CN115368762A - Hydrophobic and oleophobic coating, preparation method and application thereof - Google Patents
Hydrophobic and oleophobic coating, preparation method and application thereof Download PDFInfo
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- 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
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- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention relates to the field of coating materials, in particular to a hydrophobic and oleophobic coating, a preparation method and application thereof. The preparation method comprises the following steps: mixing ethyl orthosilicate, ethanol, water and an acid catalyst, heating and stirring, and then adding a molecular weight regulator for co-hydrolysis to obtain a nano silica sol solution; and then adding a fluorine-containing compound solution into the nano silica sol solution, diluting, adding a leveling agent, and uniformly stirring to obtain the stable and high-transparency hydrophobic and oleophobic coating. The hydrophobic and oleophobic coating obtained by the invention is suitable for glass substrates, has excellent transparency, good wear resistance and adhesion and can be stably stored.
Description
Technical Field
The invention relates to the field of coating materials, in particular to a hydrophobic and oleophobic coating, a preparation method and application thereof.
Background
In recent years, along with the rapid development of the bionic super-hydrophobic material, people pay more and more attention to the application of the bionic super-hydrophobic material in the fields of water prevention, ice prevention, oil-water separation, corrosion resistance, self-cleaning and the like, and the special structure and the components on the surface of the super-hydrophobic material can prevent water drops from wetting the surface of the bionic super-hydrophobic material, so that the aim of water prevention is fulfilled. However, in practical application, the low surface energy material on the surface of the super-hydrophobic material has weak bonding force with the base material and poor adhesion, and in addition, a special multi-layer structure of the super-hydrophobic material is easy to be damaged by friction, so that the hydrophobic property is greatly reduced, and meanwhile, a rough surface can generate diffuse reflection to light, so that the hydrophobic surface of the super-hydrophobic material is poor in transparency, and the super-hydrophobic material is difficult to be applied to surfaces such as glass, acrylic plates and the like, can also cover the original gloss of the material, and greatly limits the practical application of the super-hydrophobic material. By reducing the roughness of the surface of the hydrophobic material, particularly controlling the surface structure and morphology, the transparency of the hydrophobic material can be effectively improved, but the hydrophobicity of the surface of the material is reduced. Although the super-hydrophobic material has special wettability, water drops can roll away without wetting the surface completely, the hydrophobic material can also greatly reduce the surface energy and the adhesion force of the surface energy and the water by controlling the surface components, particularly introducing fluorine-containing materials, so that good hydrophobicity is achieved. More importantly, the method can solve the difficult problems of poor durability and stability of the super-hydrophobic material while keeping the surface hydrophobicity, keep the transparency of the super-hydrophobic material and expand the application of the super-hydrophobic material.
The invention discloses a preparation method of solvent type hydrophobic and oleophobic nano hybrid fluorosilicone resin. The invention carries out hydrolysis copolycondensation on fluorocarbon group/alkoxy group co-modified silicone oil, chlorosilane, a silane coupling agent and modified nano-silicon sol in a good fluorosilicone solvent to prepare the solvent type hydrophobic and oleophobic nano-hybrid fluorosilicone resin. Although the hydrophobic and oleophobic coating obtained by adjusting the particle size of the silica sol has good transparency and hardness, the preparation process is complex, and a catalyst needs to be added and the curing and crosslinking are carried out at high temperature. The invention provides a hydrophobic composition, which mainly takes a fluorine-containing surfactant, acidic silica sol, water and an organic solvent as matrixes, and antimony pentoxide hydrosol is added to prepare a hydrophobic film for a glass surface. The hydrophobic film has good self-hydrophobicity and wear resistance after room temperature self-drying and curing, and the coating and the glass substrate have similar refractive indexes due to the introduction of antimony pentoxide hydrosol, so that the hydrophobic film has good light transmittance. The method mainly changes the refractive index of the coating by introducing antimony pentoxide, so that the light transmittance of the coating is improved. The prior art provides a long-acting nano hydrophobic coating composition and a preparation method thereof, and the long-acting transparent nano coating is obtained by mainly adding fluorine-containing chlorosilane, polysiloxane, rare earth salt and a film-forming agent into nano silica sol and mixing and reacting the mixture. In order to improve the film forming property and hydrophobicity of the coating, the polyorganosiloxane resin needs to be introduced for crosslinking and curing. In the prior art, a hydrophobic coating is prepared by adopting a multi-step method, mainly by etching the surface of glass, depositing nano silica sol particles on the etched surface and performing fluorination modification of surface hydrophobicity, although the method can better control the structure and hydrophobicity of the surface, the process is more complicated and needs to be performed in multiple steps, in addition, the method is generally suitable for the surfaces of glass, ceramic and the like, and has narrow practicability. In the prior art, different methods are adopted to control the particle size of the nano silica sol, polymer resin and a silane coupling agent are introduced to carry out surface modification, and finally, a transparent hydrophobic wear-resistant coating is obtained in a high-temperature curing and crosslinking mode. Therefore, by controlling the particle size of the silica sol, suitable roughness and reactive groups are imparted to the surface of the material without affecting the transparency of the substrate, and modification by a hydrophobic resin or a silane coupling agent is an effective method for obtaining a stable transparent hydrophobic coating.
