Wear-resistant fluorine-free long-carbon-chain hydrophobic paint, coating, preparation method and application

Abstract

The invention relates to a wear-resistant fluorine-free long-carbon-chain hydrophobic coating, a coating, a preparation method and application. The wear-resistant fluorine-free long-carbon-chain hydrophobic coating comprises a first component and a second component, and the first component comprises a pretreating agent and a first organic solvent and is at least used for providing a reaction site; the second component comprises a siloxane compound, a catalyst and a second organic solvent, the siloxane compound comprises a long-carbon-chain hydrophobic chain segment and an epoxy anchoring chain segment, and the siloxane compound at least can be subjected to a ring-opening reaction with amino groups. A coating formed by curing the wear-resistant fluorine-free long-carbon-chain hydrophobic coating shows excellent mechanical wear resistance, chemical stability, heat resistance and ultraviolet resistance, the coating is high in transparency, and the light transmittance is larger than 98%. Compared with a fluorine-containing coating, the coating is suitable for the fields of photovoltaic glass, building glass, automobile windshields and the like, shows antifouling, waterproof and long-term storage stability, and is suitable for the application fields of biomedicine, display screen protection and the like.

Description

Technical Field

[0001] This invention belongs to the field of glass material protection technology, and relates to a wear-resistant, fluorine-free, long-chain hydrophobic coating, coating and its preparation method, and particularly to a wear-resistant, fluorine-free, long-chain hydrophobic coating, coating and its corresponding preparation method and application suitable for glass material surfaces. Background Technology

[0002] With the continuous development of technology, the demand for surface coatings is increasing. These coatings aim to improve the properties of materials, especially their properties when in contact with liquids. Hydrophobic coatings are a coating technology that improves the interaction between objects and water or other liquids by forming a layer of hydrophobic material on the surface of an object, thereby enabling a variety of practical applications.

[0003] In this context, fluorinated compounds are widely used to manufacture coatings with specific wetting behaviors due to their unique properties, such as low surface energy, high chemical stability, and hydrophobicity. However, most fluorinated compounds are not only expensive but also persistent and bioaccumulative in nature, meaning they are not easily degraded in the environment and can accumulate in organisms, including humans. Furthermore, the process of manufacturing coatings using fluorinated compounds generates greenhouse gases and other pollutants, contributing to climate change and air pollution. Patents such as CN106746736A, CN101941000A, CN106928844A, CN105420735A, and CN206725795U all utilize fluorinated compounds as raw materials.

[0004] While solid smooth surfaces with ultra-low liquid sliding angles have been reported for various practical applications, most lack mechanical and chemical stability, have complex and demanding manufacturing processes, exhibit fragile and non-covalent adhesion to the underlying substrate, and cannot withstand high temperatures, as illustrated by patents with publication numbers CN116102972A, CN116970337A, CN117487455A, CN115109447A, and CN115404004A. Therefore, it is necessary to provide a novel hydrophobic coating technology utilizing fluorine-free long-chain carbon materials to manufacture coatings with unique wetting behavior. This technology should be efficient, sustainable, low-cost, and environmentally friendly to meet the needs of different fields. Summary of the Invention

[0005] The main objective of this invention is to provide a wear-resistant, fluorine-free, long-chain hydrophobic coating suitable for glass material surfaces and its preparation method, so as to overcome the shortcomings of existing technologies where fluorine-containing chemicals are prone to causing pollution.

[0006] Another objective of this invention is to provide a wear-resistant, fluorine-free, long-chain hydrophobic coating suitable for glass material surfaces, its preparation method, and its application.

[0007] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0008] This invention provides a wear-resistant, fluorine-free, long-chain hydrophobic coating, comprising: a first component and a second component. The first component includes a pretreatment agent and a first organic solvent, wherein the pretreatment agent is at least used to provide reaction sites. The second component includes a siloxane compound, a catalyst, and a second organic solvent. The siloxane compound includes long-chain hydrophobic segments and epoxy anchoring segments, and the siloxane compound is at least capable of undergoing a ring-opening reaction with an amino group.

