Anti-fog paint, anti-fog glass and manufacturing method

Abstract

The present invention discloses an anti-fog coating, an anti-fog glass, and a manufacturing method thereof. The present invention involves synthesizing a UV absorber-modified monomer having a double bond, which is then polymerized with a silane monomer and an acrylic hydrophilic monomer. The resulting copolymer exhibits significantly improved light resistance, oxidation resistance, and weather resistance. The hydrophilic group of the acrylic hydrophilic monomer ensures anti-fog properties. The copolymer is incorporated into a silica sol to obtain an anti-fog coating. The inorganic components in the silica sol provide the coating with excellent mechanical properties, such as hardness. The siloxane in the copolymer and the siloxane in the sol undergo polycondensation during curing to form a dense three-dimensional network structure, further improving the coating's hardness and weather resistance.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority from a Chinese patent application filed with the China Patent Office on August 31, 2022, bearing application number 202211061719.7 and entitled "Anti-fog coating, anti-fog glass and manufacturing method," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of functional coatings, in particular to anti-fog paints, anti-fog glass and manufacturing methods. [Background technology]

[0003] With the advancement of intelligent automobiles, B-pillars are no longer just exterior components, but are increasingly being equipped with various functions by many host plants, such as biometric recognition of faces and fingerprints, NFC, surround view, and luminous decorations. In some B-pillar assembly products, the exterior panel leaves a transparent camera viewing angle area, and if this area becomes foggy, it can affect the normal operation of the camera and even the use of automatic (assisted) driving functions.

[0004] Applying an anti-fog coating to surfaces within the camera's viewing angle range effectively solves the problem of fogging. However, because this area is exposed to ultraviolet light for long periods of time, the coating must have high light resistance. However, conventional anti-fog coatings generally have the problem of being sensitive to light. Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide an anti-fog coating, an anti-fog glass, and a manufacturing method thereof, which solve the problems of the prior art, such as fogging in the camera viewing angle area of the outer glass of a B-pillar, and the light sensitivity of conventional anti-fog coatings. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention relates to the following inventions. A first aspect of the present invention is copolymer and silica sol, The polymerizable monomer of the copolymer includes a modified monomer of an ultraviolet absorber, a silane monomer, and an acrylic hydrophilic monomer; The modified monomer of the ultraviolet absorber is produced by a ring-opening reaction between an ultraviolet absorber having a hydroxyl group and an acrylic monomer having an epoxy group. To provide an anti-fog paint.

[0007] Preferably, the silica sol is an organic-inorganic hybrid silica sol.

[0008] In the anti-fog coating material of the present invention, the mass ratio of the copolymer to the silica sol is preferably (1 to 10):1, for example, 8:1, 5:1, 3:1, and the like.

[0009] In the anti-fog coating material of the present invention, the silica sol is produced by mixing and reacting a silicate, a catalyst, water, a third solvent, a leveling agent, and a coupling agent.

[0010] In the anti-fog coating material of the present invention, the silane monomer is one or a combination of two or more selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, methylvinyldiethoxysilane, methylvinyldimethylsilane, vinyltriisopropenoxysilane, and vinyltriacetoxysilane.

[0011] The silane monomer has a copolymerizable carbon-carbon double bond in its molecular structure, and also has a siloxane group, so as to contribute to the subsequent polycondensation with the silica sol.

[0012] In the anti-fog coating material of the present invention, the acrylic hydrophilic monomer is one or a combination of two or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

[0013] The acrylic hydrophilic monomer contains polar groups such as hydroxyl, carboxyl, amino and amide groups in its molecular structure, and therefore can increase the hydrophilicity of the copolymer.

[0014] In the anti-fog coating material of the present invention, the mass ratio of the modified monomer of the ultraviolet absorber, the silane monomer, and the acrylic hydrophilic monomer is (0.3-1):(0.3-1):(1-10). If the amount of the silane monomer added is too large, it will affect the hydrophilicity of the copolymer, and further affect the anti-fog properties of the coating.

[0015] In the anti-fog coating of the present invention, the copolymer is obtained by polymerizing the polymerizable monomers using an initiator. The initiator is a radical initiator containing a nitrogen-nitrogen double bond, preferably an azo-based initiator including, but not limited to, azobisisobutyronitrile and / or azobisdimethylvaleronitrile. Such initiators produce only radicals upon decomposition, without any side reactions.

[0016] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, and benzotriazole-based ones. In the present invention, the ultraviolet absorber having a hydroxyl group is grafted onto the acrylic monomer by a ring-opening reaction between the ultraviolet absorber having a hydroxyl group and the acrylic monomer having an epoxy group.

[0017] In the anti-fog coating material of the present invention, the hydroxyl group-containing ultraviolet absorber is one or a combination of two or more selected from the group consisting of 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0018] In the anti-fog coating material of the present invention, the ultraviolet absorber having a hydroxyl group absorbs light at 260 nm to 400 nm, preferably 320 nm to 400 nm.

[0019] The acrylic monomer having an epoxy group simultaneously has an epoxy group and a carbon-carbon double bond, and therefore can react with a hydroxyl group of an ultraviolet absorber and copolymerize with a comonomer of the copolymer, and examples thereof include one or a combination of two or more of glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (S)-glycerin methacrylate.

[0020] In the anti-fog coating of the present invention, the modified monomer of the ultraviolet absorber is preferably obtained by ring-opening reaction of an ultraviolet absorber having a hydroxyl group with an acrylic monomer having an epoxy group in a mass ratio of (0.5 to 1.8):1, using a catalyst that accounts for 25% to 40% of the total mass of the ultraviolet absorber and the acrylic monomer having an epoxy group; more preferably, the catalyst is a strongly acidic ion-exchange resin containing many strongly acidic groups, which readily reacts with H in solution. + The anionic groups contained in the resin itself can adsorb and bind other cations in the solution. Examples of ion exchange resins used in catalysts include, but are not limited to, Amberlyst-15 ion exchange resin and Amberlite IR-120 ion exchange resin. Such catalysts have advantages such as high activity and recyclability, and are therefore widely used.

