Anti-fog coating, method for manufacturing the same, and anti-fog glass

Abstract

The present application relates to an anti-fog coating, a manufacturing method thereof, and an anti-fog glass, in which the manufacturing raw materials of the anti-fog coating include a hydrophilic copolymer, an epoxy resin, a coupling agent, a curing agent, and a first solvent, the manufacturing raw materials of the hydrophilic copolymer include a hydrophilic monomer, an initiator, and a second solvent, the solubility of the epoxy resin in water is about 90% or more, and the solubility of the hydrophilic copolymer in water is about 90% or more.

Description

Technical Field

[0001] (Cross - reference to related applications) This application claims the priority of a Chinese patent application with the application number 202111305548.3 and the title "Anti - fogging Coating, Its Manufacturing Method and Anti - fogging Glass", which was filed on November 05, 2021, and the full text thereof is incorporated herein by reference.

[0002] This application relates to the technical field of vehicle glass, and particularly to anti - fogging coatings, their manufacturing methods, and anti - fogging glass.

Background Art

[0003] Automotive glass is prone to fogging under conditions where there is a large difference in temperature and humidity inside and outside the vehicle. Fogging affects the driver's visibility and may further cause accidents. When generally using air - conditioning blowing and electric heating methods to remove fog, these methods have hysteresis and high energy consumption.

[0004] Currently, a technical solution for eliminating the fogging phenomenon by manufacturing two coating layers on the glass substrate of an automobile has been disclosed. In one technical solution, the two - layer structure includes a water - absorbing anti - fogging layer that plays an anti - fogging role and a base layer that plays a connection and buffering role. The water - absorbing anti - fogging layer repeatedly absorbs and releases water during use, generating a large interfacial stress due to the expansion and contraction of the coating layer. When only using a single - layer water - absorbing anti - fogging layer, the adhesion between the coating layer and the substrate decreases due to the interfacial stress, and peeling problems are likely to occur. Therefore, it is particularly important to add a single base layer, which can tightly bond with the substrate, relieve the interfacial stress caused by the water - absorbing anti - fogging layer, and further improve the overall peel resistance. However, the process of forming two coating layers is complicated and the production cost increases.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Based on this, the present invention provides anti-fogging coatings according to various embodiments. The technical proposal is as follows. [Means for solving the problem]

[0006] An anti-fogging coating, wherein the raw materials for its manufacture include a hydrophilic copolymer, an epoxy resin, a coupling agent, a curing agent, and a first solvent, the raw materials for the hydrophilic copolymer include a hydrophilic monomer, an initiator, and a second solvent, the solubility of the epoxy resin in water is about 90% or more, and the solubility of the hydrophilic copolymer in water is about 90% or more.

[0007] In some embodiments, the hydrophilic monomer is a combination of an acrylic acid ester monomer and an acrylamide monomer.

[0008] In some embodiments, the acrylic acid ester monomer is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, or a combination thereof.

[0009] In some examples, the acrylamide monomer is acrylamide, N,N-dimethylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, or a combination thereof.

[0010] In some embodiments, the epoxy resin is an aliphatic glycidyl ether, and the aliphatic glycidyl ether is trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, sorbitol glycidyl ether, or a combination thereof.

[0011] In some embodiments, the mass ratio of the hydrophilic copolymer to the epoxy resin is approximately (1-4):1.

[0012] In some embodiments, the raw materials for producing the anti-fogging coating comprise, by weight, about 1 to about 80 parts hydrophilic copolymer, about 1 to about 20 parts epoxy resin, about 0.1 to about 10 parts coupling agent, about 0.4 to about 15 parts curing agent, and about 20 to about 50 parts first solvent.

[0013] In some embodiments, the coupling agent is γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, or a combination thereof.

[0014] In some embodiments, the curing agent is diethylenetriamine, hydroxyethylethylenediamine, isophoronediamine, or a combination thereof.

[0015] In some embodiments, the initiator is a radical initiator containing a nitrogen-nitrogen double bond.

[0016] In some examples, the first solvent and the second solvent are independently an alcohol-based solvent or an ether-based solvent.

[0017] In some embodiments, the raw materials for producing the anti-fogging coating further include a silane hydrolysis catalyst, a filler, an antioxidant, an ultraviolet absorber, a leveling agent, or a combination thereof.

[0018] In some embodiments, the silane hydrolysis catalyst is a base catalyst or an acid catalyst.

[0019] In some embodiments, the filler is nanosilica, nanoalumina, or a combination thereof.

[0020] In some embodiments, the antioxidant is triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-bis3-(3'5'di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, or a combination thereof.

[0021] In some embodiments, the UV absorber is 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a combination thereof.