[0009] In some embodiments, the pretreatment agent includes any one or a combination of two or more of 3-aminopropyl-3-ethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane.

[0010] In some embodiments, the siloxane compound is prepared by hydrolysis and condensation reaction of a first compound, a second compound and a catalyst, wherein the first compound is a fluorine-free long carbon chain compound and the second compound is an epoxysilane compound.

[0011] This invention also provides a wear-resistant, fluorine-free, long-chain hydrophobic coating, which is formed by curing the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0012] This invention also provides a method for preparing a wear-resistant, fluorine-free, long-chain hydrophobic coating, comprising:

[0013] Provide the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating;

[0014] The first component is used to pretreat the substrate surface to provide reaction sites;

[0015] The second component is applied to the pretreated substrate surface and then cured to form the wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0016] This invention also provides applications of the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating, specifically including applications in the fields of glass material surfaces, biomedicine, or display screen protection.

[0017] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0018] 1) The wear-resistant, fluorine-free, long-chain hydrophobic coating provided by the present invention, after curing, exhibits excellent mechanical wear resistance, chemical stability, heat resistance, UV resistance and long-term storage capacity, and the coating has high transparency with a light transmittance of >98%.

[0019] 2) This invention synthesizes siloxane compounds whose structure includes long carbon chain hydrophobic segments and epoxy anchoring segments. It uses fluorine-free compounds as raw materials to hydrolyze and condense with epoxy silane compounds. While providing the same hydrophobic effect and greatly reducing environmental pollution, it has practical biomedical applicability and potential as an antifouling coating, display screen, etc.

[0020] 3) Compared to fluorinated coatings, this invention uses fluorine-free long-chain carbon materials, which not only maintain excellent hydrophobicity (water contact angle reaching 90°-120°) but also effectively reduce environmental pollution, exhibiting better eco-friendliness. This coating is suitable for photovoltaic glass, architectural glass, automotive windshields, and other fields, demonstrating anti-fouling, waterproofing, and long-term storage stability, and is also suitable for applications in biomedicine and display screen protection. This invention, through a novel synthesis method, achieves environmental friendliness and low cost for fluorine-free long-chain hydrophobic coatings, possessing broad market application prospects. Detailed Implementation

[0021] As mentioned above, in view of the shortcomings of existing technologies, such as the easy pollution caused by fluorinated chemicals and the fragile and easily peeled coatings, the inventors of this case have provided an innovative method and combination through long-term research and extensive practice to overcome the shortcomings of existing technologies and provide a new way to improve hydrophobic properties without using fluorinated compounds. This is mainly achieved by designing the formation of siloxane compounds, which greatly reduces environmental pollution and makes it highly efficient, low-cost and environmentally friendly.

[0022] The following will provide a further explanation of the technical solution, its implementation process, and its principles.

[0023] One aspect of this invention provides a wear-resistant, fluorine-free, long-chain hydrophobic coating composed of two components: a first component and a second component. The first component (hereinafter also referred to as the "first solution") includes a pretreatment agent and a first organic solvent. The pretreatment agent is used at least for pretreatment of the substrate surface, providing reaction sites. The second component (hereinafter also referred to as the "second solution") includes a siloxane compound, a catalyst, and a second organic solvent. The siloxane compound contains long-chain hydrophobic segments and epoxy anchoring segments. The siloxane compound is at least capable of undergoing a ring-opening reaction with amino groups to form a robust coating.

[0024] In some embodiments, the wear-resistant, fluorine-free, long-chain hydrophobic coating is composed of a first component and a second component. Based on 100% of the total mass of the raw materials of the first component of the wear-resistant, fluorine-free, long-chain hydrophobic coating, the first component includes 2% to 50% pretreatment agent and 50% to 98% first organic solvent.

[0025] Furthermore, based on 100% of the total mass of the raw materials, the second component includes 2% to 42% siloxane compounds, 5% to 10% catalysts, and the balance being a second organic solvent.

[0026] In some specific embodiments, the pretreatment agent may include any one or a combination of two or more of 3-aminopropyl-3-ethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, but is not limited thereto.