[0021] In the anti-fog coating of the present invention, the silica sol is produced in such a manner that the mass ratio of the silicate, coupling agent, third solvent, water, and catalyst is (10-22):(5-18):(45-65):(6-15):(0.1-0.7), and the amount of the leveling agent used is 0.05% to 0.3% of the total mass of the silicate, coupling agent, third solvent, water, and catalyst.

[0022] In the anti-fog coating material of the present invention, the silica sol is The silicate is one or a combination of two or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; and / or The catalyst is an acid catalyst, which is one or a combination of two or more of acetic acid, hydrochloric acid, and nitric acid (under the acid catalyst conditions, a silica gel is formed by further crosslinking of linearly or randomly crosslinked polymers, which is more advantageous for producing a coating with excellent abrasion resistance), and / or The leveling agent is one or a combination of two or more of polyether-modified siloxane, polyester-modified polymethylalkylsiloxane, and polyether-polyester-modified hydroxyl group-containing polysiloxane, preferably polyether-modified polydimethylsiloxane (common market numbers include BYK333, BYK307, BYK306, BYK337, BYK341, etc., and the leveling agent of the present invention can effectively reduce the surface tension of the paint, prevent cissing, and increase the surface slippage), and / or the coupling agent is one or a combination of two or more of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane, and ureidopropyltriethoxysilane; It is produced by

[0023] A second aspect of the present invention provides a method for producing the above anti-fog coating material, comprising the following steps: The preparation of the modified monomer of the ultraviolet absorber includes: In a first solvent, the UV absorber having a hydroxyl group and the acrylic monomer having an epoxy group undergo a ring-opening reaction under the influence of a catalyst. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed to obtain a modified monomer of the UV absorber. (This modification process can improve the anti-aging ability of the UV absorber, and in actual use, improve the light-resistant aging ability of the coating.) The copolymer is prepared by In a second solvent, the modified monomer of the ultraviolet absorber, the silane monomer, and the acrylic hydrophilic monomer are polymerized using an initiator at a set temperature of preferably 65 to 100°C to produce the copolymer, which is an ultraviolet absorber copolymer modified with a silicone monomer and a hydrophilic monomer. The silica sol is prepared by: The method includes mixing and reacting the silicate, catalyst, water, third solvent, leveling agent, and coupling agent to produce the silica sol (preferably, the silica sol is aged for 0.5 to 7 days, and preferably, the water is deionized water). The preparation of the anti-fog coating material comprises: The copolymer and silica sol are mixed uniformly in a certain ratio to obtain the anti-fog coating material.

[0024] In the method for producing an anti-fog coating of the present invention, the first solvent and the second solvent are each independently selected from alcohol-based solvents or ether-based solvents, and examples thereof include, but are not limited to, one or a combination of two or more of 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.

[0025] A third aspect of the present invention provides anti-fog glass comprising a glass substrate and an anti-fog coating formed on a surface of the glass substrate using the above-mentioned anti-fog paint, wherein the glass substrate includes a light-transmitting region and a non-light-transmitting region, and the anti-fog coating covers at least the light-transmitting region of the glass substrate.

[0026] In the anti-fogging glass of the present invention, the visible light transmittance of the transparent region of the glass substrate is greater than 70%. Preferably, the glass substrate is soda-lime glass, aluminosilicate glass, lithium aluminosilicate glass, or boron silicate glass. The type and color of glass can be selected as needed; unless otherwise specified, ultra-white glass with a visible light transmittance of 90% or more is preferred. When the refractive power of the transparent region of the glass substrate is 110 mdpt or less, the glass substrate can achieve excellent optical quality in the transparent region, resulting in clearer images and higher visibility, which is more advantageous for collecting images in the transparent region. The glass substrate is sheet-form tempered glass, and the tempering method can include chemical tempering and / or physical tempering.

[0027] In the anti-fogging glass of the present invention, the anti-fogging coating has a thickness of 4 μm to 30 μm.

[0028] The anti-fog glass of the present invention can be used for exterior glass panes of A-pillars and / or B-pillars. Note that the smart B-pillar garnish module for an automobile includes not only the exterior glass pane but also an interior panel attached to the inside of the exterior glass pane, and may further include functional modules such as an infrared recognition module and / or a camera module, vehicle mounting members such as a ventilation membrane, and parts continuous with the automobile such as studs.

[0029] The glass substrate has a visible area that can transmit light (i.e., a light-transmitting area) in addition to the printed edge, and the anti-fog coating is installed on the side of the light-transmitting area facing the interior of the vehicle. The light-transmitting area can be a camera viewing angle area or a face recognition display area. The non-light-transmitting area is masked with ink printing to shield the substrates and functional modules of the A-pillar and B-pillar and improve overall visibility. The light-transmitting area can be oval, circular, or other design shapes.

[0030] In the anti-fogging glass of the present invention, when the distance between the boundary of the anti-fogging coating and the boundary of the light-transmitting region is d, d≦5 mm. If the distance exceeds 5 mm, the application of a subsequent structural adhesive may be affected.

[0031] In the anti-fogging glass of the present invention, the anti-fogging coating has a xenon lamp aging time of 2400 hours or more, and the sample after the xenon lamp aging test is visually inspected for the presence or absence of cracks in the coating. If no cracks are found, the glass is deemed to pass.

[0032] A fourth aspect of the present invention is Pre-treating and cleaning the glass substrate for subsequent use; applying the anti-fog paint to the surface of the light-transmitting region of the glass substrate, leveling and curing the paint, and then forming the anti-fog coating; The present invention provides a method for producing the anti-fogging glass, comprising the steps of:

[0033] The purpose of the pretreatment is not only to remove dust particles from the surface of the glass substrate, but also to improve the surface energy of the glass substrate so that the paint can be more easily spread on the surface of the substrate. Preferably, the pretreatment is performed by polishing, plasma treatment, etc., so that the surface dyne value of the light-transmitting area after the pretreatment is 60 or more.

