored and transported under conventional cold chain conditions (0-5℃), which greatly reduces storage and transportation costs.

[0058] It is understood that the addition of organic solvents during hydrolysis is generally considered to help the organic phase tetraalkoxysilane and the inorganic phase catalyst solution to become miscible. Furthermore, tetraalkoxysilane and water are not directly miscible, requiring the introduction of a certain amount of organic solvent, such as alcohols, during hydrolysis to ensure that the ratio of tetraalkoxysilane, alcohol, and water meets the requirements of the miscibility region in the three-phase diagram. However, in this application, tetraalkoxysilane and water can react at the phase interface. This interfacial reaction helps to reduce the reaction rate, control the degree of tetraalkoxysilane hydrolysis, and reduce the risk of deep reaction leading to silica particles. Additionally, the alcohol produced by the hydrolysis of tetraalkoxysilane makes the reaction system a three-phase mixture. As hydrolysis continues, the proportion of alcohol increases, which not only inhibits further hydrolysis but also promotes the miscibility of the three phases. Thus, the system formed can still form a relatively stable miscible system without the help of external organic solvents, avoiding the occurrence of hardening liquid stratification.

[0059] In some embodiments, the curing liquid includes the following raw materials: tetraalkoxysilane, siloxane containing reactive groups, solvent, and additives.

[0060] In some embodiments, the molar ratio of tetraalkoxysilane to the siloxane containing the reactive group is 1:(1 / 4 to 4). In some embodiments, the molar ratio of tetraalkoxysilane to the siloxane containing the reactive group is 1:1 / 4, 1:1 / 2, 1:1, 1:2, 1:3, 1:4, or a ratio within the range of any two of the above ratios.

[0061] In this paper, the acidic hydrolysis products of tetraalkoxysilane include silicon-containing compounds and alcohols. Since the silicon-containing compounds include siloxane crosslinkers, the molar amount of tetraalkoxysilane must be greater than or equal to the sum of the molar amount of unreacted tetraalkoxysilane and the molar amount of silicon-containing compounds produced by the reaction of tetraalkoxysilane. In the case of complete preliminary hydrolysis of tetraalkoxysilane, it can be understood that the molar ratio of tetraalkoxysilane to siloxane containing reactive groups is 1:(1 / 4 to 4). It can also be understood that the molar ratio of silicon-containing compounds to siloxanes containing reactive groups in the acidic hydrolysis products of tetraalkoxysilane is less than or equal to 1:4. The molar amount of tetraalkoxysilane in the following text is explained in the same way and will not be repeated hereafter.

[0062] By controlling the molar ratio of tetraalkoxysilane to siloxane containing reactive groups within a suitable range, it is possible to provide sufficient siloxane containing reactive groups to form stable interacting products with silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane, while also effectively reducing the impact of excessive siloxane containing reactive groups on the stability of the hardening solution.

[0063] In some embodiments, the molar ratio of tetraalkoxysilane to solvent is 1:(2-50), and the molar ratio of the sum of the moles of tetraalkoxysilane and the siloxane containing the reactive group to the molar ratio of solvent is 1:(1-30). In some embodiments, the molar ratio of tetraalkoxysilane to solvent is 1:5, 1:6, 1:8, 1:10, 1:12, 1:14, 1:15, 1:16, 1:18, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, or a ratio within the range formed by any two of the above ratios. The molar ratio of the sum of the moles of tetraalkoxysilane and the siloxane containing the reactive group to the moles of the solvent is 1:4, 1:5, 1:6, 1:8, 1:10, 1:12, 1:14, 1:15, 1:16, 1:18, 1:20, 1:22, 1:24, 1:25, 1:26, 1:28, 1:30, or a ratio within the range formed by any two of the above ratios.

[0064] It is understandable that the solvent of the hardening solution is water, the hydrolysis reaction of tetraalkoxysilane produces alcohol, and the silicon-containing compounds and siloxanes containing reactive groups in the acidic hydrolysis products of tetraalkoxysilane are organic compounds. By controlling the molar ratio of tetraalkoxysilane to solvent, and the molar ratio of the sum of the moles of tetraalkoxysilane and siloxanes containing reactive groups to solvent within a suitable range, the above substances can form a stable miscible system, slow down the occurrence of the miscible system reaction, and ensure that the performance of the hardening solution remains stable after long-term storage.

[0065] In some embodiments, the mass content of tetraalkoxysilane is 5% to 55% based on the total mass of the curing liquid. In some embodiments, the mass content of tetraalkoxysilane may be selected as 5%, 10%, 20%, 30%, 40%, 50%, 55%, or a value within a range consisting of any two of the above, based on the total mass of the curing liquid.

[0066] In this paper, the acidic hydrolysis products of tetraalkoxysilane include silicon-containing compounds and alcohols. The mass content of tetraalkoxysilane is 5% to 55%, which is equivalent to the sum of the mass content of unreacted tetraalkoxysilane and the mass content of the acidic hydrolysis products of tetraalkoxysilane being 5% to 55%. In the case of complete preliminary hydrolysis of tetraalkoxysilane, it can be understood that the mass content of silicon-containing compounds is equal to the mass content of tetraalkoxysilane minus the mass content of alcohols generated by the acidic hydrolysis of tetraalkoxysilane.

[0067] In some embodiments, the mass content of the siloxane containing the reactive group is 5% to 55% based on the total mass of the curing liquid. In some embodiments, the mass content of the siloxane containing the reactive group can be selected as 5%, 10%, 20%, 30%, 40%, 50%, 55%, or a value within a range consisting of any two of the above, based on the total mass of the curing liquid.