[0027] In some specific embodiments, the present invention also provides a method for preparing the above-mentioned siloxane compound, wherein the siloxane compound is prepared by hydrolysis and condensation reaction of a first compound, a second compound, and a catalyst. The first compound is a fluorine-free long-chain carbon compound, and the second compound is an epoxy silane compound. The present invention adjusts the hydrophobicity of the coating by polymerizing the fluorine-free long-chain carbon compound with the epoxy silane compound and controlling the carbon chain length in the fluorine-free long-chain carbon compound. While achieving hydrophobic properties, the siloxane compound can undergo a ring-opening reaction with amino groups, anchoring the siloxane compound to the substrate surface, thus providing a green, environmentally friendly, long-lasting, wear-resistant, long-chain hydrophobic coating.

[0028] Compared to patents that use fluorinated silane coupling agents for hydrolysis and condensation on the substrate surface, this invention, through the design of forming siloxane compounds, uses fluorine-free compounds as raw materials for hydrolysis and condensation with epoxy silanes. While providing the same hydrophobic effect and greatly reducing environmental pollution, it also has strong toughness and wear resistance, broadening the application field of the material and making it efficient, low-cost and environmentally friendly.

[0029] In some more specific embodiments, the first compound, a fluorine-free long-chain compound, includes any one or more combinations of propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecanyltriethoxysilane, heptadecanyltriethoxysilane, octadecyltriethoxysilane, nonadecanyltriethoxysilane, eicosyltriethoxysilane, dodecyltriethoxysilane, hexadecyltriethoxysilane, dodecyltriethoxysilane, nonadecanyltriethoxysilane, eicosyltriethoxysilane, dodecyltriethoxysilane, dodecyltriethoxysilane, etc., but is not limited thereto.

[0030] In some more specific embodiments, the second compound, an epoxysilane compound, includes, but is not limited to, any one or a combination of two or more of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(epoxyethylene-2-ylmethoxy)propyltriethoxysilane, etc.

[0031] In some specific embodiments, the catalyst can be any one of an alkaline catalyst or an acidic catalyst.

[0032] Furthermore, the alkaline catalyst may include any one or a combination of two or more of ethylamine, diethylamine, triethylamine, tripropylamine, trimethylamine, N,N-diisopropylethylamine, and triisopropylamine, with triethylamine being preferred, but not limited thereto.

[0033] Furthermore, the acidic catalyst may include any one or a combination of two or more of acetic acid, formic acid, oxalic acid, etc., but is not limited thereto.

[0034] In some more specific embodiments, the raw materials for preparing the siloxane compound, based on a total mass of 100%, include 20%–30% of a first compound, 20%–30% of a second compound, 0.2%–0.45% of a catalyst, and a second organic solvent. This invention synthesizes siloxane compounds whose structures include long-chain hydrophobic segments and epoxy anchoring segments, using fluorine-free compounds as raw materials for hydrolysis and condensation with epoxy silanes. While providing the same hydrophobic effect and significantly reducing environmental pollution, it also possesses practical biomedical applicability and potential as an antifouling coating, display screen, etc.

[0035] In some more specific embodiments, the hydrolysis-condensation reaction is carried out at room temperature for a time of less than one hour.

[0036] In some more specific embodiments, the mass ratio of the first compound to the second compound is 1:2 to 2:1.

[0037] In some specific embodiments, the sum of the first organic solvent and the second organic solvent constitutes 65% to 90% of the total mass content (i.e., mass percentage) of all raw materials in the wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0038] In some specific embodiments, the mass content of the siloxane compound in all raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating is generally controlled to be 2% to 55%.

[0039] In some specific embodiments, the mass content of the second compound, epoxy silane, in all the raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating is generally controlled to be 1% to 30%.

[0040] In some specific embodiments, the mass content of the first compound, a fluorine-free long carbon chain compound, in all the raw materials of the wear-resistant fluorine-free long carbon chain hydrophobic coating is generally controlled to be 1% to 30%.

