CN113930155B - Hydrophobic coating liquid, glass and preparation method thereof - Google Patents

Hydrophobic coating liquid, glass and preparation method thereof Download PDF

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Publication number
CN113930155B
CN113930155B CN202111367159.3A CN202111367159A CN113930155B CN 113930155 B CN113930155 B CN 113930155B CN 202111367159 A CN202111367159 A CN 202111367159A CN 113930155 B CN113930155 B CN 113930155B
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hydrophobic coating
glass
siloxane compound
hydrolysate
hydrophobic
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CN113930155A (en
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齐美美
贾迎辉
柯城
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Fuyao Glass Industry Group Co Ltd
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Fuyao Glass Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Composite Materials (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention discloses hydrophobic masking liquid, glass and a preparation method thereof. The hydrophobic masking liquid comprises: a hydrolysate of a siloxane compound, a fluorosilane compound, and a fluorocarbon-based solvent. The coating prepared by the hydrophobic coating liquid not only plays a role of hydrophobicity under the condition of not influencing the original performance of glass, but also greatly improves the abrasion resistance, the salt spray resistance and the irradiation resistance.

Description

Hydrophobic coating liquid, glass and preparation method thereof
Technical Field
The invention relates to the field of automobile glass, in particular to hydrophobic coating liquid, glass and a preparation method thereof.
Background
When the vehicle is driven in rainy days, the surface energy of the glass is higher, so rainwater, dust and the like can be adhered to the surface of the glass, the light transmission is poor, the vision definition of a driver is reduced, and the accident risk is greatly improved.
In recent years, the demand for safety of vehicle driving has been increasing. The existing main engine plants carry out hydrophobic treatment on the surface of side window glass of an automobile so as to solve the problem that rearview mirrors cannot be seen clearly in rainy days. However, the product has a short shelf life and typically fails within a half to one year due primarily to wear of the coating as the side window is raised and lowered. Therefore, the key to the wide application of hydrophobic coatings on automotive glass is to improve durability.
Patent application CN105176157A discloses a hydrophobic coating for automobile glass, which is prepared by stirring epoxy resin, amino resin, rosin modified maleic acid resin, zinc phosphate, polystyrene emulsion, trimethylolpropane, methyl methacrylate, tert-butyl alcohol perbenzoate, ethylene glycol monobutyl ether and ethyl orthosilicate to obtain a mixture A, adding a coupling agent and a catalyst, stirring to obtain a mixture B, adding silica particles, a dispersing agent, a thickening agent and a nonionic surfactant, stirring, grinding and coating on glass. The initial water contact angle can reach 115 degrees, but the hardness of the coating is only 2H, and the wear resistance is not enough.
Patent application CN105802446A discloses an abrasion-resistant super-hydrophobic coating material and a preparation method thereof. The first layer is a resin layer coated on the surface of the substrate, the second layer is a resin layer coated with a silicon dioxide and carbon nanotube composite material, and the outer surface of the second layer is modified by fluorosilane. The initial water contact angle is 157-162 degrees, the water rolling angle is 2.8-5.6 degrees, and the ultra-hydrophobic performance is achieved, but after a friction wear test with the load of 0.98N, the sliding diameter of 5mm and the sliding speed of 25mm/s, the water contact angle is reduced by 4-7 degrees, the rolling angle is increased by 1.2-1.7 degrees, and the abrasion resistance test of a vehicle cannot be met at all.
Therefore, there is a need to develop a durable hydrophobic coating for automotive glass, which not only has an excellent hydrophobic effect initially, but also has a lifetime of 3-5 years when applied to both windshield glass and side window glass.
Disclosure of Invention
The first purpose of the invention is to provide a hydrophobic coating liquid, and a coating prepared by using the hydrophobic coating liquid not only has hydrophobic effect under the condition of not influencing the original performance of glass, but also has better durability; the problems that the existing hydrophobic coating is poor in performances such as wear resistance, salt mist resistance and irradiation resistance, so that the coating is quick in failure and the like are solved.