[0068] Controlling the mass content of tetraalkoxysilane within a certain range ensures that there is enough tetraalkoxysilane to generate sufficient acidic hydrolysis products to produce enough silica inorganic particles during subsequent curing, thereby improving the wear resistance and hardness of the hardened film prepared by the curing solution. It also reduces the risk of excessive tetraalkoxysilane reacting too deeply and generating silica particles. Similarly, controlling the mass content of siloxanes containing reactive groups within a certain range ensures that there is enough siloxanes containing reactive groups to form stable interactants with silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane. This reduces the risk of further condensation of silicon-containing compounds in the acidic hydrolysis products to form silica, improving the stability of the curing solution and providing its excellent optical properties. Furthermore, sufficient siloxanes containing reactive groups can act as film-forming agents for curing, while also reducing the impact of excessive siloxanes containing reactive groups on the stability of the curing solution.

[0069] In some embodiments, the solvent content is 10% to 70% based on the total mass of the curing fluid. In some embodiments, the solvent content can be selected as 10%, 20%, 30%, 40%, 50%, 60%, 70%, or a value within a range consisting of any two of the above, based on the total mass of the curing fluid.

[0070] By controlling the mass content of the solvent in the hardening solution within a suitable range, the risk of deep reaction of silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane to form silica particles and / or hydrolysis of siloxanes containing reactive groups can be significantly reduced, thereby greatly improving the stability of the hardening solution and effectively reducing its flammability, thus ensuring its safety.

[0071] In some embodiments, the curing liquid further includes acrylate monomers, which include at least one of monofunctional acrylate monomers and polyfunctional acrylate monomers.

[0072] In some embodiments, the monofunctional acrylate monomer includes at least one of 2-phenoxyethyl acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 2-acrylate-[[1,1-binaphthyl]-2,2-di(oxy-2,1-ethidel)] ester, ethoxybisphenol A diacrylate, 4-acryloylmorpholine, N-vinylpyrrolidone, tri(2-hydroxyethyl)isocyanurate triacrylate, and their modifications.

[0073] In some embodiments, the multifunctional acrylate monomers include at least one of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, bisphenol fluorene diacrylate, 2-acrylate-[[1,1-binaphthyl]-2,2-di(oxy-2,1-ethoxy)] ester, bisphenol A diacrylate ethoxylated, bisphenol A dimethacrylate ethoxylated, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, bis-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, bis-pentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, and their modifications.

[0074] The addition of acrylate monomers helps to further improve the stability of the curing solution, so that the cured coating prepared by the curing solution can maintain stable performance.

[0075] In some embodiments, the storage temperature of the hardening fluid is 0°C to 5°C.

[0076] The hardening fluid in this application has excellent stability and can be stored stably at 0℃~5℃ for more than 2 months while still maintaining excellent wear resistance, hardness and optical properties. This greatly reduces the production, transportation and storage costs of the hardening fluid and broadens its application scope.

[0077] This application also provides a method for preparing a hardening liquid, the method comprising:

[0078] At 15℃~20℃, tetraalkoxysilane and acid solution are mixed and hydrolyzed to prepare acidic hydrolysis products, wherein the molar ratio of tetraalkoxysilane to water in hydrochloric acid solution is 1:(2~4).

[0079] At a temperature not exceeding 35°C, a siloxane containing a reactive group is added to the above acidic hydrolysis product, and the mixture is stirred until homogeneous to obtain a mixed solution.

[0080] At a temperature not exceeding 40°C, the above-mentioned mixed solution, additives, and solvent are mixed and stirred evenly to prepare a hardening liquid.

[0081] Under acidic conditions, controlling the hydrolysis reaction temperature to 15℃~20℃ and the molar ratio of tetraalkoxysilane to water in the acid solution to 1:(2~4) allows at least some of the alkoxy groups in the tetraalkoxysilane to form hydroxyl groups, effectively reducing the risk of further condensation of silicon-containing compounds in the acidic hydrolysis products to form silica particles. Subsequently, only siloxanes containing reactive groups are added. Since this acidic hydrolysis product system is insufficient to hydrolyze the siloxanes containing reactive groups, and both the acidic hydrolysis products of tetraalkoxysilane and the siloxanes containing reactive groups are organic compounds, they can be mixed uniformly under certain stirring conditions, forming… Stable interactors not only facilitate stable dispersion in solvents but also minimize the risk of silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilanes reacting deeply to form silica particles, thus preparing a curing solution with excellent stability. Finally, by adding solvents and additives at temperatures below 40°C, the degree of hydrolysis of siloxanes containing reactive groups caused by temperature is further reduced on the silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilanes. More importantly, this reduces the risk of silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilanes reacting deeply to form silica, greatly improving the stability of the curing solution.

[0082] In some embodiments, the preparation of the acidic hydrolysis product includes:

[0083] At 15℃~20℃, tetraalkoxysilane and acid solution are mixed and stirred at a speed of 600rpm~750rpm for 0.5h~2h to carry out hydrolysis reaction and prepare acidic hydrolysis product.

[0084] When the stirring speed and stirring time are within a suitable range, it is beneficial to the acidic hydrolysis of tetraalkoxysilanes, while reducing the risk of silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilanes further reacting to form silica particles.