[0034] In the method for producing anti-fog glass of the present invention, the coating method may preferably be one of spray coating, shower coating, spin coating, etc. Among these, spray coating makes it easier to apply the coating and ensures uniformity in the coating thickness. The spray coating method includes air spray coating, bell spray coating, ultrasonic spray coating, etc., and an appropriate spray coating method can be selected depending on the specific line design, shielding method, etc. The coating obtained by ultrasonic spray coating has higher uniformity, less spatter of raw materials, and high utilization rate, making it particularly suitable for actual production.

[0035] In the method for producing anti-fogging glass of the present invention, the leveling time is preferably 10 seconds to 300 seconds, the curing temperature is preferably 120°C to 200°C, and the curing time is preferably 15 minutes to 720 minutes.

[0036] The present invention involves the ring-opening reaction of a hydroxyl-containing UV absorber with an epoxy-containing acrylic monomer to synthesize a modified UV absorber monomer with a double bond, which is then polymerized with a silane monomer and an acrylic hydrophilic monomer to synthesize a silicone-modified UV absorber crosslinked copolymer. After modification with silicone, this copolymer exhibits significantly improved light resistance, oxidation resistance, and weather resistance. Furthermore, the hydrophilic groups contained in the acrylic hydrophilic monomer ensure the anti-fogging properties of the coating. When this copolymer is added to silica sol, particularly organic-inorganic hybrid silica sol, the inorganic component in the silicone portion contributes to the coating's excellent mechanical properties, such as hardness. Furthermore, upon curing, the siloxanes in the copolymer and the siloxanes in the silica sol undergo polycondensation reaction, forming a dense three-dimensional network structure, further improving the coating's hardness and weather resistance.

[0037] In order to more clearly describe the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments will be briefly described below. The drawings in the following description are some embodiments of the present invention, and it is obvious to those skilled in the art that other drawings can also be obtained based on these drawings without any creative efforts. [Brief explanation of the drawings]

[0038] [Figure 1] Schematic cross-sectional view of an anti-fogging glass according to an embodiment of the present invention used as an exterior glass pane for a B-pillar DETAILED DESCRIPTION OF THE INVENTION

[0039] In order to more clearly explain the present invention, the present invention will be further described below with reference to preferred examples. For those skilled in the art, the specific details described below should be considered as examples and not as limitations, and should not limit the scope of the claims of the present invention.

[0040] All numerical values in the present invention (including respective ranges of, for example, temperature, time, concentration, and weight) are appropriately expressed as approximations, usually modified (+) or (-) by increments of 0.1 or 1.0. It is understood that all numerical values are indicated by the preceding term "about."

[0041] A first aspect of the present invention is copolymer and silica sol, The polymerizable monomer of the copolymer includes a modified monomer of an ultraviolet absorber, a silane monomer, and an acrylic hydrophilic monomer; The modified monomer of the ultraviolet absorber is produced by a ring-opening reaction between an ultraviolet absorber having a hydroxyl group and an acrylic monomer having an epoxy group. To provide an anti-fog paint.

[0042] Preferably, the silica sol is an organic-inorganic hybrid silica sol.

[0043] In the anti-fog coating material of the present invention, the mass ratio of the copolymer to silica is preferably (1 to 10):1, for example, 5:1, 3:1, or the like.

[0044] In the anti-fog coating material of the present invention, the silica sol is produced by mixing and reacting a silicate, a catalyst, water, a third solvent, a leveling agent, and a coupling agent.

[0045] In the anti-fog coating material of the present invention, the silane monomer is one or a combination of two or more selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, methylvinyldiethoxysilane, methylvinyldimethylsilane, vinyltriisopropenoxysilane, and vinyltriacetoxysilane.

[0046] The silane monomer has a copolymerizable carbon-carbon double bond in its molecular structure as well as a siloxane group so as to contribute to the subsequent polycondensation with the silica sol.

[0047] In the anti-fog coating material of the present invention, the acrylic hydrophilic monomer is one or a combination of two or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

[0048] The acrylic hydrophilic monomer contains polar groups such as hydroxyl, carboxyl, amino and amide groups in its molecular structure, and therefore can increase the hydrophilicity of the copolymer.

[0049] In the anti-fog coating material of the present invention, the mass ratio of the modified monomer of the ultraviolet absorber, the silane monomer, and the acrylic hydrophilic monomer is (0.3-1):(0.3-1):(1-10). If the amount of the silane monomer added is too large, it will affect the hydrophilicity of the copolymer, and further affect the anti-fog properties of the coating.

[0050] In the anti-fog coating of the present invention, the copolymer is obtained by polymerizing the polymerizable monomers using an initiator. The initiator is a radical initiator containing a nitrogen-nitrogen double bond, preferably an azo-based initiator including, but not limited to, azobisisobutyronitrile and / or azobisdimethylvaleronitrile. Such initiators produce only radicals upon decomposition, without any side reactions.

[0051] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, and benzotriazole-based ones. In the present invention, the ultraviolet absorber having a hydroxyl group is grafted onto the acrylic monomer by a ring-opening reaction between the ultraviolet absorber having a hydroxyl group and the acrylic monomer having an epoxy group.

[0052] In the anti-fog coating material of the present invention, the hydroxyl group-containing ultraviolet absorber is one or a combination of two or more selected from the group consisting of 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0053] In the anti-fog coating material of the present invention, the ultraviolet absorber having a hydroxyl group absorbs light at 260 nm to 400 nm, preferably 320 nm to 400 nm.

[0054] The acrylic monomer having an epoxy group simultaneously has an epoxy group and a carbon-carbon double bond, and therefore can react with a hydroxyl group of an ultraviolet absorber and copolymerize with a comonomer of the copolymer, and examples thereof include one or a combination of two or more of glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (S)-glycerin methacrylate.