The second purpose of the invention is to provide a preparation method of the hydrophobic coating liquid.
The third purpose of the invention is to provide glass with a hydrophobic coating.
The fourth purpose of the invention is to provide a preparation method of the glass.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hydrophobic masking liquid, comprising: a hydrolysate of a siloxane compound, a fluorosilane compound, and a fluorocarbon-based solvent;
the mass ratio of the fluorosilane compound to the fluorocarbon solvent is 1: (10-500), preferably 1: (100-500); the molar ratio of the fluorosilane compound to the hydrolysate of the siloxane compound is 1: (2-10).
According to the hydrophobic coating liquid of the present invention, the preparation of the hydrolyzate of the silicone compound comprises: mixing the siloxane compound with water, adding a catalyst to adjust the pH value to promote the hydrolysis of the siloxane compound, and obtaining hydrolysate of the siloxane compound after the hydrolysis is finished; and removing water and alcohols in the hydrolysate of the siloxane compound to obtain the hydrolysate of the siloxane compound.
In the hydrolysis process, the part of O at the alkoxy end of the siloxane compound is broken, H ions in water are consumed, hydroxyl is generated, the other falling part and OH in water generate micromolecular alcohols, meanwhile, a slight polycondensation reaction also occurs between the molecules with the hydroxyl end, on one hand, the hydroxyl at the tail end of the hydrolysate and the fresh hydroxyl on the surface of the glass are dehydrated and combined to generate Si-O-Si chemical bonds, the binding force of the coating and the glass substrate is improved, on the other hand, the hydroxyl tail end of the hydrolysate can also react with a fluorosilane reagent, so that the hydrophobic coating is combined into a net shape, and the durability of the coating is improved.
The catalyst is used for promoting the hydrolysis of the siloxane compound, and preferably, the catalyst is selected from one or a combination of more than two of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, calcium hydroxide and potassium hydroxide.
Preferably, a catalyst is added to adjust the pH value to 2-6 or 8-12.
The fluorosilane compound is characterized by containing fluorine element and having lower surface energy; preferably, the fluorosilane compound is selected from R1-Si(OR2)3Or Si (R)3)mX4-mWherein R is1、R3C3-16 alkyl in which at least one H atom is replaced by F, R2Is C1-3 alkyl, X is Cl, and m is more than or equal to 1 and less than or equal to 3.
More preferably, the fluorosilane compound is selected from one or a combination of two or more of trifluoropropyltrimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5, 5-heptafluoropentyl (trimethoxy) silane, triethoxy (1H,1H,2H, 2H-nonafluorohexyl) silane, nonafluorohexyltrimethoxysilane, perfluorooctyltrichlorosilane, perfluorooctyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane, and perfluorohexadecyl-1H, 1H,2H, 2H-triethoxysilane, heptadecafluorodecyltriisopropoxysilane.
The siloxane compound is wear-resistant rigid siloxane, and the structural formula of the siloxane compound is as follows: si (OR)4)4-n(R5)nOR [ Si (OR) ]4)3]2R5(ii) a Wherein R is4、R5Independently selected from C1-3 alkyl or alkenyl, and n is 1 or 2.
More preferably, the siloxane compound is selected from the group consisting of propyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, diethoxymethylvinylsilane, dimethyldiethoxysilane, methyltripropoxysilane, vinyltris [ (1-methylvinyl) oxy ] silane, vinyltriisopropoxysilane, 1, 2-bis (triethoxysilyl) ethane, 1, 2-bis (trimethoxysilyl) ethane, dimethyldimethoxysilane, dimethyldiethoxysilane, and a combination of two or more thereof.
The fluorocarbon solvent has the characteristics of low surface tension, low boiling point, easy spreading and easy volatilization. Preferably, the fluorocarbon solvent is selected from one or a combination of two or more of fluoroalcohols, fluoroethers and hydrofluorocarbons.