[0085] In some embodiments, the step of preparing the mixed solution includes:

[0086] At a temperature not exceeding 35°C, a siloxane containing a reactive group is added to the above acidic hydrolysis product, and the stirring speed is 650 rpm to 800 rpm for 0.4 h to 1 h to obtain a mixed solution.

[0087] By controlling the stirring speed and time within a suitable range in the mixed solution of the acidic hydrolysis product of tetraalkoxysilane and the siloxane containing reactive groups, the formation of stable interacting products between the silicon-containing compound in the acidic hydrolysis product of tetraalkoxysilane and the siloxane containing reactive groups can be ensured to the greatest extent. This effectively reduces the risk of deep reaction between the silicon-containing compound in the acidic hydrolysis product of tetraalkoxysilane and the siloxane containing reactive groups in subsequent operations to generate silica particles.

[0088] In some embodiments, the step of preparing the hardening solution includes:

[0089] At a temperature not exceeding 40°C, the above mixed solution is mixed with a solvent at a stirring speed of 650 rpm to 800 rpm for 0.4 h to 1 h. Then, the additives are added and stirring is continued for 0.2 h to 1 h to prepare the hardening solution.

[0090] Controlling the stirring speed, stirring time, and feeding sequence of the hardening solution helps to form a more stable hardening solution.

[0091] In some embodiments, the molar ratio of tetraalkoxysilane to siloxane containing reactive groups is 1:(1 / 4 to 4).

[0092] By controlling the molar ratio of tetraalkoxysilane to siloxane containing reactive groups added in the preparation of the hardening solution within a suitable range, the siloxane containing reactive groups can provide sufficient protection for silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane, thereby greatly reducing the risk of deep reaction of silicon-containing compounds in the acidic hydrolysis products of tetraalkoxysilane to form silica particles.

[0093] In some embodiments, the solvent includes an organic solvent, which includes alcohol solvents.

[0094] In some embodiments, the solvent includes water, and the curing liquid does not contain any organic solvents other than the alcohol produced by the hydrolysis of tetraalkoxysilane.

[0095] Water-based hardening fluid has excellent safety.

[0096] In some implementations, the temperature of the hydrolysis reaction can be controlled at 15°C to 20°C by using an ice-water bath.

[0097] In some embodiments, the acid includes at least one of hydrochloric acid, nitric acid, and acetic acid.

[0098] Understandably, alkaline catalysts, such as ammonia, are preferred hydrolysis aids in the preparation of nano-silica particles using tetraethyl or ethyl silicate (TEOS). However, alkaline catalysts accelerate the hydrolysis of TEOS to form nano-silica particles, increasing the difficulty of controlling the cross-linking degree of the silicon-oxygen cross-linking in the curing solution, which is detrimental to the stability of the curing solution. In this application, hydrochloric acid, nitric acid, and acetic acid are used as catalysts to promote the hydrolysis of tetraalkoxysilanes. This effectively controls the cross-linking degree of the silicon-oxygen cross-linking formed in the curing solution, greatly reducing the risk of deep hydrolysis of tetraethyl or ethyl silicate to form silica particles, and significantly improving the stability of the curing solution.

[0099] In some embodiments, the concentration of the acid solution is 0.025 mol / L to 0.03 mol / L. In some embodiments, the concentration of the acid solution may be selected from 0.025 mol / L, 0.026 mol / L, 0.027 mol / L, 0.028 mol / L, 0.029 mol / L, 0.03 mol / L, or a value within the range of any two of the above.

[0100] In some implementations, the mass of the solvent is greater than the mass of water in the acid solution.

[0101] Understandably, under hydrolyzable conditions, siloxanes containing reactive groups undergo hydrolysis. This hydrolysis disrupts the stable interaction between the silicon-containing compound in the acidic hydrolysis product of tetraalkoxysilane and the siloxane itself, leading to a deeper reaction of the silicon-containing compound in the tetraalkoxysilane's acidic hydrolysis product to form silica, thus reducing the stability of the hardening solution. In this application, controlling the concentration of the acid solution and / or the mass of the solvent added in the third step to be greater than the mass of water in the acid solution added in the first step effectively reduces or even prevents the hydrolysis of the siloxanes containing reactive groups. This ensures that the stable interaction between the siloxanes containing reactive groups and the acidic hydrolysis product of tetraalkoxysilane remains stably dispersed in the hardening solution, improving its stability and allowing for long-term storage.

[0102] In some embodiments, the auxiliaries include at least one of catalysts and surfactants.

[0103] This application also provides a coating comprising a substrate and a hardened film layer located on at least one side of the substrate, the hardened film layer being prepared by a hardening liquid provided in this application or a hardening liquid prepared by a method for preparing a hardening liquid provided in this application.

[0104] In some embodiments, the substrate includes at least one selected from polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR-39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and cyclic polyolefin resin.

[0105] In some implementations, the curing liquid is cured into a hardened film by heating.

[0106] The heating temperature can reach up to 120℃. The high temperature not only helps the hardening liquid to solidify into a film, but also helps the acidic hydrolysis products of tetraalkoxysilane to further condense into silicon dioxide, thereby improving the wear resistance, scratch resistance and hardness of the hardened film.

[0107] In some embodiments, the curing liquid further includes a photoinitiator, which is cured into a curing film by UV light. The photoinitiator includes at least one of 2-methyl-2-hydroxy-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, and 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO).

[0108] UV light provides energy, which not only helps the curing solution solidify into a film, but also the high energy helps the acidic hydrolysis products of tetraalkoxysilane to deeply condense into silicon dioxide, improving the wear resistance, scratch resistance and hardness of the cured film.