[0055] In the anti-fog coating of the present invention, preferably, the modified monomer of the ultraviolet absorber is obtained by ring-opening reaction of an ultraviolet absorber having a hydroxyl group and an acrylic monomer having an epoxy group in a mass ratio of (0.5 to 1.8):1, with a catalyst accounting for 25% to 40% of the total mass of both the ultraviolet absorber and the acrylic monomer having an epoxy group, and more preferably, the catalyst is a strongly acidic ion exchange resin containing many strongly acidic groups, which easily converts to H in solution. + The anionic groups contained in the resin itself dissociate the cations, and the dissociated cations can adsorb and bind other cations in the solution. Examples of ion exchange resins used in catalysts include, but are not limited to, Amberlyst-15 ion exchange resin and Amberlite IR-120 ion exchange resin. Such catalysts have advantages such as high activity and recyclability, and are therefore widely used.

[0056] In the anti-fog coating of the present invention, the silica sol is produced in such a manner that the mass ratio of the silicate, coupling agent, third solvent, water, and catalyst is (10-22):(5-18):(45-65):(6-15):(0.1-0.7), and the amount of the leveling agent used is 0.05% to 0.3% of the total mass of the silicate, coupling agent, third solvent, water, and catalyst.

[0057] In the anti-fog coating material of the present invention, the silica sol is The silicate is one or a combination of two or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; and / or The catalyst is an acid catalyst, which is one or a combination of two or more of acetic acid, hydrochloric acid, and nitric acid (under the acid catalyst conditions, a silica gel is formed by further crosslinking of linearly or randomly crosslinked polymers, which is more advantageous for producing a coating with excellent abrasion resistance), and / or The leveling agent is one or a combination of two or more of polyether-modified siloxane, polyester-modified polymethylalkylsiloxane, and polyether-polyester-modified hydroxyl group-containing polysiloxane, preferably polyether-modified polydimethylsiloxane (common market numbers include BYK333, BYK307, BYK306, BYK337, BYK341, etc., and the leveling agent of the present invention can effectively reduce the surface tension of the paint, prevent cissing, and increase the surface slippage), and / or The coupling agent is one or a combination of two or more of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane, and ureidopropyltriethoxysilane. It is produced by

[0058] A second aspect of the present invention provides a method for producing the above anti-fog coating material, comprising the following steps:

[0059] The preparation of the modified monomer of the ultraviolet absorber includes: In a first solvent, the UV absorber having a hydroxyl group and the acrylic monomer having an epoxy group undergo a ring-opening reaction under the influence of a catalyst. After the reaction is completed, the catalyst is removed by filtration, and then the solvent is removed to obtain a modified monomer of the UV absorber. (This modification process can improve the anti-aging ability of the UV absorber, and in actual use, improve the light-resistant aging ability of the coating.)

[0060] The copolymer is prepared by In a second solvent, the modified monomer of the ultraviolet absorber, the silane monomer, and the acrylic hydrophilic monomer are polymerized using an initiator at a set temperature of preferably 65 to 100°C to produce the copolymer, which is an ultraviolet absorber copolymer modified with a silicone monomer and a hydrophilic monomer.

[0061] The silica sol is prepared by: The method includes mixing and reacting the silicate, catalyst, water, third solvent, leveling agent, and coupling agent to produce the silica sol (preferably, the silica sol is aged for 0.5 to 7 days, and preferably, the water is deionized water).

[0062] The preparation of the anti-fog coating material comprises: The copolymer and silica sol are mixed uniformly in a certain ratio to obtain the anti-fog coating material.

[0063] In the method for producing an anti-fog coating of the present invention, the first solvent and the second solvent are each independently selected from alcohol-based solvents or ether-based solvents, and examples thereof include, but are not limited to, one or a combination of two or more of 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.

[0064] A third aspect of the present invention provides anti-fog glass, as shown in FIG. 1 , comprising a glass substrate 1 and an anti-fog coating 2 formed on the surface of the glass substrate 1 using the above-mentioned anti-fog paint, wherein the glass substrate 1 includes a light-transmitting region 11 and a non-light-transmitting region, and the anti-fog coating 2 covers at least the light-transmitting region 11 of the glass substrate 1.

[0065] In the anti-fogging glass of the present invention, the visible light transmittance of the light-transmitting region 11 of the glass substrate 1 is greater than 70%. Preferably, the glass substrate 1 is soda-lime glass, aluminosilicate glass, lithium aluminosilicate glass, or boron silicate glass. The type and color of glass can be selected as needed; unless otherwise specified, ultra-white glass with a visible light transmittance of 90% or more is preferred. When the refractive power of the light-transmitting region 11 of the glass substrate 1 is 110 mdpt or less, the glass substrate 1 can achieve excellent optical quality in the light-transmitting region 11, resulting in clearer images and higher recognition, which is more advantageous for image collection in the light-transmitting region 11. The glass substrate 1 is a sheet-form tempered glass, and the tempering method can be chemical tempering and / or physical tempering.

[0066] In the anti-fogging glass of the present invention, the anti-fogging coating 2 has a thickness of 4 μm to 30 μm.

[0067] The anti-fog glass of the present invention can be used for exterior glass panes of A-pillars and / or B-pillars, as shown in Fig. 1. The smart B-pillar garnish module for an automobile includes not only the exterior glass pane but also an interior panel attached to the inside of the exterior glass pane, and may further include functional modules such as an infrared recognition module and / or a camera module, vehicle mounting members such as a ventilation membrane, and parts continuous with the automobile such as studs.

[0068] The anti-fog coating 2 is installed on the side of the light-transmitting area 11 facing the interior of the vehicle. The light-transmitting area 11 can be the viewing angle area of a camera or the display area for face recognition. The non-light-transmitting area can be shielded by ink printing. The purpose of the ink layer 3 is to shield the substrates and functional modules of the A-pillar and B-pillar and improve overall visibility. The light-transmitting area 11 can be oval, circular, or other design shapes.