More preferably, the fluorocarbon solvent is one or a combination of two or more selected from the group consisting of 1H, 1H-pentafluoropropanol, methyl nonafluorobutyl ether, 1H, 2H-perfluorodipropyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,1,2,2,3, 3-heptafluoro-3-methoxypropane, ethyl nonafluorobutyl ether, perfluoropentane, perfluorooctane and perfluoroheptane, perfluorohexylethylene, perfluorobutylethylene, 1,1,2,2,3,3,4, 5-octafluorocyclopentane, octafluoronaphthalene, and 1H-perfluoro-1-octyne.
The second aspect of the invention provides a preparation method of more than one hydrophobic masking liquid, which comprises the following steps:
mixing the siloxane compound with water, and adding a catalyst to hydrolyze the siloxane compound to obtain a hydrolysate of the siloxane compound;
removing water and alcohols in the hydrolysate of the siloxane compound to obtain the hydrolysate of the siloxane compound;
and mixing the hydrolysate of the siloxane compound, the fluorosilane compound and the fluorocarbon solvent to obtain the hydrophobic coating liquid.
According to the preparation method of the durable hydrophobic coating liquid, the hydrolysis temperature is 40-80 ℃, and the hydrolysis time is 4-24 hours.
The third aspect of the present invention provides a glass, as shown in fig. 1, comprising a glass body and a hydrophobic coating formed on the surface of the glass body, wherein the hydrophobic coating is formed by curing the above hydrophobic coating liquid. Preferably, the thickness of the hydrophobic coating is 20-200 nm.
According to the glass of the invention, the water contact angle of the hydrophobic coating is preferably greater than 85 degrees after a 1000-turn abrasion resistance test of a rotary abrasion machine.
The glass according to the invention preferably has a water contact angle of more than 100 DEG after the hydrophobic coating has been subjected to a 100-hour UV radiation resistance test
The glass is used as automobile glass and has outer surface and inner surface, and the hydrophobic coating is on the outer surface of the automobile glass. The glass body of the automobile glass is single-piece toughened glass or laminated glass, one surface of the single-piece toughened glass, which is close to the outside of the automobile, is an outer surface, and one surface of the single-piece toughened glass, which is close to the inside of the automobile, is an inner surface; the laminated glass comprises an outer glass plate, a middle bonding layer and an inner glass plate, wherein the outer glass plate is provided with a first surface close to the outside of the vehicle and a second surface close to the middle bonding layer, the inner glass plate is provided with a third surface close to the middle bonding layer and a fourth surface close to the inside of the vehicle, the first surface of the outer glass plate is the outer surface of the vehicle window glass, and the fourth surface of the inner glass plate is the inner surface of the vehicle window glass.
The fourth aspect of the invention provides a preparation method of more than one glass with hydrophobic coating, which comprises the following steps:
and coating the hydrophobic coating liquid on the clean surface of the glass body, and then curing to form the hydrophobic coating.
On one hand, the curing can promote the chemical reaction between the reagent containing Si-OH bonds in the hydrophobic coating liquid and OH-Si on the surface of clean glass to form Si-O-Si chemical bonds, so that the binding force between the coating and the glass is improved, and on the other hand, the volatilization of the solvent in the hydrophobic coating liquid can be accelerated by the curing.
The coating adopts the modes of wiping, brushing, spraying, roll coating or curtain coating and the like.
Preferably, the dyne value of the clean surface of the glass body is less than or equal to 10 mN/m.
Preferably, the surface to be coated of the glass body is polished and cleaned by using a cerium dioxide polishing solution, and the surface to be coated of the glass body is formed after being dried.
Preferably, the curing is thermosetting, and comprises pre-curing at 50-65 ℃ for 3-10 minutes, and then curing at 80-100 ℃ for 20-90 minutes.
The hydrophobic coating liquid of the present invention is used to form hydrophobic coating on the surface of automobile glass, and the antiwear performance, salt fog resistance and irradiation resistance of the hydrophobic coating liquid are all raised greatly, and the transparent coating has no influence on the original performance of the glass. The hydrophobic coating liquid is simple to prepare, and the coating can be cured at low temperature.