[0109] This application also provides some embodiments of the application of the curing liquid in the field of lenses.

[0110] In this article, the lens field includes, but is not limited to, ophthalmic lenses, lenses used in optical instruments in photography or astronomy, optical aiming lenses, eye protection goggles, optical components of lighting systems, or window glass.

[0111] Example

[0112] The following embodiments are provided to better understand the present invention and are not intended to limit the scope of the invention, nor do they constitute a limitation on the content and protection scope of the invention. Where specific experimental steps or conditions are not specified in the embodiments, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Reagents or instruments used, unless otherwise specified, are all commercially available conventional reagent products.

[0113] I. Preparation Method

[0114] Example 1

[0115] At 20°C, tetraethyl silicate and hydrochloric acid solution were mixed. The concentration of the hydrochloric acid solution was 0.03M. The molar ratio of water in the tetraethyl silicate and hydrochloric acid solution was 1:4. The concentration of the hydrochloric acid solution was 0.03M. The stirring speed was controlled at 650 rpm. After stirring for 1 hour, the acidic hydrolysis product of tetraethyl silicate was obtained.

[0116] At 30°C, 3-(2,3-epoxypropoxy)propyltrimethoxysilane was added to the above acidic hydrolysis product (the molar ratio of tetraethyl silicate to 3-(2,3-epoxypropoxy)propyltrimethoxysilane was 1:4), mixed, and stirred at a speed of 700 rpm for 0.5 h to obtain a mixed solution.

[0117] At 40°C, pure water (tetraethyl silicate to pure water mass ratio of 7:6) was added to the above mixed solution, and the stirring speed was 700 rpm for 0.5 h. Then, aluminum triacetylacetonate (tetraethyl silicate to aluminum triacetylacetonate mass ratio of 60:1) was added and stirred for 10 min. Finally, BYK348 (commercially available, tetraethyl silicate to BYK348 mass ratio of 200:1) was added and stirred for 20 min to prepare the hardening solution.

[0118] Examples 2-3

[0119] The preparation methods of the hardening liquids in Examples 2 and 3 are similar to those of the hardening liquid in Example 1, except that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution in Example 1 was adjusted so that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution is 1:3 and 1:2, respectively, as shown in Table 1.

[0120] Examples 4-7

[0121] The preparation methods of the hardening liquids in Examples 4 to 7 are similar to those of the hardening liquid in Example 1, except that the mass content of tetraethyl silicate in the hardening liquid in Example 1 was adjusted so that the mass content of tetraethyl silicate in the hardening liquid was 15%, 40%, 50%, and 12%, respectively, as shown in Table 1.

[0122] Examples 8-10

[0123] The preparation methods of the hardening liquids in Examples 8-10 are similar to those of the hardening liquid in Example 1, except that the mass content of tetraethyl silicate and water in the hardening liquid in Example 1 was adjusted so that the mass content of tetraethyl silicate in the hardening liquid was 55%, 10%, and 5%, respectively, and the mass content of water in the hardening liquid was 10%, 60%, and 70%, respectively, as detailed in Table 1.

[0124] Example 11

[0125] The preparation method of the hardening liquid in Example 11 is similar to that of the hardening liquid in Example 1, except that the hydrolysis temperature of the acidic hydrolysis product prepared in Example 1 was adjusted to 15°C, as shown in Table 1.

[0126] Example 12

[0127] The preparation method of the hardening solution in Example 12 is similar to that of the hardening solution in Example 1, except that the concentration of hydrochloric acid used to prepare the acidic hydrolysis product in Example 1 was adjusted to make the concentration of hydrochloric acid 0.025M, as shown in Table 1.

[0128] Table 1 Preparation parameters of the examples

[0129]

[0130]

[0131] Example 13

[0132] The preparation method of the hardening solution in Example 13 is similar to that of the hardening solution in Example 1, except that the solvent in the hardening solution in Example 1 is adjusted so that the solvent in the hardening solution is ethanol. The specific preparation method is as follows:

[0133] At 20°C, tetraethyl silicate and hydrochloric acid solution were mixed. The concentration of the hydrochloric acid solution was 0.03M. The molar ratio of water in the tetraethyl silicate and hydrochloric acid solution was 1:4. The concentration of the hydrochloric acid solution was 0.03M. The stirring speed was controlled at 650 rpm. After stirring for 1 hour, the acidic hydrolysis product of tetraethyl silicate was obtained.

[0134] At 30°C, 3-(2,3-epoxypropoxy)propyltrimethoxysilane was mixed with the above acidic hydrolysis product (the molar ratio of tetraethyl silicate to 3-(2,3-epoxypropoxy)propyltrimethoxysilane was 1:4), and the mixture was stirred at 700 rpm for 0.5 h to obtain a mixed solution.

[0135] At 40°C, ethanol (tetraethyl silicate to ethanol mass ratio of 7:6) was added to the above mixed solution, and the stirring speed was 700 rpm for 0.5 h. Then, aluminum triacetylacetonate (tetraethyl silicate to aluminum triacetylacetonate mass ratio of 60:1) was added and stirred for 10 min. Finally, BYK3455 (tetraethyl silicate to BYK3455 mass ratio of 200:1) was added and stirred for 20 min to prepare the hardening solution.