Although the nano silica sol with controllable particle size can be prepared by a sol-gel method, and the transparency of the coating surface of the nano silica sol can be adjusted, two problems exist at present, on one hand, after the silica sol with a certain particle size is obtained, the silicon hydroxyl groups in the sol are continuously condensed in the subsequent storage process, the particle size is continuously increased, and finally gel is formed, so that the stable storage is difficult; on the other hand, the excessive molecular weight of the silica-bonded silica sol can cause the precipitation of silica sol, the too small cross-linked network formed by the molecular weight has poor film forming property, and a transparent and stable hydrophobic coating can not be obtained, in addition, most of the solvents commonly used by the sol-gel method are ethanol, the wettability of the solvents to the base material is poor, the drying speed is too fast, the leveling property of the film is poor, and the transparency of the coating is influenced, so that the problem of how to adjust the molecular weight of the silica sol and solve the storage and leveling property of the silica sol is a problem which needs to be solved urgently at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides the hydrophobic and oleophobic coating which has excellent transparency, good wear resistance and adhesion and can be stably stored.
The invention also provides a preparation method of the hydrophobic and oleophobic coating, the process is simple and convenient, and the prepared hydrophobic and oleophobic coating is suitable for glass substrates.
The invention adopts the following technical scheme:
the hydrophobic and oleophobic coating consists of a nano silica sol solution, a fluorine-containing compound solution and a leveling agent; the grain diameter of the silicon dioxide in the nano silica sol solution is 1-30 nm.
The technical proposal is further improved that the nano silica sol solution is prepared by the following method: uniformly mixing ethyl orthosilicate and an ethanol aqueous solution, stirring to obtain a uniform transparent solution, then dropwise adding an acid catalyst to adjust the pH value of the system, heating the system to 30-60 ℃, reacting for 6-12 h, adding a molecular weight regulator, continuously reacting for 6-12 h, cooling to obtain a nano silica sol solution;
the molecular weight regulator is one of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane and 3-glycidyl ether oxypropyl trimethoxy silane;
the acid catalyst is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
the mass ratio of ethanol to water in the ethanol water solution is 60-95;
the mass ratio of the ethyl orthosilicate to the ethanol aqueous solution is 40-5;
the pH is 1-5.
The technical proposal is further improved in that the mass ratio of the tetraethoxysilane to the molecular weight regulator is 90-99.5.
The technical proposal is further improved in that the fluorine-containing compound solution is tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
The further improvement of the technical proposal is that the fluorine-containing compound solution is obtained by stirring the fluorine-containing compound and ethanol water solution for 10min to 120min at the temperature of between 20 and 60 ℃.
According to a further improvement of the above technical solution, the mass ratio of the fluorine-containing compound to the ethanol aqueous solution is from 0.5 to 99.5.
The technical proposal is further improved in that the flatting agent is one or more of ethylene glycol dimethyl ether, isopropanol, N-butanol, ethylene glycol monomethyl ether and N, N-dimethylformamide.
A preparation method of a hydrophobic and oleophobic coating comprises the following steps: diluting the nano silica sol solution with ethanol, stirring for 20-50 min, adding a fluorine-containing compound solution and a flatting agent, ultrasonically dispersing for 5-30 min, and filtering to obtain a stable and high-transparency hydrophobic and oleophobic coating;
the mass ratio of the nano silica sol solution to the ethanol is 1:1-1;
the mass ratio of the nano silica sol solution to the fluorine-containing compound solution is 1:1-20;
the mass ratio of the nano silica sol solution to the flatting agent is 100.
The application of the hydrophobic and oleophobic coating comprises cleaning glass substrate, treating with plasma machine, coating the hydrophobic and oleophobic coating on the surface of the glass substrate by spraying, dip coating, roller coating, spin coating or brush coating, and drying and volatilizing the solvent to obtain the glass containing the hydrophobic and oleophobic coating.
The further improvement of the technical scheme is that the drying mode of the hydrophobic and oleophobic coating is room temperature drying or heating drying.