Drawings
FIG. 1 is a schematic view of a glass having a hydrophobic coating according to the present invention;
reference numerals in the drawings indicate: 100 is a glass body, and 101 is a hydrophobic coating.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) in increments of 0.1 or 1.0 as appropriate. All numerical designations should be understood as preceded by the term "about".
As shown in fig. 1, the present invention provides a glass, which comprises a glass body 100 and a hydrophobic coating 101 formed on the surface of the glass body 100, wherein the hydrophobic coating 101 is formed by curing a hydrophobic coating liquid.
The test procedure involved in the present invention includes:
contact angle test:
the glass was tested using a portable contact angle measuring instrument manufactured by KRUSS, germany, using a two-drop measurement with water and diiodomethane as the test liquids.
And (3) testing the wear resistance:
in table 1, an abrasion resistance tester, a single-head rotary abrasion machine, and a load of 4.9N, manufactured by Taber corporation, usa were used, 300 revolutions were set at a speed of 40 revolutions per minute, and after completion, a contact angle index was measured at the abraded portion. In table 2, the contact angle index was measured for the worn portion after setting 1000 revolutions under the same conditions.
And (3) testing irradiation resistance:
an ultraviolet lamp is adopted to carry out irradiation test on a sample, an irradiation light source is an ozone-free quartz tube type medium-pressure mercury vapor arc lamp, the arc length is 300mm +/-14 mm, the working power is 750 +/-50W, the surface with the durable coating is right opposite to the light source, the distance between the surface with the durable coating and a lamp shaft is 230mm, the surface with the durable coating rotates around a central shaft at the speed of 5r/min, the temperature of the sample is kept at 45 +/-5 ℃ in the process, and the irradiation time is 100 hours.
Salt spray resistance test:
the method comprises the steps of putting glass in a salt spray test box, spraying saline water containing (5 +/-0.5) wt.% of sodium chloride and having a pH value of 6.5-7.2 through a spraying device, allowing salt spray to sink onto a test piece to be tested, and observing the surface state of the test piece after 300 hours. The temperature of the test chamber is required to be (35 +/-2) DEG C.
And (3) testing acid resistance:
the automobile glass with hydrophobic coating is coated at 0.1N, H2SO4The solution of (2) is soaked for 3 hours and then taken out.
Example 1
The hydrophobic coating liquid 1 is prepared and used for preparing glass with a hydrophobic coating, and the preparation method comprises the following steps:
mixing 10g of 1, 2-bis (triethoxysilyl) ethane with 5g of water, dropwise adding 5 wt.% hydrochloric acid to adjust the pH value to 4, stirring for 10 hours at 45 ℃ to hydrolyze the siloxane compound to obtain a clear solution, and removing water and ethanol in the mixed solution by reduced pressure distillation to obtain a reagent A.
0.3g of reagent A is taken and added with 0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 50g of hydrophobic solvent ethyl nonafluorobutyl ether, and the mixture is continuously stirred for 30min to obtain hydrophobic coating liquid 1 for standby.
Polishing and cleaning a glass plate with the size of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 1 on the surface of the glass, pre-curing for 5 minutes at 60 ℃, and curing for 30 minutes at 80 ℃ to obtain the glass with the hydrophobic coating.
Example 2
The hydrophobic coating liquid 2 is prepared and used for preparing glass with a hydrophobic coating, and the method comprises the following steps:
0.15g of reagent A is taken and added with 0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 50g of hydrophobic solvent ethyl nonafluorobutyl ether, and the mixture is continuously stirred for 30min to obtain hydrophobic coating liquid 2 for standby.
Polishing and cleaning a glass plate with the size of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 2 on the surface of the glass, pre-curing for 5 minutes at 60 ℃, and curing for 30 minutes at 80 ℃ to obtain the glass with the hydrophobic coating.