[0069] In the anti-fogging glass of the present invention, when the distance between the boundary of the anti-fogging coating 2 and the boundary of the light-transmitting region 11 is d, d≦5 mm. If the distance exceeds 5 mm, the application of the structural adhesive 4 may be affected.

[0070] In the anti-fogging glass of the present invention, the anti-fogging coating 2 has a xenon lamp aging time of 2400 hours or more, and the sample after the xenon lamp aging test is inspected for the occurrence of cracks in the coating appearance. If no cracks are found, the glass is deemed to pass.

[0071] A fourth aspect of the present invention is Pretreating and cleaning the glass substrate 1; The anti-fogging paint is applied to the surface of the light-transmitting region 11 of the glass substrate 1, leveled, and cured, and then the anti-fogging coating 2 is formed. The present invention provides a method for producing the anti-fogging glass, comprising the steps of:

[0072] The purpose of the pretreatment is not only to remove dust particles from the surface of the glass substrate 1, but also to improve the energy of the glass substrate 1 so that the paint can be more easily spread on the surface of the substrate 1. Preferably, the pretreatment is performed by polishing, plasma treatment, etc., so that the surface dyne value of the light-transmitting region 11 after the pretreatment is 60 or more.

[0073] In the method for producing anti-fog glass of the present invention, the coating method may preferably be one of spray coating, shower coating, spin coating, etc. Among these, spray coating makes it easier to apply the coating and ensures uniformity in the coating thickness. The spray coating method includes air spray coating, bell spray coating, ultrasonic spray coating, etc., and an appropriate spray coating method can be selected depending on the specific line design, shielding method, etc. The coating obtained by ultrasonic spray coating has higher uniformity, less spatter of raw materials, and high utilization rate, making it particularly suitable for actual production.

[0074] In the method for producing anti-fogging glass of the present invention, the leveling time is preferably 10 seconds to 300 seconds, the curing temperature is preferably 120°C to 200°C, and the curing time is preferably 15 minutes to 720 minutes.

[0075] Example 1 Specifically, in this example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0076] 1) In preparing a modified monomer of an ultraviolet absorber, 1.23 g of 2,2',4,4'-tetrahydroxybenzophenone was weighed and placed in a flask, followed by 1.42 g of glycidyl methacrylate and 25 g of propylene glycol methyl ether. After uniform stirring, 0.72 g of Amberlyst-15 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the modified monomer of the UV absorber was set aside for later use.

[0077] 2) In the preparation of the copolymer, 1 g of modified monomer of UV absorber, 1 g of methylvinyldiethoxysilane, 2 g of hydroxybutyl acrylate, and 50 g of propylene glycol ethyl ether were weighed into a three-necked flask, and 0.1 g of azobisdimethylvaleronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0078] 3) In preparing the silica sol, Ethyl orthosilicate, KH560 (γ-glycidoxypropyltrimethoxysilane), absolute ethanol, water, and hydrochloric acid were weighed out in a mass ratio of 10:8:45:7:0.24. The ethyl orthosilicate, KH560, absolute ethanol, and water were first placed in a reaction bottle and stirred uniformly. After uniform stirring, 1% mass fraction of hydrochloric acid was added drop by drop. Finally, BYK307 leveling agent was added in an amount of 0.05% of the total mass of the ethyl orthosilicate, KH560, absolute ethanol, water, and hydrochloric acid. The mixture was thoroughly stirred for 3 hours until uniform, and then aged for 2 days to obtain a silica sol.

[0079] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 8:1 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0080] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0081] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0082] Example 2 Specifically, in this example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0083] 1) In preparing a modified monomer of an ultraviolet absorber, 1.23 g of 2,2',4,4'-tetrahydroxybenzophenone was weighed and placed in a flask, followed by 1.42 g of glycidyl methacrylate and 25 g of propylene glycol methyl ether. After uniform stirring, 0.72 g of Amberlyst-15 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the modified monomer of the UV absorber was set aside for later use.

[0084] 2) In the preparation of the copolymer, 1 g of modified monomer of UV absorber, 1 g of methylvinyldiethoxysilane, 5 g of hydroxybutyl acrylate, and 50 g of propylene glycol ethyl ether were weighed into a three-necked flask, and 0.1 g of azobisdimethylvaleronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0085] 3) In preparing the silica sol, Ethyl orthosilicate, KH560, absolute ethanol, water, and hydrochloric acid were weighed out in a mass ratio of 10:8:45:7:0.24. The ethyl orthosilicate, KH560, absolute ethanol, and water were first placed in a reaction bottle and stirred uniformly. Then, hydrochloric acid with a mass fraction of 1% was added drop by drop. Finally, BYK307 leveling agent was added in an amount of 0.05% of the total mass of the ethyl orthosilicate, KH560, absolute ethanol, water, and hydrochloric acid. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0086] 4) In preparing the anti-fog coating, The copolymer was added to the silica sol in a mass ratio of 8:1, and the mixture was stirred at room temperature for 4 hours to make the reaction solution sufficiently homogenous.

[0087] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0088] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0089] Example 3 Specifically, in this example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0090] 1) In preparing a modified monomer of an ultraviolet absorber, 1.23 g of 2,4-dihydroxybenzophenone was weighed and placed in a flask, followed by 1.42 g of (S)-glycerin methacrylate and 25 g of ethylene glycol methyl ether. After uniform stirring, 0.72 g of Amberlite IR-120 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining UV absorber-modified monomer reaction solution was set aside for later use.