[0136] Example 14

[0137] The curing solution of Example 14 was prepared in a similar manner to that of Example 1, except that acrylate monomers were introduced into the curing solution in Example 1. The specific preparation method is as follows:

[0138] At 20°C, tetraethyl silicate and hydrochloric acid solution were mixed. The concentration of the hydrochloric acid solution was 0.03M. The molar ratio of water in the tetraethyl silicate and hydrochloric acid solution was 1:4. The concentration of the hydrochloric acid solution was 0.03M. The stirring speed was controlled at 650 rpm. After stirring for 1 hour, the acidic hydrolysis product of tetraethyl silicate was obtained.

[0139] At 30°C, 3-(2,3-epoxypropoxy)propyltrimethoxysilane was mixed with the above acidic hydrolysis product (the molar ratio of tetraethyl silicate to 3-(2,3-epoxypropoxy)propyltrimethoxysilane was 1:4), and the mixture was stirred at 700 rpm for 0.5 h to obtain a mixed solution.

[0140] At 40°C, trimethylolpropane triacrylate (tetraethyl silicate to trimethylolpropane triacrylate mass ratio of 6:1) was added to the above mixed solution and stirred until homogeneous. Then, water (tetraethyl silicate to water mass ratio of 7:6) was added, and the stirring speed was 700 rpm for 0.5 h. Subsequently, aluminum triacetylacetonate (tetraethyl silicate to aluminum triacetylacetonate mass ratio of 60:1) was added and stirred for 10 min. Finally, BYK3455 (tetraethyl silicate to BYK3455 mass ratio of 200:1) was added and stirred for 20 min to prepare the hardening solution.

[0141] Example 15

[0142] The preparation method of the curing solution in Example 15 is similar to that of the curing solution in Example 1, except that the type of alkoxy group containing the reactive group in the curing solution of Example 1 is adjusted so that the alkoxy group containing the reactive group is methacryloyloxypropyltrimethoxysilane. The specific preparation method is as follows:

[0143] At 20°C, tetraethyl silicate and hydrochloric acid solution were mixed. The concentration of the hydrochloric acid solution was 0.03M. The molar ratio of water in the tetraethyl silicate and hydrochloric acid solution was 1:4. The concentration of the hydrochloric acid solution was 0.03M. The stirring speed was controlled at 650 rpm. After stirring for 1 hour, the acidic hydrolysis product of tetraethyl silicate was obtained.

[0144] At 30°C, methacryloxypropyltrimethoxysilane was mixed with the above acidic hydrolysis product (the molar ratio of tetraethyl silicate to methacryloxypropyltrimethoxysilane was 1:4), and the mixture was stirred at 700 rpm for 0.5 h to obtain a mixed solution.

[0145] At 40°C, water (tetraethyl silicate to water mass ratio of 7:6) was added to the above mixed solution, and the stirring speed was 700 rpm for 0.5 h. Then, aluminum triacetylacetonate (tetraethyl silicate to aluminum triacetylacetonate mass ratio of 60:1) was added, and the mixture was stirred for 10 min. Finally, BYK3455 (tetraethyl silicate to BYK3455 mass ratio of 200:1) was added, and the mixture was stirred for 20 min to prepare the hardening solution.

[0146] Comparative Example 1

[0147] The preparation method of the hardening solution in Comparative Example 1 is similar to that in Example 1, except that Comparative Example 1 directly introduces silica particles instead of tetraethyl silicate. The specific preparation method is as follows:

[0148] At 30°C, 50 wt% aqueous silica dispersion (purchased from Hangzhou Jiupeng New Materials Co., Ltd.) and 3-(2,3-epoxypropoxy)propyltrimethoxysilane were mixed at a mass ratio of 1:1 and stirred at 700 rpm for 0.5 h. Then, at 40°C, pure water (silica to pure water mass ratio of 7:6) was added to the above mixed solution and stirred at 700 rpm for 0.5 h. Subsequently, aluminum triacetylacetonate (silica to aluminum triacetylacetonate mass ratio of 60:1) was added and stirred for 10 min. Finally, BYK348 (silica to BYK348 mass ratio of 200:1) was added and stirred for 20 min to prepare the hardening solution.

[0149] Comparative Example 2

[0150] The preparation method of the hardening solution in Comparative Example 2 is similar to that of the hardening solution in Example 1, except that the concentration of hydrochloric acid in the preparation of the acidic hydrolysis product in Example 1 was adjusted so that the concentration of hydrochloric acid in the preparation of the acidic hydrolysis product is 0.1M, as shown in Table 2.

[0151] Comparative Example 3

[0152] The preparation method of the hardening solution in Comparative Example 3 is similar to that of the hardening solution in Example 1, except that the hydrolysis temperature in the preparation of the acidic hydrolysis product in Example 1 was adjusted to make the hydrolysis temperature in the preparation of the acidic hydrolysis product 30°C, as shown in Table 2.

[0153] Comparative Example 4

[0154] The preparation method of the hardening solution in Comparative Example 4 is similar to that of the hardening solution in Example 1, except that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution in the preparation of the acidic hydrolysis product in Example 1 was adjusted so that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution is 1:5, as shown in Table 2.

[0155] Comparative Example 5

[0156] The preparation method of the hardening solution of Comparative Example 5 is similar to that of the hardening solution of Example 1, except that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution in the preparation of the acidic hydrolysis product in Example 1 was adjusted so that the molar ratio of tetraethyl silicate to water in the hydrochloric acid solution is 1:1, as shown in Table 2.