Example 3
The hydrophobic coating liquid 3 is prepared and used for preparing glass with a hydrophobic coating, and the method comprises the following steps:
0.06g of the reagent A is taken and added with 0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 50g of hydrophobic solvent ethyl nonafluorobutyl ether, and the mixture is continuously stirred for 30min to obtain hydrophobic coating liquid 3 for standby.
Polishing and cleaning a glass plate with the thickness of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 3 on the surface of the glass, precuring for 5 minutes at the temperature of 60 ℃, and curing for 30 minutes at the temperature of 80 ℃ to obtain the glass with the hydrophobic coating.
Example 4
The hydrophobic coating liquid 4 is prepared and used for preparing glass with a hydrophobic coating, and the method comprises the following steps:
0.15g of reagent A is added with 0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 20g of hydrophobic solvent ethyl nonafluorobutyl ether, and the mixture is continuously stirred for 30min to obtain hydrophobic coating liquid 4 for later use.
Polishing and cleaning a glass plate with the size of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 4 on the surface of the glass, pre-curing for 5 minutes at 60 ℃, and curing for 30 minutes at 80 ℃ to obtain the glass with the hydrophobic coating.
Example 5
The hydrophobic coating liquid 5 is prepared in the embodiment, and the glass with the hydrophobic coating is prepared by using the hydrophobic coating liquid, and the preparation method comprises the following steps:
0.15g of reagent A is taken and added with 0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 10g of hydrophobic solvent ethyl nonafluorobutyl ether, and the mixture is continuously stirred for 30min to obtain hydrophobic coating liquid 5 for standby.
Polishing and cleaning a glass plate with the thickness of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 5 on the surface of the glass, pre-curing for 5 minutes at 60 ℃, and curing for 30 minutes at 80 ℃ to obtain the glass with the hydrophobic coating.
Example 6
The hydrophobic coating liquid 6 is prepared and used for preparing glass with a hydrophobic coating, and the method comprises the following steps:
10g of propyltrimethoxysilane was mixed with 5g of water, acetic acid was added dropwise to adjust pH to 5, the mixture was stirred at 50 ℃ for 4 hours to hydrolyze the siloxane compound to obtain a clear solution, and water and methanol in the mixture were removed by distillation under reduced pressure to obtain a reagent B.
0.1g of reagent B, 0.1g of perfluorodecyl triethoxysilane and 20g of hydrophobic solvent 1H, 1H-pentafluoropropanol are mixed and stirred for 30min to obtain hydrophobic coating liquid 6 for later use.
Polishing and cleaning a glass plate with the size of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 6 on the surface of the glass, pre-curing for 3 minutes at 50 ℃, and curing for 25 minutes at 85 ℃ to obtain the glass with the hydrophobic coating.
Example 7
The hydrophobic coating liquid 7 is prepared in the embodiment, and the glass with the hydrophobic coating is prepared by using the hydrophobic coating liquid, and the preparation method comprises the following steps:
10g of vinyltriethoxysilane was mixed with 5g of water, nitric acid was added to adjust the pH to 4, the mixture was stirred at 40 ℃ for 6 hours to hydrolyze the siloxane compound to obtain a clear solution, and water and ethanol in the mixture were removed by distillation under reduced pressure to obtain reagent C.
0.1g of reagent C, 0.15g of triethoxy (1H,1H,2H, 2H-nonafluorohexyl) silane and 20g of hydrophobic solvent perfluoropentane are mixed and stirred for 30min to obtain hydrophobic coating liquid 7 for later use.
Polishing and cleaning a glass plate with the thickness of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 7 on the surface of the glass, pre-curing for 3 minutes at 50 ℃, and curing for 20 minutes at 100 ℃ to obtain the glass with the hydrophobic coating.
Example 8
The hydrophobic coating liquid 8 is prepared and used for preparing glass with a hydrophobic coating, and the method comprises the following steps:
10g of vinyltriisopropoxysilane was mixed with 5g of water, sodium hydroxide was added to adjust the pH to 10, and the mixture was stirred at 40 ℃ for 8 hours to hydrolyze the siloxane compound to obtain a clear solution, and water and ethanol in the mixture were removed by distillation under reduced pressure to obtain a reagent D.