[0091] 2) In the preparation of the copolymer, 0.3 g of a modified monomer of an ultraviolet absorber, 0.3 g of KH570 (γ-methacryloxypropyltrimethoxysilane), 2 g of hydroxyethyl methacrylate, and 50 g of ethylene glycol ethyl ether were weighed into a three-necked flask, and 0.1 g of azobisisobutyronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0092] 3) In preparing the silica sol, Propyl orthosilicate, γ-methacryloxypropyltrimethoxysilane, anhydrous methanol, water, and nitric acid were weighed out in a mass ratio of 10:8:45:7:0.24. First, propyl orthosilicate, γ-methacryloxypropyltrimethoxysilane, anhydrous ethanol, and water were placed in a reaction bottle and stirred uniformly. Then, nitric acid was added dropwise. Finally, a polyether-modified siloxane leveling agent was added in an amount of 0.05% of the total mass of the propyl orthosilicate, γ-methacryloxypropyltrimethoxysilane, anhydrous ethanol, water, and nitric acid. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0093] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 3:1 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0094] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0095] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0096] Example 4 Specifically, in this example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0097] 1) In preparing a modified monomer of an ultraviolet absorber, 1.07 g of 2,2'-hydroxy-4-methoxybenzophenone was weighed and placed in a flask, followed by 1.42 g of 4-hydroxybutyl acrylate glycidyl ether and 25 g of ethylene glycol propyl ether. After uniform stirring, 0.72 g of Amberlyst-15 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the UV absorber-modified monomer was set aside for later use.

[0098] 2) In the preparation of the copolymer, 0.8 g of modified monomer of UV absorber, 1 g of vinyltriethoxysilane, 2 g of hydroxybutyl methacrylate, and 50 g of ethylene glycol butyl ether were weighed into a three-necked flask, and 0.175 g of azobisdimethylvaleronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0099] 3) In preparing the silica sol, Methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, water, and acetic acid were weighed out in a mass ratio of 10:8:45:7:0.24. First, the methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, and water were placed in a reaction bottle and stirred uniformly. After that, acetic acid was added drop by drop. Finally, BYK333 leveling agent was added in an amount of 0.05% of the total mass of the methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, water, and acetic acid. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0100] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 5:1 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0101] 5) Preparation of anti-fogging glass A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0102] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0103] Example 5 Specifically, in this example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0104] 1) In preparing a modified monomer of an ultraviolet absorber, 1.07 g of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone was weighed and placed in a flask, followed by 1.42 g of glycidyl methacrylate and 25 g of propylene glycol propyl ether. After uniform stirring, 0.72 g of Amberlite IR-120 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the UV absorber-modified monomer was set aside for later use.

[0105] 2) In the preparation of the copolymer, 0.5 g of modified monomer of UV absorber, 0.5 g of vinyltrimethoxysilane, 5 g of hydroxyethyl acrylate, and 50 g of propylene glycol butyl ether were weighed into a three-necked flask, and 0.175 g of azobisisobutyronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0106] 3) In preparing the silica sol, Butyl orthosilicate, divinyltriaminopropyltrimethoxysilane, absolute ethanol, water, and nitric acid were weighed out in a mass ratio of 10:8:45:7:0.24. First, the butyl orthosilicate, divinyltriaminopropyltrimethoxysilane, absolute ethanol, and water were placed in a reaction bottle and stirred uniformly. Then, nitric acid was added dropwise. Finally, 0.05% of the total mass of the butyl orthosilicate, divinyltriaminopropyltrimethoxysilane, absolute ethanol, water, and nitric acid was added as a polyether polyester-modified hydroxyl group-containing polysiloxane leveling agent. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0107] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 5:1 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0108] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0109] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0110] (Comparative Example 1) Specifically, in this comparative example, an anti-fogging paint and an anti-fogging glass were produced as follows.

[0111] 1) In preparing a modified monomer of an ultraviolet absorber, 1.07 g of 2,2'-hydroxy-4-methoxybenzophenone was weighed and placed in a flask, followed by 1.42 g of 4-hydroxybutyl acrylate glycidyl ether and 25 g of ethylene glycol propyl ether. After uniform stirring, 0.72 g of Amberlyst-15 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the UV absorber-modified monomer was set aside for later use.

[0112] 2) In the preparation of the copolymer, 0.8 g of modified monomer of ultraviolet absorber, 2 g of hydroxybutyl methacrylate, and 50 g of ethylene glycol butyl ether were weighed into a three-necked flask, and 0.175 g of azobisdimethylvaleronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0113] 3) In preparing the silica sol, Methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, water, and acetic acid were weighed out in a mass ratio of 10:8:45:7:0.24. First, the methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, and water were placed in a reaction bottle and stirred uniformly. After that, acetic acid was added drop by drop. Finally, BYK333 leveling agent was added in an amount of 0.05% of the total mass of the methyl orthosilicate, γ-aminopropyltriethoxysilane, absolute ethanol, water, and acetic acid. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0114] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 5:1 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0115] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0116] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0117] (Comparative Example 2) Specifically, in this comparative example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0118] 1) In preparing a modified monomer of an ultraviolet absorber, 1.23 g of 2,4-dihydroxybenzophenone was weighed and placed in a flask, followed by 1.42 g of (S)-glycerin methacrylate and 25 g of ethylene glycol methyl ether. After uniform stirring, 0.72 g of Amberlite IR-120 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the UV absorber-modified monomer was set aside for later use.

[0119] 2) In the preparation of the copolymer, 0.3 g of a modified monomer of an ultraviolet absorber, 0.3 g of KH570 (γ-methacryloxypropyltrimethoxysilane), 2 g of hydroxyethyl methacrylate, and 50 g of ethylene glycol ethyl ether were weighed into a three-necked flask, and 0.1 g of azobisisobutyronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0120] 3) Preparation of Anti-Fog Glass A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was carried out with a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0121] The copolymer produced in step 2) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180° C. to obtain an anti-fogging glass.

[0122] (Comparative Example 3) Specifically, in this comparative example, an anti-fog coating material and an anti-fog glass were produced as follows.