[0157] Comparative Example 6

[0158] The preparation method of the hardening solution of Comparative Example 6 is similar to that of the hardening solution of Example 1, except that the type of tetraalkoxysilane in the acidic hydrolysis product prepared in Example 1 and the molar ratio of tetraalkoxysilane to water in the hydrochloric acid solution were adjusted so that the tetraalkoxysilane is dimethyldiethoxysilane and the molar ratio of dimethyldiethoxysilane to water in the hydrochloric acid solution is 1:2, as shown in Table 2.

[0159] Table 2 Preparation parameters of the comparative examples

[0160]

[0161]

[0162] II. Testing Methods

[0163] Taking Example 1 as an example:

[0164] Preparation of the hardened lens: Hang the handle of the CR-39 lens on the hook so that it can hang down naturally; fix the hook with the moving arm clamp of the lifting immersion coating machine; place an ice-water bath on the stage of the coating machine, and then place the beaker containing the hardening solution prepared in Example 1 into the ice-water bath; set the starting position of the moving arm according to the upper edge of the beaker and the solution depth, ensuring that when the moving arm starts to fall, the lower edge of the lens is about 2 cm higher than the upper edge of the beaker, and when the moving arm stops falling, the upper edge of the lens is about 0.5 cm lower than the liquid surface of the beaker; then set the residence time of the lens in the hardening solution to about 45 seconds and the lifting speed (2.0-3.0 mm / s). After the lens completes one immersion coating according to the set coating parameters, it is removed from the hook and immediately placed in a forced-air drying oven with a set curing temperature of 70°C. The lens is then suspended in the oven using the same hook method. After the drying time (20 minutes) is reached, the lens is removed and transferred to a forced-air drying oven with a set curing temperature of 120°C. Again, the lens is suspended in the oven using the same hook method. After the curing time (2 hours) is reached, the lens is removed and allowed to cool naturally at room temperature. Other embodiments and comparative examples follow the same preparation method as Example 1.

[0165] Preparation of pencil hardness samples: Hang the handle of the CR-39 plate on the hook and let it hang down naturally; fix the hook with the moving arm clamp of the lifting immersion coating machine; place an ice-water bath on the stage of the coating machine, and then place the beaker containing the hardening solution prepared in Example 1 (which was placed at 0-5℃ for 15×24h) into the ice-water bath; set the starting position of the moving arm according to the upper edge of the beaker and the solution depth, ensuring that when the moving arm starts to fall, the lower edge of the plate is about 2cm higher than the upper edge of the beaker, and when the moving arm stops falling, the upper edge of the scale (5cm) of the plate is about 0.5cm lower than the liquid surface of the beaker; then set the residence time of the plate in the hardening solution to about 45 seconds and the lifting speed (2.0-3.0mm / s). After the substrate completes one immersion coating according to the set coating parameters, it is removed from the hook and immediately placed in a forced-air drying oven with a set curing temperature of 70°C. The lens is also suspended in the oven using the hook method. After the drying time (20 minutes) is reached, the lens is removed and transferred to a forced-air drying oven with a set curing temperature of 120°C. The lens is again suspended in the oven using the hook method. After the curing time (2 hours) is reached, the lens is removed and allowed to cool naturally at room temperature. Other embodiments and comparative examples follow the same preparation method as Example 1.

[0166] 1) Testing the viscosity of the hardening solution

[0167] The viscosity of the hardener was tested in accordance with GB / T 10247-2008 standard.

[0168] Initial viscosity: The initial viscosity of the freshly prepared hardened liquid was tested at 25°C using a slab viscometer, model DVNXRNCP, with an accuracy of ±5 cps.

[0169] 15×24h storage viscosity: After the hardening liquid to be tested is placed at 0-5℃ for 15×24h, its viscosity at 25℃ is tested again using a cone-plate viscometer. This is the 15×24h viscosity. The smaller the difference between the 15×24h viscosity and the initial viscosity, the better the stability of the hardening liquid.

[0170] 2) Hardening liquid permeability test

[0171] The transmittance of the hardening solution was tested according to GB / T 14571.4-2022 standard. After storing the prepared hardening solution for 15 days, the transmittance in the range of 400nm to 800nm ​​was tested using a UV-vis spectrophotometer. The testing equipment was a Shimadzu UV-1800.

[0172] 3) Testing the abrasion resistance of hardened lenses

[0173] Haze testing of hardened lenses: The haze of hardened lenses was tested according to GB / T 2410-2008 standard. Hardened lenses prepared with the prepared hardening solution, hardened lenses prepared with the hardening solution after 15 days of storage, and hardened lenses after abrasion resistance testing were tested using a haze meter. The testing equipment used was a Japanese Denshoku NDH8000.

[0174] Initial abrasion resistance: The abrasion resistance of the lens was tested according to GB 10810.5-2012 standard. The initially prepared hardened lens was placed on an abrasion tester (A20-339, Jinliang Industrial Co., Ltd.), using 0000# steel wool, with a total load of 500g. The swing arm travel was 4cm, the swing frequency was 100 times / minute, and the test cycle was 1000 times. Subsequently, the hardened lens was subjected to a haze test, and the haze value after abrasion resistance was compared with the haze value of the same lens before abrasion resistance. The change in haze was used as an indicator of initial abrasion resistance. A large change in haze indicates poor abrasion resistance, while a small change in haze indicates good abrasion resistance.

[0175] 15×24h Abrasion Resistance: After the curing solution was placed at 0-5℃ for 15×24h, it was removed and coated, dried, and cured on a CR-39 lens according to the above-described method for preparing cured lenses. The prepared cured lens was then subjected to an abrasion resistance test. The haze change value obtained at this time was used as an indicator of the 15×24h abrasion resistance; the smaller the difference between the haze change value before and after 15×24h abrasion resistance and the initial haze change value before and after abrasion resistance, the better the stability of the curing solution.