0.1g of the reagent D, 0.15g of perfluorodecyl trichlorosilane and 20g of hydrophobic solvent perfluoropentane are mixed and stirred for 30min to obtain hydrophobic coating liquid 8 for later use.
Polishing and cleaning a glass plate with the thickness of 300mm multiplied by 300mm by using cerium dioxide polishing solution, airing, uniformly spraying hydrophobic coating liquid 8 on the surface of the glass, precuring for 3 minutes at 50 ℃, and curing for 20 minutes at 100 ℃ to obtain the glass with the hydrophobic coating.
Comparative example 1
A300 mm by 300mm glass plate was cleaned with alcohol on the glass surface as a blank comparative example 1.
Comparative example 2
This comparative example, which prepared hydrophobic coating liquid 9 (without addition of reagent a compared to example 4) and used it to prepare hydrophobic coated glass, comprises the following processes:
0.1g of perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane and 20g of hydrophobic solvent ethyl nonafluorobutyl ether are mixed and stirred for 30min to obtain hydrophobic coating liquid 9 for later use.
Polishing and cleaning a glass plate with the size of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly spraying hydrophobic coating liquid 6 on the surface of the glass, pre-curing for 5 minutes at 60 ℃, and curing for 30 minutes at 80 ℃ to obtain the glass with the hydrophobic coating.
Comparative example 3
The comparative example adopts a common hydrophobic coating liquid formula to prepare the hydrophobic coating liquid 10, and uses the hydrophobic coating liquid to prepare the glass with the hydrophobic coating, and comprises the following processes:
1.5g of perfluorooctyl trichlorosilane is dissolved in 50g of hexane solution, mixed and stirred for 30min to obtain the hydrophobic masking liquid 10 for standby.
Polishing and cleaning a glass plate with the thickness of 300mm multiplied by 300mm by using cerium dioxide polishing solution, drying in the air, uniformly wiping and coating the hydrophobic coating solution 7 on the surface of the glass, and standing at room temperature for 2 days to obtain the glass with the hydrophobic coating.
The glass obtained in the above examples and comparative examples was subjected to performance tests, and the specific results are shown in table 1 below:
TABLE 1 results of performance test of glasses obtained in examples and comparative examples
Figure BDA0003361085650000091
In the above examples and comparative examples, examples 1 to 3 were conducted using the same composition, and the content of the hydrolyzate of abrasion resistant silicone compound (agent A) in the hydrophobic coating liquid was changed.
Examples 2, 4 and 5, the low surface energy agent and the hydrolysate (agent A) of the abrasion resistant silicone compound were used in the same amounts, and the solvent content in the hydrophobic coating liquid was changed.
Examples 6, 7 and 8 were carried out while changing the kinds of the hydrolyzate of the silicone compound, the fluorosilane compound and the fluorocarbon-based solvent, the curing temperature and the curing time, and also had excellent hydrophobic effect and durability.
Examples 1 to 8, the rolling angle range was 11 to 14 degrees, which not only ensures that water drops and the like easily slide down to achieve the hydrophobic effect, but also ensures that the durable hydrophobic coating liquid is economical and efficient in process implementation.
Comparison of comparative example 1 with examples 1-8 shows that the hydrophobic coating has a stable hydrophobic effect.
Comparison of comparative example 2 with example 4 shows that increasing the hydrolysate of the abrasion resistant silicone compound is effective in improving the abrasion resistance effect.
Comparison of comparative example 3 with examples 1-8 shows that the hydrophobic coating has excellent salt spray resistance, radiation resistance, abrasion resistance and the like, and has good durability.
Analysis of the data in Table 1 reveals that, at a given concentration of the low surface energy fluorosilane compound, the content of the hydrolysate of the abrasion resistant siloxane compound is increased, the hydrophobic property is decreased, and the abrasion resistance is improved. When the content of hydrolysate of the wear-resistant siloxane compound is constant, the concentration of the low-surface-energy fluorine silane compound is increased, and the hydrophobic property is improved. Therefore, the invention requires that the concentration of the low surface energy fluorine silane compound and the content of hydrolysate of the wear-resistant siloxane compound are in a certain range, so that the coating can achieve the optimal effect.