[0123] 1) In preparing a modified monomer of an ultraviolet absorber, 1.23 g of 2,2',4,4'-tetrahydroxybenzophenone was weighed and placed in a flask, followed by 1.42 g of glycidyl methacrylate and 25 g of propylene glycol methyl ether. After uniform stirring, 0.72 g of Amberlyst-15 ion exchange resin was added and the mixture was heated to 60°C and reacted for 3 hours. After the reaction was complete, the ion exchange resin was filtered, and the filtrate was rotary evaporated to remove the solvent. The remaining reaction solution of the modified monomer of the UV absorber was set aside for later use.

[0124] 2) In the preparation of the copolymer, 1 g of modified monomer of UV absorber, 1 g of methylvinyldiethoxysilane, 2 g of hydroxybutyl acrylate, and 50 g of propylene glycol ethyl ether were weighed into a three-necked flask, and 0.1 g of azobisdimethylvaleronitrile was added. The mixture was stirred and reacted at 75°C for 3 hours to obtain a copolymer.

[0125] 3) In preparing the silica sol, Ethyl orthosilicate, KH560, absolute ethanol, water, and hydrochloric acid were weighed out in a mass ratio of 10:8:45:7:0.24. The ethyl orthosilicate, KH560, absolute ethanol, and water were first placed in a reaction bottle and stirred uniformly. Then, hydrochloric acid with a mass fraction of 1% was added drop by drop. Finally, BYK307 leveling agent was added in an amount of 0.05% of the total mass of the ethyl orthosilicate, KH560, absolute ethanol, water, and hydrochloric acid. The mixture was stirred thoroughly for 3 hours until the mixture was uniform, and then aged for 2 days to obtain a silica sol.

[0126] 4) In preparing the anti-fog coating, The copolymer was added to silica sol in a mass ratio of 5:0.3 and stirred at room temperature for 4 h to obtain an anti-fog coating, which was then left to stand for later use.

[0127] 5) In preparing anti-fogging glass, A 3.2 mm thick white soda-lime tempered glass substrate was used, and pre-polishing treatment was performed using a nano-cerium oxide polishing solution so that the surface dyne value of the glass substrate was 70.

[0128] The anti-fog coating material produced in step 4) was applied to the surface of the pretreated glass substrate, leveled for 30 seconds, and then cured at 180°C to obtain anti-fog glass.

[0129] (Performance test) The anti-fogging glass coatings produced in the examples and comparative examples were subjected to performance tests. The test methods are as follows, and the test results are shown in Table 1.

[0130] 1) Pencil hardness test for evaluating coating hardness The hardness of the coating was tested according to standard GB / T6739 2066 "Method for measuring pencil hardness of coating film". 2) Xenon lamp aging test For the xenon lamp aging test, the test piece was placed in a xenon weather meter, and the test conditions were: black panel temperature 90±2°C, relative humidity 20±10%, and irradiation intensity between 300nm and 400nm 66W / m 2 The irradiation time was 2400 hours, and the sample after the xenon lamp aging test was visually inspected for the presence or absence of cracks in the coating. If no cracks were found, the sample was rated as passed. 3) Anti-fogging test The anti-fogging glass was left in an environment of 20°C and 50% RH for 1 hour, then transferred to the surface of 100 mL or more of 35°C water (5 cm above the water surface), and visually observed to measure the fogging time (s). 4) Cross-cut test for evaluating adhesion The coating adhesion was tested according to standard GB / T9286-1998 "Scratch test for base and varnish coatings" and was deemed to have passed if small pieces peeled off at the intersections of the cuts and the actual damage within the cross-cut area was within 5%.

[0131] Table 1 shows the performance test results for Comparative Examples 1 to 3 and Examples 1 to 5.

[0132] [Table 1]

[0133] As can be seen from Table 1, the anti-fog glasses of Examples 1 to 5 all meet the requirements for xenon lamp aging resistance and have anti-fog properties, and their use in B-pillar garnish glass prevents glass fogging from affecting camera use and ensures driving safety. Furthermore, Examples 1 to 5 have high coating pencil hardness, which reduces the problem of coating scratches during transportation and other processes in actual production.

[0134] Comparing Example 1 and Example 2, the mass of the acrylic hydrophilic monomer in Example 2 is higher than that of Example 1, and the anti-fogging property of Example 2 is better. This explains that the acrylic hydrophilic monomer affects the anti-fogging property of the coating, that is, the higher the content of the acrylic hydrophilic monomer, the better the anti-fogging property.

[0135] Comparing Comparative Example 1 with Example 4, the coating of Comparative Example 1 does not meet the requirements for xenon lamp aging resistance because no silane monomer is added to Comparative Example 1. This explains why the light resistance and weather resistance of the copolymer are poor when the UV absorber is not silicone-modified.

[0136] Comparing Comparative Example 2 with Example 3, the coating in Comparative Example 2 did not meet the adhesion requirements and had poor hardness because silica sol was not added, which explains why the high content of silyloxy groups in silica sol has good bonding strength with glass and can improve the hardness of the coating.

[0137] Comparing Comparative Example 3 with Example 1, the ratio of copolymer to silica sol in Comparative Example 3 was higher than that in Example 1, so the coating of Comparative Example 3 did not meet the adhesion requirements and had poor hardness, but had good anti-fogging properties. This explains why the ratio of copolymer to silica affects the anti-fogging properties and abrasion resistance of the coating. In other words, the higher the ratio of copolymer to silica, the better the anti-fogging properties and the worse the abrasion resistance.