[0176] 4) Pencil hardness test of the hardened film layer

[0177] The pencil hardness of the hardened film was tested according to GB / T 2410-2008 standard. A pencil hardness tester and a standard-compliant pencil were slid across the prepared pencil hardness sample. The total weight of the pencil hardness tester was 750g, and the pencil brand was Mitsubishi.

[0178] Table 3 Performance test table for each embodiment and comparative example

[0179]

[0180]

[0181] III. Analysis of Test Results for Each Embodiment and Comparative Example

[0182] Comparing the data from Examples 1, 2, and 3 above, it can be seen that when the molar ratio of tetraethyl silicate to water in hydrochloric acid decreases, the acidic hydrolysis of tetraethyl silicate is suppressed, which causes a slight increase in the viscosity of the hardening solution and a decrease in the light transmittance. However, at the same time, the risk of silicon-containing compounds in the acidic hydrolysis products of tetraethyl silicate further reacting to form silica particles also decreases. Therefore, the storage stability of the hardening solution is not significantly affected. However, the reduced degree of hydrolysis of tetraethyl silicate will result in a decrease in the amount of silica particles generated, which in turn slightly reduces the wear resistance of the hardened film.

[0183] Comparing the data from Examples 1, 4, 5, 6, 7, 8, 9, and 10, it is clear that the content of tetraethyl orthosilicate (TES) has a direct impact on the wear resistance of the hardened film. Within a certain range, a higher TES content results in better wear resistance of the hardened film. However, if the TES content exceeds a certain range, the resulting hardened film will become too hard, and insufficient film-forming material may further lead to brittleness or even detachment of the hardened film, resulting in a decrease in the pencil hardness of the hardened film.

[0184] As can be seen from Examples 1 and 11-12, controlling the acid hydrolysis temperature of tetraethyl silicate below 20°C, or the concentration of hydrochloric acid catalyzing the acid hydrolysis to be 0.025M to 0.03M, will not significantly affect the degree of hydrolysis and condensation of tetraethyl silicate, or its subsequent combination with epoxysiloxane, thus not impacting the storage performance, light transmittance, and wear resistance of the hardening solution and the hardened film.

[0185] A comparison of Examples 1 and 15 shows that, compared to methacryloyloxypropyltrimethoxysilane, the interaction product formed by 3-(2,3-epoxypropoxy)propyltrimethoxysilane and tetraethyl silicate is more stable, resulting in a hardening liquid with better dispersion stability and a hardened coating with superior wear resistance.

[0186] As can be seen from the comparison between Example 1 and Comparative Example 1, when the wear-resistant components in the hardening solution are directly provided by the aqueous dispersion of silica, the hardening solution has more inorganic phase and can provide excellent wear resistance when the hardening solution is freshly prepared; however, the light transmittance of the hardening solution is lower, and the stability of the hardening solution is poor. The sedimentation of silica will increase with the extension of storage time, which makes it impossible to effectively maintain the wear-resistant components of the hardening solution, resulting in a significant decrease in wear resistance.

[0187] As can be seen from the comparison between Example 1 and Comparative Example 2, when the concentration of hydrochloric acid is higher than 0.03M during the acidic hydrolysis of tetraethyl silicate, it will not only greatly increase the degree of hydrolysis and polycondensation of tetraethyl silicate, but also cause the subsequently added siloxane containing reactive groups to undergo hydrolysis. The direct mutual stabilizing effect between the two is destroyed, resulting in a decrease in the storage stability of the hardening solution and a decrease in the wear resistance of the hardened film layer prepared from the hardening solution after 15 days of storage.

[0188] As can be seen from the comparison between Example 1 and Comparative Example 3, when the temperature is higher than 20°C during the hydrolysis of tetraethyl silicate, the degree of hydrolysis and polycondensation of tetraethyl silicate will be greatly increased. Even if a siloxane containing reactive groups is added later, it is difficult to provide a good stabilizing effect, which will still lead to a decrease in the storage stability of the hardening solution and a decrease in the wear resistance of the hardened film layer prepared from the hardening solution after 15 days of storage.

[0189] As can be seen from the comparison between Example 1 and Comparative Example 4, the increase in acid and water content during the hydrolysis of tetraethyl silicate also leads to a greater degree of hydrolysis and condensation, resulting in a decrease in the storage stability of the hardening solution and a decrease in the wear resistance of the hardened film prepared from the hardening solution after 15 days of storage.

[0190] As can be seen from the comparison between Example 1 and Comparative Example 5, when the water content required for the hydrolysis of tetraethyl silicate is insufficient, the tetraethyl silicate in the hardening solution is mostly still in the organic phase, which leads to an increase in the viscosity of the solution. At the same time, it inhibits the hydrolysis and condensation of tetraethyl silicate. Although it can improve the storage stability of the hardening solution, the required wear-resistant components are also greatly reduced, which greatly reduces the wear resistance of the hardened film.

[0191] As can be seen from the comparison between Example 1 and Comparative Example 6, compared with introducing dimethyldiethoxysilane into the curing solution for acidic hydrolysis, the introduction of tetraethyl silicate into the curing solution for acidic hydrolysis in this application results in a more superior wear resistance in the subsequent curing into a hardened film layer.