[0041] In some specific embodiments, the catalyst has a mass content of 0.7% to 5% in all raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0042] In some specific embodiments, the first organic solvent and the second organic solvent are each independently selected from any one or a combination of two or more of isopropanol, ethanol, ethyl acetate, butyl acetate, etc., but are not limited thereto.

[0043] In summary, this invention achieves environmental friendliness and low cost of fluorine-free long-chain hydrophobic coatings through a novel synthesis method, and has broad market application prospects.

[0044] Another aspect of the present invention provides a wear-resistant, fluorine-free, long-chain hydrophobic coating, which is formed by curing the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0045] Furthermore, the wear-resistant, fluorine-free, long-chain hydrophobic coating is composed of wear-resistant, fluorine-free, long-chain hydrophobic paint. The first component is used to pretreat the substrate surface to provide reaction sites; the second component is applied to the pretreated substrate surface, and then cured to form the wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0046] In some specific embodiments, the contact angle between the wear-resistant, fluorine-free long-chain hydrophobic coating and water is 90°–120°. This invention polymerizes fluorine-free long-chain compounds with epoxy silane compounds, and adjusts the hydrophobicity of the coating by controlling the carbon chain length of the fluorine-free long-chain compound, thereby obtaining a long-chain wear-resistant, fluorine-free long-chain hydrophobic coating for glass materials with a water contact angle of 90°–120°. Compared to fluorine-containing coatings, this invention uses fluorine-free long-chain materials, which not only maintain excellent hydrophobicity with a water contact angle of 90°–120°, but also effectively reduces environmental pollution and has better eco-friendliness.

[0047] In some specific embodiments, the contact angle between the wear-resistant, fluorine-free long carbon chain hydrophobic coating surface and water is preferably 115° to 120°.

[0048] In some specific embodiments, the light transmittance of the wear-resistant, fluorine-free, long-chain hydrophobic coating is >98%, preferably >99%.

[0049] In some specific embodiments, the thickness of the wear-resistant, fluorine-free, long-chain hydrophobic coating is 50nm to 300nm, preferably 100nm to 200nm.

[0050] Another aspect of the present invention provides a method for preparing the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating, comprising:

[0051] Provide the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating;

[0052] The first component is used to pretreat the substrate surface, providing sites for subsequent reactions;

[0053] The second component is applied to the pretreated substrate surface and then cured to form the wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0054] In some specific implementations, the preparation method specifically includes:

[0055] The first component of the wear-resistant, fluorine-free, long-chain hydrophobic coating is used to pretreat the substrate surface to provide subsequent reaction sites. Then, the second component of the wear-resistant, fluorine-free, long-chain hydrophobic coating is uniformly coated on the pretreated substrate surface. The material is then cured in an oven to form a wear-resistant, fluorine-free, long-chain hydrophobic coating.

[0056] The coating preparation mechanism of this invention lies in the fact that the pretreatment agent in the first component causes amino functional groups to form on the glass surface, which then undergo a ring-opening reaction with the epoxy groups on the siloxane compound in the second component. Therefore, the resulting coating structure is stable, not easily detached, and possesses long carbon chains, making the self-cleaning material more stable and environmentally friendly.

[0057] In some specific embodiments, the curing temperature of the wear-resistant, fluorine-free long carbon chain hydrophobic coating is 80℃~120℃, and the curing time is more than 1 hour, preferably more than 3 hours.

[0058] Furthermore, the pretreatment includes: soaking the substrate in a piranha solution (7 mL concentrated sulfuric acid, 3 mL hydrogen peroxide) for more than 24 hours, and then soaking it in the first component for more than 30 minutes.

[0059] Furthermore, the pretreatment includes soaking the fish in a piranha solution for 24 hours, rinsing it with deionized water, soaking it in the first component solution for more than half an hour, rinsing it with deionized water again, and then drying it.

[0060] In some embodiments, the method of applying the second component to the pretreated substrate surface includes coating, preferably spraying.

[0061] In some specific embodiments, the coating method includes spraying, which may specifically include: loading the second component into a sealed spray bottle and then spraying it evenly onto the glass substrate.