[0022] In some embodiments, the raw materials for the production of the anti-fogging coating further include an accelerator, the accelerator being methyllithium, triethylaluminum, ethylmagnesium iodide, methylzinc chloride, trimethyllead hydride, or a combination thereof.

[0023] This application further provides a method for manufacturing the above-mentioned anti-fogging coating, the technical proposal being as follows. A method for producing an anti-fogging paint includes the steps of: mixing a hydrophilic monomer, an initiator, and a second solvent, carrying out a polymerization reaction to produce a hydrophilic copolymer; and mixing the hydrophilic copolymer, an epoxy resin, a coupling agent, a curing agent, and a first solvent, carrying out a crosslinking reaction to produce an anti-fogging paint.

[0024] The anti-fog glass includes a glass substrate and an anti-fog coating layer on the glass substrate, the anti-fog coating layer being formed from the anti-fog paint applied to the glass substrate, and the thickness of the anti-fog coating layer being approximately 5 μm to 30 μm.

[0025] In some embodiments, the glass substrate is a curved glass plate, the curved glass plate has a convex surface and a concave surface, the anti-fogging coating layer is provided on the concave surface, the anti-fogging coating has a maximum thickness and a minimum thickness, and the difference between the maximum thickness and the minimum thickness is about 1 μm to 5 μm.

[0026] In some embodiments, the anti-fogging glass further includes an intermediate adhesive layer and another glass substrate. The glass substrate coated with the anti-fogging coating layer, the intermediate adhesive layer and the another glass substrate are laminated in sequence to form a laminated glass, and the anti-fogging coating layer is located on the surface of the glass substrate opposite to the intermediate adhesive layer.

[0027] Details of one or more embodiments of the present application are described below, and other features, objects and advantages of the present application will become apparent from the specification and claims.

[0028] Hereinafter, in order to more clearly explain the technical solutions in the embodiments or the prior art of the present application, the drawings necessary for the description of the embodiments or the prior art will be briefly introduced. As is clear, the drawings described below are only embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings on the premise of not exerting creative labor.

Brief Description of the Drawings

[0029] [Figure 1] It is a structural schematic diagram of anti-fogging glass manufactured in one embodiment.

Modes for Carrying Out the Invention

[0030] Hereinafter, the technical solutions in the embodiments of the present application will be clearly and completely described. As is clear, the described embodiments are only some embodiments of the present application, not all embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art on the premise of not performing creative labor are included in the protection scope of the present application.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this application pertains. The terms used herein are for illustrative purposes only and are not intended to limit this application.

[0032] term Terms and expressions used herein have the following meanings unless otherwise stated or contradicted:

[0033] In this application, the scope of the terms “and / or,” “or / and,” and “and / or” used includes any one of two or more related enumeration items, including any and all combinations of related enumeration items, the aforementioned any and all combinations including any two related enumeration items, any more related enumeration items, or all related enumeration items.

[0034] In this specification, "one or more types" refers to one, two, or more of the enumerated items. Here, "more types" refers to two or more types.

[0035] As used herein, “that combination,” “that any combination,” and “that any combination scheme” include all appropriate combination schemes of any two or any two or more items of the enumerated items.

[0036] In this specification, the term "preferably" is used solely to describe a more effective embodiment or example, and should not be understood as limiting the scope of protection of this application.

[0037] In this application, technical features described in open format include both closed technical means consisting of the enumerated features and open technical means containing the enumerated features.

[0038] In this application, unless otherwise specified, a numerical interval includes both endpoints.

[0039] Unless otherwise specified, the percentage content in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0040] Unless otherwise specified, the percentage concentration relating to this application is referred to as the final concentration. The final concentration refers to the proportion of the added component in the system after the component has been added.

[0041] Unless otherwise specified, the temperature parameter in this application may be constant temperature processing or processing within a certain temperature range. In the constant temperature processing, the temperature can vary within the accuracy range of the instrument control.

[0042] The "solubility" in this application, unless otherwise specified, refers to the mass of solute that dissolves in water when it reaches a saturated state at 20°C.

[0043] The anti-fogging coating comprises a hydrophilic copolymer, epoxy resin, coupling agent, curing agent, and a first solvent as raw materials for production, the raw materials for production of the hydrophilic copolymer comprising a hydrophilic monomer, initiator, and second solvent, the solubility of the epoxy resin in water being 90% or more, and the solubility of the hydrophilic copolymer in water being 90% or more.