Through the data testing results in table 1 above, examples 1-8 have superior abrasion resistance compared to comparative examples 1-3, and are tested to meet the requirements of abrasion resistance Taber, load 4.9N, and 1000 rpm in the automobile regulation ECE R43, and the specific results are shown in table 2 below:
TABLE 2 results of water contact angle of glass obtained in examples 1 to 5 after a load of 4.9N and abrasion of 1000 rpm
Figure BDA0003361085650000101
From the results in table 2, it can be seen that the addition of the abrasion resistant siloxane compounds in examples 1 to 8 effectively improves the abrasion resistance of the hydrophobic coating, so that the water contact angle of the coating after 1000 r abrasion is greater than 85 °, and the water contact angle of the coating after abrasion in examples 3 to 6 is greater than 90 ° still has the hydrophobic function.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (15)

1. A hydrophobic coating solution, comprising: a hydrolysate of a siloxane compound, a fluorosilane compound, and a fluorocarbon-based solvent;
the structural formula of the fluorosilane compound is as follows: r1-Si(OR2)3Or Si (R)3)mX4-m(ii) a Wherein R is1、R3C3-16 alkyl in which at least one H atom is replaced by F, R2Is C1-3 alkyl, X is Cl, m is more than or equal to 1 and less than or equal to 3;
the structural formula of the siloxane compound is as follows: si (OR)4)4-n(R5)nOR [ Si (OR) ]4)3]2R5(ii) a Wherein R is4、R5Independently selected from C1-3 alkyl or alkenyl, n is 1 or 2;
the mass ratio of the fluorosilane compound to the fluorocarbon solvent is 1: (10-500);
the molar ratio of the fluorosilane compound to the hydrolysate of the siloxane compound is 1: (2-10);
the preparation of the hydrolysate of the siloxane compound comprises: mixing the siloxane compound with water, adding a catalyst to adjust the pH value to promote the hydrolysis of the siloxane compound, and obtaining hydrolysate of the siloxane compound after the hydrolysis is finished; and removing water and alcohols in the hydrolysate of the siloxane compound to obtain the hydrolysate of the siloxane compound.
2. The hydrophobic coating solution as recited in claim 1, wherein the catalyst is selected from one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, calcium hydroxide and potassium hydroxide.
3. The hydrophobic coating solution as claimed in claim 1, wherein a catalyst is added to adjust the pH to 2 to 6 or 8 to 12.
4. The hydrophobic masking liquid as claimed in claim 1, wherein the mass ratio of the fluorosilane compound to the fluorocarbon-based solvent is 1: (100-500).
5. The hydrophobic masking liquid as claimed in claim 1, wherein the fluorocarbon-based solvent is one or a combination of two or more selected from fluoroalcohols, fluoroethers and hydrofluorocarbons.
6. The hydrophobic coating solution as claimed in claim 1, wherein the fluorosilane compound is selected from the group consisting of trifluoropropyltrimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3,3,4,4,5,5, 5-heptafluoropentyl (trimethoxy) silane, triethoxy (1H,1H,2H, 2H-nonafluorohexyl) silane, nonafluorohexyltrimethoxysilane, perfluorooctyltrichlorosilane, perfluorooctyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorotetradecyl-1H, 1H,2H, 2H-triethoxysilane, perfluorohexadecyl-1H, 1H,2H, 2H-triethoxysilane, heptadecafluorodecyltriisopropoxysilane, or a combination of two or more thereof.
7. The hydrophobic coating solution as claimed in claim 1, wherein the siloxane compound is selected from the group consisting of propyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, diethoxymethylvinylsilane, dimethyldiethoxysilane, methyltripropoxysilane, vinyltris [ (1-methylvinyl) oxy ] silane, vinyltriisopropoxysilane, 1, 2-bis (triethoxysilyl) ethane, 1, 2-bis (trimethoxysilyl) ethane, dimethyldimethoxysilane, dimethyldiethoxysilane, and a combination of two or more thereof.