[0192] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and not to limit them. Although this application 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 or all of the technical features therein. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application, and they should all be covered within the scope of the claims and specification of this application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any way. This application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A hardening liquid, characterized in that, This includes acidic hydrolysis products of tetraalkoxysilanes, siloxanes containing reactive groups, solvents, and auxiliaries.

2. The hardening liquid according to claim 1, characterized in that, The tetraalkoxysilane includes the structure shown in Formula I. Among them, R1, R2, R3, and R4 each independently include C. 1-4 At least one of the alkyl groups, optionally, the tetraalkoxysilane includes at least one of tetraethyl silicate, tetramethyl silicate, tetrapropyl silicate, and tetrabutyl silicate; and / or The siloxane containing reactive groups includes at least one of the structures shown in Formula II-1, Formula II-2, Formula III, and Formula IV. Among them, R 11 R 12 R 13 R 15 R 16 R 17 R 21 R 23 R 24 R 25 R 31 R 33 R 34 R 35 Each independently includes C 1-4 Alkyl, C 1-4 At least one of the alkoxy groups, R 14 R 18 R 22 R 32 Including C 1-8 Alkyl, C 1-8 Alkoxy, C 1-8 At least one of cycloalkyl and aromatic groups, and R 11 R 12 R 13 At least one of them includes C 1-4 At least one of the alkoxy groups, R 15 R 16 R 17 At least one of them includes C 1-4 At least one of the alkoxy groups, R 23 R 24 R 25 At least one of them includes C 1-4 At least one of the alkoxy groups, R 33 R 34 R 35 At least one of them includes C 1-4 At least one of alkoxy groups; optionally, the siloxane containing the reactive group comprises at least one of γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxypropyl)triethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane; and / or The solvent includes water, and the hardening solution does not include any organic solvents other than the alcohol produced by the acidic hydrolysis of the tetraalkoxysilane; and / or The auxiliary agent includes at least one of a catalyst and a surfactant. The catalyst includes at least one of aluminum, zinc, iron, or cobalt metal acetylacetone compounds, diamides, imidazoles, amines, organic sulfonic acids and their amine salts, alkali metal salts of carboxylic acids, and cyclic azide compounds. The surfactant includes at least one of BYK347, BYK3455, BYK348, BYK3410, BYK307, Borchi GolLA50, Capstone FS35, and Megaface F477; and / or The curing liquid also includes acrylate monomers, which include at least one of monofunctional acrylate monomers and polyfunctional acrylate monomers.

3. The hardening liquid according to claim 1, characterized in that, The molar ratio of the tetraalkoxysilane to the siloxane containing the reactive group is 1:(1 / 4 to 4), and can be 1:(0.5 to 3).

4. The hardening liquid according to claim 2, characterized in that, The molar ratio of the tetraalkoxysilane to the solvent is 1:(2-50), optionally 1:(8-25), and the molar ratio of the sum of the moles of the tetraalkoxysilane and the siloxane containing the reactive group to the moles of the solvent is 1:(1-30), optionally 1:(5-20).

5. The hardening liquid according to any one of claims 1 to 4, characterized in that, Based on the total mass of the hardening liquid, the mass content of the tetraalkoxysilane is 5% to 55%, optionally 15% to 55%; and / or Based on the total mass of the hardening liquid, the mass content of the siloxane containing reactive groups is 5% to 55%, optionally 15% to 55%; and / or Based on the total mass of the hardening liquid, the solvent content is 10% to 70%, and optionally 10% to 60%.

6. The hardening liquid according to any one of claims 1 to 4, characterized in that, The storage temperature of the hardening liquid is 0℃~5℃.

7. A method for preparing a hardening liquid according to any one of claims 1 to 6, characterized in that, The preparation method includes: At 15℃~20℃, tetraalkoxysilane and acid solution are mixed and hydrolyzed to prepare acidic hydrolysis products, wherein the molar ratio of the tetraalkoxysilane to water in the acid solution is 1:(2~4). At a temperature not exceeding 35°C, the acidic hydrolysis product is mixed with a siloxane containing a reactive group and stirred until homogeneous to obtain a mixed solution. The curing liquid is prepared by mixing the mixed solution, additives and solvent at a temperature not exceeding 40°C and stirring until homogeneous.

8. The preparation method according to claim 7, characterized in that, The molar ratio of the tetraalkoxysilane to the siloxane containing the reactive group is 1:(1 / 4 to 4), optionally 1:(0.5 to 3); and / or The tetraalkoxysilane includes at least one of tetraethyl silicate, tetramethyl silicate, tetrapropyl silicate, and tetrabutyl silicate; and / or The siloxane containing the reactive group comprises at least one of γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxypropyl)triethoxysilane, 3-(2,3-epoxypropoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane; and / or The solvent includes water, and the hardening solution does not include organic solvents other than the alcohol produced by the hydrolysis of the tetraalkoxysilane; and / or The auxiliary agent includes at least one of a catalyst and a surfactant; and / or The concentration of the acid solution is 0.025 mol / L to 0.03 mol / L; and / or The mass of the solvent is greater than the mass of water in the acid solution.

9. A coating, characterized in that, It includes a substrate and a hardened film layer located on at least one side of the substrate, the hardened film layer being prepared by the hardening liquid according to claims 1 to 6 or the hardening liquid prepared by the preparation method according to claims 7 to 8.

10. The application of a curing liquid according to claims 1 to 6 or a curing liquid prepared by the preparation method according to claims 7 to 8 in the field of lenses.

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