[0062] In summary, this invention prepares a long-chain, wear-resistant, fluorine-free, long-chain hydrophobic coating on the surface of glass materials by anchoring silicon-oxygen bonds with hydrophobic siloxane compounds. The prepared transparent coating has excellent protective and functional properties.

[0063] This invention employs a novel "reactive" chemical method and uses a feasible synthesis method to obtain a transparent "liquid" fully hydrophobic solid coating. The developed solid smooth coating has high mechanical durability, chemical stability, heat resistance, UV resistance, and long-term storage capability.

[0064] Another aspect of the present invention provides the application of the aforementioned wear-resistant, fluorine-free, long-chain hydrophobic coating or wear-resistant, fluorine-free, long-chain hydrophobic coating in the field of substrate protection, specifically in the fields of glass material surface, biomedical or display screen protection, exhibiting anti-fouling, waterproof and long-term storage stability.

[0065] Furthermore, the coating is applicable to at least one of the following glass material substrates: photovoltaic glass surface, architectural glass (such as building glass) surface, automotive windshield, etc.

[0066] To more clearly illustrate the technical features, objectives, and beneficial effects of this invention, a detailed explanation of the technical solution will now be provided. Many specific details are set forth in the following description to provide a thorough understanding of the invention; however, the invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below. Furthermore, the technical features involved in the various embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.

[0067] Unless otherwise specified, the raw materials and reagents used in the embodiments of this application were all purchased commercially.

[0068] In this invention, all numerical parameters (e.g., temperature, time, concentration, weight, etc., including their respective ranges) can generally be appropriately adjusted by increments or decrements of 0.1 or 1.0. All these numerical parameters can be understood as being preceded by the term "approximately".

[0069] Example 1

[0070] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0071] Step (b): The first compound (octyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0072] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B1, and set aside for use.

[0073] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B1 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0074] Example 2

[0075] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0076] Step (b): The first compound (dodecyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0077] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B2, and set aside for use.

[0078] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B2 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0079] Example 3

[0080] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0081] Step (b): The first compound (hexadecyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0082] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B3, and set aside for use.

[0083] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B3 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0084] Example 4

[0085] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0086] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0087] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B4, and set aside for use.

[0088] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B4 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0089] Example 5

[0090] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0091] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(ethylene oxide-2-ylmethoxy)propyltriethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and a 3 g hydrophobic siloxane compound solution was obtained after 30 minutes.

[0092] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B5, and set aside for use.

[0093] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B5 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 120°C and the time is 2 hours.

[0094] Example 6

[0095] Step (a): Mix the pretreatment agent (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) with isopropanol to obtain the first solution A (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane content is 20wt%), which is ready for use.

[0096] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0097] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B6, and set aside for use.

[0098] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B6 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0099] Example 7

[0100] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0101] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (trimethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and a 3 g hydrophobic siloxane compound solution was obtained after 30 minutes.

[0102] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B7, and set aside for use.

[0103] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B7 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0104] Example 8

[0105] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed with ethyl acetate, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0106] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 39.13:60.12:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0107] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B8, and set aside for use.

[0108] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B8 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0109] Example 9

[0110] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 20wt%) is obtained and is ready for use.

[0111] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 60.12:39.13:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and a 3 g hydrophobic siloxane compound solution was obtained after 30 minutes.

[0112] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B9, and set aside for use.

[0113] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B9 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 100℃ and the time is 3 hours.

[0114] Example 10

[0115] Step (a): After the pretreatment agent (3-aminopropyl-3-ethoxysilane) is mixed evenly with isopropanol, the first solution A (3-aminopropyl-3-ethoxysilane content is 50wt%) is obtained and is ready for use.

[0116] Step (b): The first compound (eicosyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0117] Step (c): Add 10 mL of the second organic solvent (isopropanol) to the hydrophobic siloxane compound solution, mix well to obtain the second solution B10, and set aside for use.

[0118] Step (d): The first solution A prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution B10 prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 90℃ and the time is 5 hours.

[0119] Example 11

[0120] Step (a): The pretreatment agent (N-(2-aminoethyl)-3-aminopropyltriethoxysilane) was mixed with butyl acetate to obtain the first solution (N-(2-aminoethyl)-3-aminopropyltriethoxysilane content was 2wt%), which was then set aside for use.