The invention has the beneficial effects that:
(1) By introducing the molecular weight regulator, the molecular weight and the particle size of the silica sol can be effectively controlled, and functional amino or epoxy groups are introduced to improve the binding force and the adhesive force between the coating and a base material.
(2) By controlling the preparation process and the addition mode of the molecular weight regulator and finally by a dilution method, the good stability of the silica sol can be ensured when the high molecular weight is kept, and the subsequent continuous crosslinking is prevented from forming gel.
(3) By introducing the high-boiling-point leveling agent, the influence of agglomeration caused by too fast drying of the coating on the transparency of the coating can be prevented.
Drawings
FIG. 1 is a schematic representation of the contact angle of a hydrophobic and oleophobic glass made in example 1 of the invention to water;
FIG. 2 is a scanning electron micrograph of the hydrophobic coating prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples for better understanding of the present invention, but the embodiments of the present invention are not limited thereto.
The hydrophobic and oleophobic coating consists of a nano silica sol solution, a fluorine-containing compound solution and a leveling agent; the grain diameter of the silicon dioxide in the nano silica sol solution is 1-30 nm.
Further, the nano silica sol solution is prepared by the following method: uniformly mixing ethyl orthosilicate and an ethanol aqueous solution, stirring to obtain a uniform transparent solution, then dropwise adding an acid catalyst to adjust the pH value of the system, heating the system to 30-60 ℃, reacting for 6-12 h, adding a molecular weight regulator, continuously reacting for 6-12 h, cooling to obtain a nano silica sol solution;
the molecular weight regulator is one of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane and 3-glycidyl ether oxypropyl trimethoxy silane;
the acid catalyst is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
the mass ratio of ethanol to water in the ethanol water solution is 60-95;
the mass ratio of the ethyl orthosilicate to the ethanol aqueous solution is (40);
the pH is 1-5.
Further, the mass ratio of the tetraethoxysilane to the molecular weight regulator is 90-99.5.
Further, the fluorine-containing compound solution is tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.
Further, the fluorine-containing compound solution is obtained by stirring a fluorine-containing compound and an ethanol water solution at the temperature of 20-60 ℃ for 10-120 min.
Further, the mass ratio of the fluorine-containing compound to the aqueous ethanol solution is from 0.5 to 20.
Further, the flatting agent is one or more of ethylene glycol dimethyl ether, isopropanol, N-butanol, ethylene glycol monomethyl ether and N, N-dimethylformamide.
A preparation method of a hydrophobic and oleophobic coating comprises the following steps: diluting the nano silica sol solution with ethanol, stirring for 20-50 min, adding a fluorine-containing compound solution and a flatting agent, ultrasonically dispersing for 5-30 min, and filtering to obtain a stable and high-transparency hydrophobic and oleophobic coating;
the mass ratio of the nano silica sol solution to the ethanol is 1:1-1;
the mass ratio of the nano silica sol solution to the fluorine-containing compound solution is 1:1-20;
the mass ratio of the nano silica sol solution to the flatting agent is 100.
The application of the hydrophobic and oleophobic coating comprises cleaning glass substrate, treating with plasma machine, coating the hydrophobic and oleophobic coating on the surface of the glass substrate by spraying, dip coating, roller coating, spin coating or brush coating, and drying and volatilizing the solvent to obtain the glass containing the hydrophobic and oleophobic coating.
Further, the drying mode of the hydrophobic and oleophobic coating is room temperature drying or heating drying.
Example 1
Stirring 2 parts of heptadecafluorodecyltrimethoxysilane and 98 parts of an ethanol aqueous solution (90 parts of ethanol and 8 parts of water) at 40 ℃ for 60min to obtain a fluorine-containing compound solution;
uniformly mixing 10 parts of tetraethoxysilane and 90 parts of ethanol aqueous solution (81 parts of ethanol and 9 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L of hydrochloric acid aqueous solution to adjust the pH value of the system to 3, heating to 40 ℃, reacting for 8 hours, adding 1 part of 3-glycidyl ether oxypropyltrimethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 12 hours, cooling, and obtaining a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 16nm;
taking 10 parts of nano silica sol solution, adding 100 parts of ethanol, stirring for 30min, adding 2 parts of fluorine-containing compound solution and 0.5 part of n-butyl alcohol, ultrasonically dispersing for 15min, and filtering by using 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass for 120s by using a plasma machine, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in a 60 ℃ oven for 30min to obtain the hydrophobic and oleophobic glass.