[0044] This invention involves using a hydrophilic monomer to carry out a polymerization reaction with the action of an initiator to produce a highly soluble hydrophilic copolymer. Subsequently, the hydrophilic copolymer is reacted with a highly soluble epoxy resin using a curing agent. Here, the hydrophilic copolymer is a linear polymer, and the linear hydrophilic copolymer can crosslink with the epoxy resin to form a strong semi-interpenetrating network structure, which is advantageous for improving surface adhesion, abrasion resistance, toughness, and heat resistance. The semi-interpenetrating network structure releases stress generated after the coating layer absorbs and releases water, making it difficult for the coating layer to peel off the glass substrate. At the same time, the coupling agent can play an important connecting role between the paint and the glass substrate, and the manufactured paint can be applied directly to the glass substrate in a single layer and is less prone to peeling. By applying the anti-fogging paint of this invention in a single layer to the glass substrate, the base layer between the anti-fogging water-absorbing layer and the glass substrate layer can be omitted, and the hard coating layer on the outer surface of the anti-fogging water-absorbing layer can also be omitted, simplifying the production process and reducing production costs. Furthermore, the anti-fog coating layer of the present invention has excellent water absorption properties, a good anti-fog effect, can actively prevent fogging of glass, has a long service life, and can significantly reduce the energy consumption of automobiles.

[0045] Higher solubility indicates that the material has more polar groups and is more likely to form a coating layer with higher water absorption. Preferably, the solubility of the hydrophilic copolymer in water is about 95% or higher.

[0046] In one embodiment, the hydrophilic monomer is a combination of an acrylic acid ester monomer and an acrylamide monomer.

[0047] By using a combination of acrylic acid ester monomers and acrylamide monomers, both can undergo polymerization reactions as hydrophilic monomers under the action of an initiator to produce hydrophilic copolymers with a linear structure and high solubility.

[0048] Acrylic acid ester polymers have good film-forming properties and good adhesion to substrates, and acrylic acid ester monomers can provide different functions depending on their different side chain structures. In one preferred example, the side chains of the acrylic acid ester monomers used all contain hydrophilic groups, which can increase the hydrophilicity of the coating layer, and monomers containing methyl groups can be used to ensure the hardness and water resistance of the coating layer. Acrylic acid amide monomers not only provide hydrophilic amide groups but can also perform a crosslinking action.

[0049] The hydrophilic monomer may optionally contain hydroxyl groups, carboxyl groups, epoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, cyano groups, amide groups, etc., in its molecular structure.

[0050] Selectively, the acrylic acid ester monomer is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, or a combination thereof.

[0051] The acrylamide monomer is selectable to be acrylamide, N,N-dimethylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, or a combination thereof.

[0052] The above-mentioned hydrophilic monomers can be polymerized under the action of an initiator to produce hydrophilic copolymers.

[0053] Selectively, the initiator is a radical initiator containing a nitrogen-nitrogen double bond.

[0054] In some embodiments, the initiator is an azo initiator and includes, but is not limited to, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobisisobutylamidine hydrochloride, azobisisobutylmidazoline hydrochloride, and 2-(carbamoylazo)isobutyronitrile. This type of initiator decomposes to produce only one type of radical and does not cause other side reactions.

[0055] To make it easier to understand, the polymerization reaction described above is carried out in the second solvent.

[0056] The second solvent is optionally an alcohol-based or ether-based solvent, and includes, but is not limited to, n-butanol, isobutanol, ethanol, methanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether. These organic solvents are compatible with the hydrophilic monomers mentioned above and can also be compatible with components such as epoxy resins, so that the final coating does not suffer from problems such as phase separation.

[0057] To make it easier to understand, the polymerization reaction described above is carried out under an inert atmosphere.

[0058] The gas providing the inert atmosphere may be nitrogen, argon, or helium. The inert gas can prevent the influence of moisture in the air on the system reaction.

[0059] After producing a hydrophilic copolymer, the hydrophilic copolymer, epoxy resin, coupling agent, curing agent, and first solvent are mixed and a crosslinking reaction is carried out to produce an anti-fogging paint.

[0060] Selectively, the epoxy resin is an aliphatic glycidyl ether.

[0061] The aliphatic glycidyl ether is trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, sorbitol glycidyl ether, or a combination thereof.

[0062] Aliphatic glycidyl ethers contain ring-opening crosslinkable epoxy groups in their molecular structure, and also contain hydrophilic groups.

[0063] Preferably, the aliphatic glycidyl ether contains at least two functional groups in its molecular structure.

[0064] In one embodiment, the mass ratio of the hydrophilic copolymer to the epoxy resin is (1-4):1.

[0065] Selectively, the coupling agent is a silane coupling agent, such as γ-methacryloxypropyltrimethoxysilane (KH570), γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), divinyltriaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, or a combination thereof. The silane coupling agent can be hydrolyzed to produce Si-OH groups, which can bond more tightly to the glass substrate.