[0121] Step (b): The first compound (propyltriethoxysilane): the second compound (3-(2,3-epoxypropoxy)propyltrimethoxysilane): the catalyst (triethylamine) were mixed in a mass ratio of 48.62:50.63:0.75, and 2 mL of the second organic solvent (isopropanol) was added. After mixing thoroughly, the mixture was reacted at room temperature, and 3 g of hydrophobic siloxane compound solution was obtained after 30 minutes.

[0122] Step (c): Add 10 mL of the second organic solvent (butyl acetate) to the hydrophobic siloxane compound solution, mix well to obtain the second solution, and set aside for use.

[0123] Step (d): The first solution prepared in step (a) is used to pretreat the glass substrate. After drying, the second solution prepared in step (c) is applied to the glass substrate by spraying. After curing in an oven, a transparent, wear-resistant, fluorine-free long carbon chain hydrophobic coating is obtained. The curing temperature is 80℃ and the time is 5 hours.

[0124] Comparative Example 1

[0125] Uncoated blank glass substrate

[0126] Comparative Example 2

[0127] The difference between this comparative example and Example 10 is that no pretreatment agent was added.

[0128] Comparative Example 3

[0129] The difference between this comparative example and Example 10 is that the first compound is not added during polymerization.

[0130] Comparative Example 4

[0131] The difference between this comparative example and Example 10 is that no second compound was added during polymerization.

[0132] The inventors of this case characterized the coating test data of the above embodiments and comparative examples, and the results are shown in Table 1.

[0133] Table 1. Coating test data for Examples 1-11 and Comparative Examples 1-4

[0134]

[0135]

[0136] The results in Table 1 above show that:

[0137] By gradually increasing the carbon chain length of the long carbon branches in the carbon-silicon polymer, the coating can achieve a more superior hydrophobic effect. Preferably, the present invention uses eicosyltriethoxysilane as the first compound to react with the second compound to form a siloxane compound, controlling the reaction time to 30 minutes, and then performing a ring-opening reaction with an amino group. Isopropanol is used as the first organic solvent, which greatly reduces environmental pollution while also expanding the application field of the material due to its long carbon chain properties, making it highly efficient, low-cost and environmentally friendly.

[0138] In summary, this invention prepares a wear-resistant, fluorine-free, long-chain hydrophobic coating through a simple process, which is beneficial for practical applications.

[0139] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0140] Obviously, the embodiments of the present invention shown above are only intended to illustrate the principles of the invention and not to limit its implementation. Those skilled in the art can make other modifications or alterations to the present invention based on the above description. While it is impossible to exhaustively list all embodiments, any obviously deducible changes to the technical solutions are still protected by this invention.

Claims

1. A wear-resistant, fluorine-free, long-chain hydrophobic coating, characterized in that, include: A first component and a second component, the first component comprising a pretreatment agent and a first organic solvent, the pretreatment agent being used at least to provide reaction sites; The second component includes a siloxane compound, a catalyst, and a second organic solvent. The siloxane compound comprises a long-chain hydrophobic segment and an epoxy anchoring segment, and the siloxane compound is capable of undergoing a ring-opening reaction with at least an amino group.

2. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 1, characterized in that: The pretreatment agent includes any one or a combination of two or more of 3-aminopropyl-3-ethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane. And / or, based on 100% of the total mass of raw materials, the first component includes 2% to 50% pretreatment agent and 50% to 98% first organic solvent.

3. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 1, characterized in that: The siloxane compound is prepared by hydrolysis and condensation reaction of a first compound, a second compound and a catalyst. The first compound is a fluorine-free long carbon chain compound and the second compound is an epoxy silane compound. Preferably, the first compound comprises any one or a combination of two or more of the following: propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecanyltriethoxysilane, heptadecanyltriethoxysilane, octadecyltriethoxysilane, nonadecanyltriethoxysilane, eicosyltriethoxysilane, dodecyltriethoxysilane, hexadecyltriethoxysilane, heptadecanyltriethoxysilane, octadecyltriethoxysilane, nonadecanyltriethoxysilane, eicosyltriethoxysilane, dodecyltriethoxysilane, and dodecyltriethoxysilane. Preferably, the second compound comprises any one or a combination of two of 3-(2,3-epoxypropoxy)propyltrimethoxysilane and 3-(epoxyethylene-2-ylmethoxy)propyltriethoxysilane.

4. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 1, characterized in that: Based on 100% of the total mass of raw materials, the second component includes 2% to 42% siloxane compounds, 5% to 10% catalysts, and the balance being a second organic solvent; And / or, the catalyst comprises a basic catalyst or an acidic catalyst. Preferably, the basic catalyst comprises any one or a combination of two or more of ethylamine, diethylamine, triethylamine, tripropylamine, trimethylamine, N,N-diisopropylethylamine, and triisopropylamine, with triethylamine being particularly preferred. Preferably, the acidic catalyst comprises any one or a combination of two or more of acetic acid, formic acid, and oxalic acid.

5. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 3, characterized in that: The raw materials for preparing the siloxane compound, based on a total mass of 100%, include 20%–30% of a first compound, 20%–30% of a second compound, 0.2%–0.45% of a catalyst, and a second organic solvent. And / or, the hydrolysis-condensation reaction is carried out at room temperature for a time of less than 1 hour; And / or, the mass ratio of the first compound to the second compound is 1:2 to 2:

1.

6. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 1, characterized in that: Both the first organic solvent and the second organic solvent independently include any one or a combination of two or more of isopropanol, ethanol, ethyl acetate, and butyl acetate; And / or, the sum of the first organic solvent and the second organic solvent constitutes 65% to 90% of the total mass content of all raw materials in the wear-resistant, fluorine-free, long-chain hydrophobic coating; And / or, the siloxane compound has a mass content of 2% to 55% in all raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating; And / or, the catalyst has a mass content of 0.7% to 5% in all raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating; And / or, the epoxy silane compound has a mass content of 1% to 30% in all raw materials of the wear-resistant, fluorine-free, long-chain hydrophobic coating; And / or, the fluorine-free long carbon chain compound has a mass content of 1% to 30% in all raw materials of the wear-resistant fluorine-free long carbon chain hydrophobic coating.

7. A wear-resistant, fluorine-free, long-chain hydrophobic coating, characterized in that, It is formed by curing the wear-resistant, fluorine-free, long-chain hydrophobic coating according to any one of claims 1-6.

8. The wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 7, characterized in that: The contact angle between the surface of the wear-resistant, fluorine-free, long-chain hydrophobic coating and water is 90° to 120°, preferably greater than or equal to 115° to 120°; and / or, the light transmittance of the wear-resistant, fluorine-free, long-chain hydrophobic coating is greater than 98%, preferably greater than 99%. And / or, the thickness of the wear-resistant, fluorine-free, long-chain hydrophobic coating is 50nm to 300nm, preferably 100nm to 200nm.

9. The method for preparing the wear-resistant, fluorine-free, long-chain hydrophobic coating according to claim 7 or 8, characterized in that, include: Provide a wear-resistant, fluorine-free, long-chain hydrophobic coating according to any one of claims 1-6; The first component is used to pretreat the substrate surface to provide reaction sites; The second component is applied to the pretreated substrate surface and then cured to form the wear-resistant, fluorine-free, long carbon chain hydrophobic coating. Preferably, the pretreatment includes: soaking the substrate in a piranha solution for more than 24 hours, and then soaking it in the first component for more than 30 minutes; Preferably, the curing temperature is 80℃~120℃ and the time is more than 1 hour, preferably more than 3 hours; And / or, methods of applying the second component to the pretreated substrate surface include coating, preferably spraying.

10. The application of the wear-resistant, fluorine-free, long-chain hydrophobic coating of any one of claims 1-6 or the wear-resistant, fluorine-free, long-chain hydrophobic coating of claim 7 or 8 in the fields of glass material surface, biomedical, or display screen protection, preferably, the glass material includes photovoltaic glass, architectural glass, or automotive windshield.

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