8. The hydrophobic coating solution according to claim 1, wherein the fluorocarbon-based solvent is one or a combination of two or more selected from the group consisting of 1H, 1H-pentafluoropropanol, methyl nonafluorobutyl ether, 1H, 2H-perfluorodipropyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,1,2,2,3, 3-heptafluoro-3-methoxypropane, ethyl nonafluorobutyl ether, perfluoropentane, perfluorooctane and perfluoroheptane, perfluorohexylethylene, perfluorobutylethylene, 1,1,2,2,3,3,4, 5-octafluorocyclopentane, octafluoronaphthalene, and 1H-perfluoro-1-octyne.
9. The hydrophobic coating solution as claimed in any one of claims 1 to 8, wherein the preparation method comprises the following steps:
mixing the siloxane compound with water, and adding a catalyst to hydrolyze the siloxane compound to obtain a hydrolysate of the siloxane compound;
removing water and alcohols in the hydrolysate of the siloxane compound to obtain a hydrolysate of the siloxane compound;
and mixing the hydrolysate of the siloxane compound, the fluorosilane compound and the fluorocarbon solvent to obtain the hydrophobic coating liquid.
10. A glass comprising a glass body and a hydrophobic coating formed on the surface of the glass body, wherein the hydrophobic coating is formed by curing the hydrophobic coating liquid according to any one of claims 1 to 8.
11. The glass of claim 10, wherein the hydrophobic coating has a water contact angle greater than 85 ° after a 1000-turn abrasion resistance test using a rotary abrader.
12. The glass of claim 11, wherein the hydrophobic coating exhibits a water contact angle greater than 100 ° when subjected to a 100 hour uv light exposure test.
13. A method of making the glass of any one of claims 10-12, comprising:
and coating the hydrophobic coating liquid on the clean surface of the glass body, and then curing to form the hydrophobic coating.
14. The method for preparing glass according to claim 13, wherein the dyne value of the clean surface of the glass body is less than or equal to 10 mN/m.
15. The method for preparing glass according to claim 13, wherein the curing is thermal curing, and comprises pre-curing at 50-65 ℃ for 3-10 minutes, and then curing at 80-100 ℃ for 20-90 minutes.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5997943A (en) * 1996-04-02 1999-12-07 Saint-Gobain Vitrage Compound for a non-wettable coating, process for treatment of glass with the aid of the compound and products obtained
WO2021115318A1 (en) * 2019-12-09 2021-06-17 佛山市思博睿科技有限公司 Superhydrophobic water-repellent liquid, preparation method, and application thereof in waterproof sound-permeable mesh

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2175848C (en) * 1995-06-05 2000-01-11 Ppg Industries Ohio, Inc. Water repellent surface treatment with integrated primer
JP4643696B2 (en) * 2008-09-03 2011-03-02 株式会社ソフト９９コーポレーション 2-part water repellent treatment for painted surfaces
CN103992045A (en) * 2014-05-15 2014-08-20 奇瑞汽车股份有限公司 Double-component hydrophobing agent and application thereof
CN108948829B (en) * 2018-07-16 2020-03-27 福耀玻璃工业集团股份有限公司 Water-repellent oil-repellent agent and water-repellent oil-repellent automobile glass
CN110511673B (en) * 2019-09-27 2021-12-07 深圳市信濠光电科技股份有限公司 Anti-fingerprint masking liquid and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5997943A (en) * 1996-04-02 1999-12-07 Saint-Gobain Vitrage Compound for a non-wettable coating, process for treatment of glass with the aid of the compound and products obtained
WO2021115318A1 (en) * 2019-12-09 2021-06-17 佛山市思博睿科技有限公司 Superhydrophobic water-repellent liquid, preparation method, and application thereof in waterproof sound-permeable mesh

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