[0066] Further options may be available, the raw materials for the anti-fogging coating further comprising a silane hydrolysis catalyst. The addition of the silane hydrolysis catalyst can accelerate the hydrolysis of the silane coupling agent.

[0067] The silane hydrolysis catalyst can be selected to be either a base catalyst or an acid catalyst.

[0068] The base catalyst includes, but is not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0069] The acid catalyst includes, but is not limited to, nitric acid, hydrochloric acid, and acetic acid.

[0070] The curing agent may be selected to be diethylenetriamine, hydroxyethylethylenediamine, isophoronediamine, or a combination thereof.

[0071] The first solvent is selectively chosen from alcoholic or etheric solvents and includes, but is not limited to, n-butanol, isobutanol, ethanol, methanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether. These organic solvents are compatible with the hydrophilic monomers mentioned above and can also be compatible with components such as epoxy resins, so that the final coating layer does not suffer from phase separation or other problems. The first solvent may be the same as or different from the second solvent.

[0072] In some embodiments, the raw materials for producing the anti-fogging coating consist of, by weight, about 1 to about 80 parts by weight of a hydrophilic copolymer, about 1 to about 20 parts by weight of an epoxy resin, about 0.1 to about 10 parts by weight of a coupling agent, about 0.4 to about 15 parts by weight of a curing agent, and about 20 to about 50 parts by weight of a first solvent.

[0073] The raw materials for the anti-fogging coating may optionally further include one or more of the following: fillers, antioxidants, ultraviolet absorbers, and leveling agents.

[0074] By adding a filler, the abrasion resistance and heat resistance of the coating layer can be improved. In one embodiment, the filler is nanosilica, nanoalumina, or a combination thereof. The primary particle size of the filler is preferably 20 nm or less, and commercially available examples include Evonik's AERROSIL A200, AEROXIDE ALU C, WACKER HDKV15, N20, etc.

[0075] The amount of filler added is preferably 0.05% to 0.20% (100% of the total paint volume).

[0076] By adding antioxidants and UV absorbers, the aging resistance and weather resistance of the coating layer can be improved. Antioxidants include triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-bis-3-(3'5'-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, or a combination thereof. UV absorbers include 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a combination thereof.

[0077] In some preferred embodiments, the antioxidant is triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and the ultraviolet absorber is 2,2',4,4'-tetrahydroxybenzophenone, with the added masses being 0.5% to 1.5% and 0.1% to 0.5%, respectively (100% of the total paint mass).

[0078] By adding a leveling agent, problems such as orange peel texture and repellency on the coating layer can be reduced, and the surface of the coating layer can be made smoother and flatter. Examples of leveling agents include BYK-345, BYK-333, BYK-307, BYK337, and BYK341 from BYK GmbH in Germany.

[0079] Preferably, the amount of leveling agent added may be 150 ppm to 600 ppm in terms of the total mass of the system.

[0080] Optionally, the raw materials for the anti-fogging coating further include an accelerator, which is an organic compound formed by the direct bonding of metal atoms and carbon atoms, and by adding the accelerator, the toughness and wear resistance of the coating layer can be improved by utilizing the complexing action of the metal. In one embodiment, the accelerator is methyllithium, triethylaluminum, ethylmagnesium iodide, methylzinc chloride, trimethyllead hydride, or a combination thereof.

[0081] In one embodiment, the amount of accelerator added is 0.5% to 3%, preferably 1% to 1.8% (100% of the total paint mass).

[0082] To make it easier to understand, other functional additives may be added to the anti-fogging coating of the present invention as needed.

[0083] One embodiment of the present invention provides a method for manufacturing anti-fog glass, comprising the following steps:

[0084] Step 1: Production of hydrophilic copolymer Approximately 5 to 35 parts by weight of hydrophilic monomer and approximately 40 to 85 parts by weight of solvent are added to the reaction flask, then an inert gas is passed through and the mixture is stirred and dispersed, after which the initiator is added and the reaction is carried out at a constant temperature for a constant time.

[0085] Step 2: Manufacturing of anti-fog paint Approximately 1 to 80 parts by weight of hydrophilic copolymer, approximately 1 to 20 parts by weight of epoxy resin, approximately 0.1 to 10 parts by weight of coupling agent, approximately 0.5 to 15 parts by weight of curing agent, and approximately 20 to 50 parts by weight of first solvent are uniformly stirred and reacted at a constant temperature for a constant time to obtain an anti-fogging coating.

[0086] Step 3: Manufacturing of anti-fog glass Figure 1 shows a schematic diagram of the structure of the anti-fog glass of this embodiment.