[0138] It goes without saying that the above-described embodiments of the present invention are merely examples for clarifying the present invention and are not intended to limit the embodiments of the present invention. In addition to the above description, those skilled in the art may be able to make other changes or modifications to the present invention, and it is not possible to cover all embodiments. Any obvious changes or modifications based on the technical solutions of the present invention are within the scope of the claims of the present invention. [Explanation of symbols]

[0139] 1. Glass substrate 11 Translucent area 2. Anti-fog coating 3 Ink Layer 4. Structural adhesives

Claims

1. copolymer and silica sol, The polymerizable monomer of the copolymer includes a modified monomer of an ultraviolet absorber, a silane monomer, and an acrylic hydrophilic monomer; The modified monomer of the ultraviolet absorber is produced by a ring-opening reaction between an ultraviolet absorber having a hydroxyl group and an acrylic monomer having an epoxy group. An anti-fog paint characterized by:

2. the mass ratio of the copolymer to the silica sol is (1 to 10):1; The anti-fog coating according to claim 1 ,

3. The silica sol is prepared by mixing and reacting a silicate, a catalyst, water, a third solvent, a leveling agent, and a coupling agent; In the process for producing the silica sol, the mass ratio of the silicate, the coupling agent, the third solvent, the water, and the catalyst is (10 to 22):(5 to 18):(45 to 65):(6 to 15):(0.1 to 0.7); The amount of the leveling agent used is 0.05% to 0.3% of the total mass of the silicate, coupling agent, third solvent, water, and catalyst; The anti-fog coating according to claim 1 ,

4. the silane monomer is one or a combination of two or more selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, methylvinyldiethoxysilane, methylvinyldimethylsilane, vinyltriisopropenoxysilane, and vinyltriacetoxysilane; and / or The acrylic hydrophilic monomer is one or a combination of two or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate. The anti-fog coating according to claim 1 ,

5. the mass ratio of the modifying monomer, the silane monomer, and the acrylic hydrophilic monomer of the ultraviolet absorber is (0.3 to 1):(0.3 to 1):(1 to 10); The anti-fog coating according to claim 1 ,

6. the copolymer is obtained by polymerizing the polymerizable monomer with an initiator, and the initiator is an azo-based initiator; The anti-fog coating according to claim 1 ,

7. the ultraviolet absorber having a hydroxyl group is one or a combination of two or more selected from the group consisting of 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and / or The acrylic monomer having an epoxy group is one or a combination of two or more selected from the group consisting of glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (S)-glycerin methacrylate. The anti-fog coating according to claim 1 ,

8. The ultraviolet absorber having a hydroxyl group absorbs light in the range of 260 nm to 400 nm. The anti-fog coating according to claim 1 ,

9. the ultraviolet absorber having a hydroxyl group and an acrylic monomer having an epoxy group are subjected to a ring-opening reaction in the presence of a catalyst to produce the ultraviolet absorber-modified monomer, and the catalyst is a strongly acidic ion exchange resin; The anti-fog coating according to claim 1 ,

10. The silicate is one or a combination of two or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; and / or the catalyst is one or a combination of two or more of acetic acid, hydrochloric acid, and nitric acid; and / or the leveling agent is one or a combination of two or more of polyether-modified siloxane, polyester-modified polymethylalkylsiloxane, and polyether-polyester-modified hydroxyl-containing polysiloxane; and / or The coupling agent is one or a combination of two or more of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane, and ureidopropyltriethoxysilane. The anti-fog coating according to claim 3 .

11. A method for producing the anti-fog coating material according to any one of claims 1 to 10, The preparation of the modified monomer of the ultraviolet absorber includes: a ring-opening reaction of the ultraviolet absorber having a hydroxyl group and the acrylic monomer having an epoxy group in a first solvent by the aid of a catalyst; after completion of the reaction, removing the catalyst by filtration; and then removing the solvent to obtain a modified monomer of the ultraviolet absorber; The copolymer is prepared by In a second solvent, the modified monomer of the ultraviolet absorber, the silane monomer, and the acrylic hydrophilic monomer are polymerized in the presence of an initiator at a set temperature to produce the copolymer, which is an ultraviolet absorber copolymer modified with a silicone monomer and a hydrophilic monomer; The silica sol is prepared by: mixing and reacting a silicate, a catalyst, water, a third solvent, a leveling agent, and a coupling agent to produce the silica sol; and The preparation of the anti-fog coating material comprises: The copolymer and silica sol are uniformly mixed in a given ratio to obtain the anti-fog coating material. A method for producing an anti-fog paint.

12. A glass substrate and an anti-fog coating formed on the surface of the glass substrate using the anti-fog paint according to any one of claims 1 to 10, the glass substrate includes a light-transmitting region and a light-non-transmitting region; the anti-fog coating covers at least the light-transmitting region of the glass substrate; The anti-fogging glass is characterized by:

13. The visible light transmittance of the light-transmitting region of the glass substrate is greater than 70%, the refractive power of the light-transmitting region of the glass substrate is 110 mdpt or less, and the glass substrate is a sheet-form tempered glass.

13. The anti-fogging glass according to claim 12,

14. The thickness of the anti-fog coating is 4 μm to 30 μm.

13. The anti-fogging glass according to claim 12,

15. The anti-fogging glass is used as an exterior glass pane for an A-pillar and / or a B-pillar.

13. The anti-fogging glass according to claim 12,

16. When the distance between the boundary of the anti-fogging coating and the boundary of the light-transmitting area is d, d≦5 mm; 16. The anti-fogging glass according to claim 15,

17. The xenon lamp aging time of the anti-fog coating is 2400 hours or more.

13. The anti-fogging glass according to claim 12,

18. A method for producing anti-fogging glass according to any one of claims 12 to 17, Pre-treating and cleaning the glass substrate for subsequent use; applying the anti-fog paint to the surface of the light-transmitting region of the glass substrate, leveling and curing the paint, and then forming the anti-fog coating; Including, A method for producing anti-fogging glass.

19. The pretreatment is polishing and / or plasma treatment, and the surface dyne value of the light-transmitting region after the pretreatment is 60 or more.

19. The method for producing anti-fogging glass according to claim 18.

20. The leveling time is 10 seconds to 300 seconds, the curing temperature is 120°C to 200°C, and the curing time is 15 minutes to 720 minutes.

19. The method for producing anti-fogging glass according to claim 18.

Images