[0087] The surface of the glass substrate 01 is cleaned. Thoroughly cleaning the glass is advantageous for applying the coating solution more sufficiently and uniformly.

[0088] To make it clear, the cleaning process consists of physical cleaning, chemical cleaning, and a combination of physical and chemical cleaning. Physical cleaning in the cleaning process includes gauze wiping, powder polishing, plasma treatment, or a combination thereof. Polishing powders in physical cleaning include nano-cerium oxide, nano-aluminum oxide, nano-magnesium oxide, or a combination thereof. Chemical cleaning includes alkaline cleaning, acid cleaning, fish-eater solution immersion, or a combination thereof. The cleaning process aims to remove dust particles from the glass and activate the surface, and the cleaning method is not limited to those described above, but may be any method that can achieve the objective.

[0089] Subsequently, the anti-fog paint is applied to the glass surface using a specific application method. After the anti-fog paint is leveled on the glass surface, it is cured at a certain temperature for a certain period of time. After curing, an anti-fog coating layer 02 is formed. The anti-fog coating layer 02 can adhere firmly to the surface of the glass substrate 01 by chemical bonding, and the thickness of the anti-fog coating layer is approximately 5 μm to 30 μm.

[0090] The application method can be selected from spin coating, shower coating, spray coating, dip coating, or spray coating. In one embodiment, the application is spray coating. By employing a spray coating process, the thickness of the coating layer can be controlled more precisely, and uniformity of the overall thickness of the coating layer can be ensured.

[0091] The curing temperature is selectable between approximately 120°C and 200°C, and the curing time is selectable between approximately 20 min and 720 min.

[0092] In one embodiment, the anti-fog coating can be manufactured and used as an anti-fog spray. The driver can then spray the anti-fog spray onto the car's glass, effectively preventing fogging of the glass, extending its lifespan, and significantly reducing the energy consumption of the vehicle.

[0093] The anti-fog glass comprises a glass substrate and an anti-fog coating layer on the glass substrate, wherein the anti-fog coating layer is formed from the anti-fog paint applied to the glass substrate, and the thickness of the anti-fog coating layer is approximately 5 μm to 30 μm.

[0094] In one embodiment, the glass substrate may be a curved glass plate, the curved glass plate having a convex surface and a concave surface, the anti-fog coating layer being provided on the concave surface, the anti-fog coating layer having a maximum thickness and a minimum thickness, the difference between the maximum thickness and the minimum thickness being approximately 1 μm to 5 μm.

[0095] Forming an anti-fogging coating layer on the concave surface can be achieved by a spray-coating process, which allows for more precise control of the coating layer thickness and ensures overall uniformity of the coating thickness.

[0096] In one embodiment, the anti-fog glass further includes an intermediate adhesive layer and another glass substrate, and the glass substrate coated with an anti-fog coating layer, the intermediate adhesive layer and the other glass substrate are sequentially laminated to form laminated glass, and the anti-fog coating layer is located on the surface of the glass substrate opposite to the intermediate adhesive layer.

[0097] The following will provide further explanation with reference to specific examples and comparative examples. Unless otherwise specified, the raw materials used in the following specific examples may all be commercially available products, the equipment used may all be commercially available products unless otherwise specified, and the processes involved are all typically selected by those skilled in the art unless otherwise specified.

[0098] Example 1 This embodiment provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0099] Step 1: Production of hydrophilic copolymer 2 g of hydroxyethyl acrylate, 4 g of acrylamide, and 40 g of propylene glycol methyl ether were weighed and placed in a reaction flask. After protecting the flask by venting it with nitrogen gas and stirring it uniformly, 0.15 g of azobisisobutyronitrile was added. The reaction flask was placed in an oil bath at 70°C and stirred for 12 hours to obtain a hydrophilic copolymer with a solubility of 94%.

[0100] Step 2: Manufacturing of anti-fog paint 7.5 g of the hydrophilic copolymer produced in Step 1 and 5 g of epoxy resin EX-313 (a commercially available product from Nagase ChemteX Corporation, belonging to the glycerin triglycidyl ether class with a solubility of 99%) were taken in a mass ratio of 1.5:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 0.5 g of silane coupling agent KH550 and 0.6 g of diethylenetriamine were added. After uniform stirring, the mixture was reacted at room temperature for 2 hours to obtain anti-fogging paint 1.

[0101] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 150°C for 2 hours to obtain anti-fog glass.

[0102] Example 2 This embodiment provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0103] Step 1: Production of hydrophilic copolymer 2 g of hydroxyethyl acrylate, 4 g of acrylamide, and 40 g of propylene glycol methyl ether were weighed and placed in a reaction flask. The flask was protected by aeration with nitrogen gas and mixed uniformly. Then, 0.15 g of azobisisobutyronitrile was added, and the reaction flask was placed in an oil bath at 70°C and stirred for 12 hours to obtain a hydrophilic copolymer with a solubility of 94%.

[0104] Step 2: Manufacturing of anti-fog paint 12 g of the hydrophilic copolymer produced in Step 1 and 3 g of epoxy resin EX-614B (a commercially available product from Nagase ChemteX Corporation, belonging to the sorbitol glycidyl ether class with a solubility of 94%) were taken in a mass ratio of 4:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 0.5 g of silane coupling agent KH560 and 0.4 g of diethylenetriamine were added. After uniform stirring, the mixture was reacted at room temperature for 2 hours to obtain anti-fogging paint 2.

[0105] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 160°C for 2 hours to obtain anti-fog glass.

[0106] Example 3 This embodiment provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0107] Step 1: Production of hydrophilic copolymer 1 g of hydroxyethyl methacrylate, 4 g of N,N-dimethylacrylamide, and 40 g of propylene glycol methyl ether were weighed and placed in a reaction flask. The flask was protected by aeration with nitrogen gas and mixed uniformly. Then, 0.1 g of azobisisobutyronitrile was added, and the reaction flask was placed in an oil bath at 70°C and stirred for 12 hours to obtain a hydrophilic copolymer with a solubility of 92%.

[0108] Step 2: Manufacturing of anti-fog paint 7.5 g of the hydrophilic copolymer produced in Step 1 and 5 g of epoxy resin EX-313 (a commercially available product from Nagase ChemteX Corporation, belonging to the glycerin triglycidyl ether class with a solubility of 99%) were taken in a mass ratio of 1.5:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 0.5 g of silane coupling agent KH550 and 1.3 g of hydroxyethyl ethylenediamine were added. After uniform stirring, the mixture was reacted at room temperature for 3 hours to obtain anti-fogging paint 3.

[0109] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 150°C for 2 hours to obtain anti-fog glass.

[0110] Example 4 This embodiment provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0111] Step 1: Production of hydrophilic copolymer 1.5 g of hydroxyethyl methacrylate, 5 g of N,N-dimethylacrylamide, and 55 g of propylene glycol methyl ether were weighed and placed in a reaction flask. The flask was protected by aeration with nitrogen gas and mixed uniformly. Then, 0.15 g of azobisisobutyronitrile was added, and the reaction flask was placed in an 80°C oil bath and stirred for 1 hour to obtain a hydrophilic copolymer with a solubility of 93%.

[0112] Step 2: Manufacturing of anti-fog paint 6 g of the hydrophilic copolymer produced in Step 1 and 6 g of epoxy resin EX-512 (a commercially available product from Nagase ChemteX Corporation, belonging to the polyglycerol polyglycidyl ether class, with a solubility of 100%) were taken in a mass ratio of 1:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 0.5 g of silane coupling agent KH550 and 1.2 g of hydroxyethyl ethylenediamine were added. After uniform stirring, the mixture was reacted at room temperature for 1 hour to obtain anti-fogging paint 4.

[0113] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 200°C for 1 hour to obtain anti-fog glass.

[0114] Example 5 This embodiment provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0115] Step 1: Production of hydrophilic copolymer 6 g of hydroxyethyl acrylate and 40 g of propylene glycol methyl ether were weighed and placed in a reaction flask. The flask was protected by aeration with nitrogen gas and mixed uniformly. Then, 0.15 g of azobisisobutyronitrile was added, and the reaction flask was placed in an oil bath at 70°C and stirred for 12 hours to obtain a hydrophilic copolymer with a solubility of 92%.

[0116] Step 2: Manufacturing of anti-fog paint 7.5 g of the hydrophilic copolymer produced in Step 1 and 5 g of epoxy resin EX-313 (a commercially available product from Nagase ChemteX Corporation, belonging to the glycerin triglycidyl ether class with a solubility of 99%) were taken in a mass ratio of 1.5:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 0.5 g of silane coupling agent KH550 and 0.6 g of diethylenetriamine were added. After uniform stirring, the mixture was reacted at room temperature for 2 hours to obtain anti-fogging paint 5.

[0117] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 150°C for 2 hours to obtain anti-fog glass.

[0118] Comparative Example 1 This comparative example provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0119] Step 1: Production of hydrophilic copolymer 2 g of hydroxyethyl acrylate, 4 g of acrylamide, and 40 g of propylene glycol methyl ether were weighed and placed in a reaction flask. After protecting the flask by venting it with nitrogen gas and stirring it uniformly, 0.15 g of azobisisobutyronitrile was added. The reaction flask was placed in an oil bath at 70°C and stirred for 12 hours to obtain a hydrophilic copolymer with a solubility of 94%.

[0120] Step 2: Manufacturing of anti-fog paint 10 g of the hydrophilic copolymer produced in Step 1 and 5 g of epoxy resin EX-313 (a commercially available product from Nagase ChemteX Corporation, belonging to the glycerin triglycidyl ether class with a solubility of 99%) were taken in a mass ratio of 2:1. The two were uniformly mixed with 50 g of anhydrous ethanol, and then 1.5 g of isophorone diamine was added. After uniform stirring, the mixture was reacted at room temperature for 2 hours to obtain anti-fogging paint 6.

[0121] Step 3: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 2 was applied to the glass substrate, and cured at 150°C for 2 hours to obtain anti-fog glass.

[0122] Comparative Example 2 This comparative example provides anti-fog glass and a method for manufacturing the same. The steps are as follows:

[0123] Step 1: Manufacturing of anti-fog paint 6g of epoxy resin EX-313 (a commercially available product from Nagase ChemteX Corporation, belonging to the glycerin triglycidyl ether group with a solubility of 99%) was taken, uniformly mixed with 50g of anhydrous ethanol, and then 1.5g of hydroxyethyl ethylenediamine was added. After uniform stirring, the mixture was reacted at room temperature for 2 hours to obtain anti-fogging paint 7.

[0124] Step 2: Manufacturing of anti-fog glass The surface of the glass substrate was cleaned, the anti-fog coating produced in step 1 was applied to the glass substrate, and cured at 120°C for 2 hours to obtain anti-fog glass.

[0125] The anti-fog glass manufactured as described above was subjected to performance evaluation, and the evaluation requirements were as follows: Anti-fog performance evaluation: Anti-fog glass was left in a 20°C, 50% RH environment for 1 hour, then transferred to a surface of 35°C water (5 cm above the water surface) with 100 ml or more of water, and the fogging time (s) was measured visually. Boiling resistance: The anti-fog glass was placed in 100°C boiling water for 2 hours, removed, and its appearance was observed. OK: No whitening, peeling, flaking, or detachment is observed in the coating layer. NG: Whitening, peeling, flaking, or detachment of the coating layer is observed. Alkali resistance: Anti-fog glass was immersed in 0.1n NaOH for 3 hours, removed, washed with deionized water, dried, and its appearance was observed. OK: No whitening, peeling, flaking, or detachment is observed in the coating layer. NG: Whitening, peeling, flaking, or detachment of the coating layer is observed. Abrasion resistance: Abrasion resistance tests were conducted on anti-fog glass using Taber 5131 in the USA, under test conditions with a load of 4.9 N / 400 mm. 2 (20mm*20mm friction surface), worn 5000 times at 40 cycles / min, with the friction cloth replaced every 1000 cycles. After the test, the appearance was observed, and a haze test was performed using a Nippon Shinsha HZ-V3 haze meter. OK: No cracks, peeling, or detachment are observed in the coating layer, and the haze change value is less than 2. NG: Cracks, peeling, or detachment are observed in the coating layer, and the haze change value is less than 2.

[0126] The evaluation results are shown in Table 1.

[0127] [Table 1]

[0128] As is clear from Table 1, the single-layer anti-fog glass of Examples 1 to 5 all met the requirements for anti-fog performance evaluation, boil resistance, and alkali resistance, reducing the number of processes and production costs. Specifically, it can delay the time it takes for the glass to fog up, has good anti-fog properties, ensures driving safety, and reduces the energy consumption of the vehicle. At the same time, it has good boil resistance and alkali resistance and is not easily peeled off. Furthermore, the single-layer anti-fog glass of Examples 1 to 4 also had excellent abrasion resistance. In Example 5, since only acrylate-based monomers were used as hydrophilic monomers, the abrasion resistance of the coating layer was slightly reduced. This is because the crosslinking action of the acrylamide-based monomer was insufficient, the crosslinking density decreased, and the strength of the coating layer decreased.

[0129] As a comparative example, Comparative Example 2, lacking a hydrophilic copolymer and coupling agent, failed to meet the requirements for boiling resistance, alkali resistance, and abrasion resistance. It also showed that the connection between the anti-fog coating layer and the glass substrate was poor, causing stress to be generated after the coating layer absorbed water and underwent expansion and contraction, leading to easy peeling of the coating layer from the substrate. Furthermore, the hydrophilic copolymer did not form a semi-interpenetrating network structure with the epoxy resin, resulting in a weak network structure and making the surface difficult to peel. Comparative Example 1, lacking a coupling agent, exhibited poor boiling resistance, demonstrating that the coupling agent plays an important role in connecting the coating layer and the substrate.

[0130] The technical features of the embodiments described above can be combined in any way, and for the sake of brevity, not all possible combinations of the technical features in the embodiments described above have been described. However, as long as these combinations of technical features are inconsistent, they should be considered to fall within the scope described herein.

[0131] The above embodiments illustrate only a few embodiments of the present application, and while the description is more specific and detailed, it should not be understood as limiting the scope of the claims. Those skilled in the art can make some modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection. Therefore, the scope of protection of this application is subject to the appended claims.

Claims

1. A method for manufacturing anti-fogging paint, The process involves mixing a hydrophilic monomer, an initiator, and a second solvent, carrying out a polymerization reaction, and producing a hydrophilic copolymer with a linear structure. The process includes the steps of mixing the hydrophilic copolymer, epoxy resin, coupling agent, curing agent, and first solvent, which are raw materials for manufacturing an anti-fogging coating, and carrying out a crosslinking reaction, wherein the hydrophilic copolymer crosslinks with the epoxy resin to form a semi-interpenetrating network structure, thereby manufacturing the anti-fogging coating. The solubility of the epoxy resin in water is 90% or more relative to the mass of water. The solubility of the hydrophilic copolymer in water is 90% or more relative to the mass of water. The hydrophilic monomer is a combination of an acrylic acid ester monomer and an acrylamide monomer. The acrylic acid ester monomers are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, or a combination thereof. The acrylamide monomer is acrylamide, N,N-dimethylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, or a combination thereof. The epoxy resin is an aliphatic glycidyl ether. The aliphatic glycidyl ether is trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, sorbitol glycidyl ether, or a combination thereof. A method for producing an anti-fogging coating, characterized in that the mass ratio of the hydrophilic copolymer to the epoxy resin is (1 to 4):

1.

2. The method for producing an anti-fogging paint according to claim 1, characterized in that the raw materials for producing the anti-fogging paint comprise, by weight, 1 to 80 parts by weight of a hydrophilic copolymer, 1 to 20 parts by weight of an epoxy resin, 0.1 to 10 parts by weight of a coupling agent, 0.4 to 15 parts by weight of a curing agent, and 50 parts by weight of a first solvent.

3. The method for producing an anti-fogging coating according to claim 1, characterized in that the coupling agent is γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, or a combination thereof.

4. The method for producing an anti-fogging paint according to claim 1, characterized in that the curing agent is diethylenetriamine, hydroxyethylethylenediamine, isophoronediamine, or a combination thereof.

5. The method for producing an anti-fogging paint according to claim 1, characterized in that the initiator is a radical initiator containing a nitrogen-nitrogen double bond.

6. The method for producing an anti-fogging coating according to claim 1, characterized in that the first solvent and the second solvent are each independently an alcohol-based solvent or an ether-based solvent.

7. The method for producing an anti-fogging paint according to claim 1, characterized in that the raw materials for producing the anti-fogging paint further include a silane hydrolysis catalyst, a filler, an antioxidant, an ultraviolet absorber, a leveling agent, or a combination thereof.

8. The silane hydrolysis catalyst is a base catalyst or an acid catalyst. and / or, the filler is nanosilica, nanoalumina, or a combination thereof. and / or the antioxidant is triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-bis-3-(3'5'di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, or a combination thereof. The method for producing an anti-fogging coating according to claim 7, characterized in that the ultraviolet absorber is 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a combination thereof.

9. The method for producing an anti-fogging paint according to claim 1, characterized in that the raw material for producing the anti-fogging paint further comprises an accelerator, the accelerator being methyllithium, triethylaluminum, ethylmagnesium iodide, methylzinc chloride, trimethyllead hydride, or a combination thereof.

10. A method for manufacturing anti-fog glass, The method includes applying an anti-fog coating produced by the method for producing an anti-fog coating according to any one of claims 1 to 9 to a glass substrate to form an anti-fog coating layer. A method for manufacturing anti-fog glass, characterized in that the thickness of the anti-fog coating layer is 5 μm to 30 μm.

11. The glass substrate is a curved glass plate, the curved glass plate has a convex surface and a concave surface, the anti-fog coating layer is provided on the concave surface, the anti-fog coating layer has a maximum thickness and a minimum thickness, and the difference between the maximum thickness and the minimum thickness is 1 μm to 5 μm. and / or, the anti-fog glass further comprises an intermediate adhesive layer and another glass substrate, wherein the glass substrate coated with an anti-fog coating layer, the intermediate adhesive layer and the other glass substrate are sequentially laminated to form laminated glass, and the anti-fog coating layer is located on the surface of the glass substrate opposite to the intermediate adhesive layer, characterized in that the method for manufacturing anti-fog glass according to claim 10.

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