FIG. 1 is a schematic representation of the contact angle of the water-and oil-repellent glass prepared in example 1 with water. It can be seen that the water drop appears elliptical on the coating surface with a contact angle of about 115 deg., indicating that the coating produced has good hydrophobic properties.
FIG. 2 is a scanning electron micrograph of the superhydrophobic coating prepared in example 1. It can be seen that the surface of the coating is relatively flat, a dense network structure coating is formed between the silica sol, and no obvious protrusion or particle exists.
Example 2
Stirring 20 parts of heptadecafluorodecyltrimethoxysilane and 80 parts of an aqueous ethanol solution (64 parts of ethanol and 16 parts of water) at 50 ℃ for 120min to obtain a fluorine-containing compound solution;
uniformly mixing 40 parts of tetraethoxysilane and 60 parts of ethanol aqueous solution (36 parts of ethanol and 24 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding acetic acid aqueous solution to adjust the pH value of the system to 4, heating to 30 ℃, reacting for 12 hours, adding 2 parts of gamma-aminopropyltrimethoxysilane, maintaining the temperature at 30 ℃, continuing to react for 6 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 30nm;
adding 200 parts of ethanol into 10 parts of nano silica sol solution, stirring for 50min, adding 0.5 part of fluorine-containing compound solution and 1 part of N, N-dimethylformamide, ultrasonically dispersing for 30min, and filtering by using 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass in a plasma machine for 240s, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in an oven at 70 ℃ for 40min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has no obvious particles and has a contact angle to water of 113 degrees.
Example 3
Stirring 0.5 part of heptadecafluorodecyltrimethoxysilane and 99.5 parts of ethanol aqueous solution (98.5 parts of ethanol and 1 part of water) at 60 ℃ for 10min to obtain a fluorine-containing compound solution;
uniformly mixing 5 parts of ethyl orthosilicate and 95 parts of ethanol aqueous solution (90.25 parts of ethanol and 4.75 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L sulfuric acid aqueous solution to adjust the pH of the system to 5, heating to 30 ℃, reacting for 6 hours, adding 0.025 parts of gamma-aminopropyltriethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 6 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 1nm;
taking 10 parts of nano silica sol solution, adding 10 parts of ethanol, stirring for 20min, adding 10 parts of fluorine-containing compound solution and 1 part of isopropanol, ultrasonically dispersing for 5min, and filtering by adopting 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the glass surface by using an ethanol aqueous solution, placing the glass surface in a plasma machine for processing for 240s, then brushing the hydrophobic and oleophobic coating on the glass surface by adopting a brushing mode, and then placing the glass surface at room temperature for drying for 120min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has no obvious particles and has a contact angle of 111 degrees to water.
Example 4
Stirring 5 parts of heptadecafluorodecyltrimethoxysilane and 95 parts of an aqueous ethanol solution (85.5 parts of ethanol and 9.5 parts of water) at 40 ℃ for 120min to obtain a fluorine-containing compound solution;
uniformly mixing 20 parts of ethyl orthosilicate and 80 parts of ethanol aqueous solution (56 parts of ethanol and 24 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L nitric acid aqueous solution to adjust the pH value of the system to 1, heating to 30 ℃, reacting for 6 hours, adding 1 part of 3-glycidyl ether oxypropyltrimethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 6 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 27nm;
taking 10 parts of nano silica sol solution, adding 50 parts of ethanol, stirring for 50min, adding 4 parts of fluorine-containing compound solution and 0.1 part of ethylene glycol dimethyl ether, ultrasonically dispersing for 30min, and filtering by using 400-mesh filter cloth to obtain a stable and high-transparency hydrophobic and oleophobic coating;
ultrasonically cleaning and drying the surface of glass by using an ethanol aqueous solution, treating the glass for 180s by using a plasma machine, then coating the hydrophobic and oleophobic coating on the surface of the glass by adopting a spin coating mode, and drying the glass in an oven at 80 ℃ for 10min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has no obvious particles and has a contact angle to water of 116 degrees.
Example 5
Stirring 12 parts of heptadecafluorodecyltrimethoxysilane and 88 parts of an aqueous ethanol solution (80 parts of ethanol and 8 parts of water) at 50 ℃ for 120min to obtain a fluorine-containing compound solution;
uniformly mixing 15 parts of ethyl orthosilicate and 85 parts of ethanol aqueous solution (80 parts of ethanol and 5 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding acetic acid aqueous solution to adjust the pH of the system to 4, heating to 40 ℃, reacting for 12 hours, adding 1 part of gamma-aminopropyltriethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 8 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 23nm;
taking 10 parts of nano silica sol solution, adding 80 parts of ethanol, stirring for 30min, adding 2 parts of fluorine-containing compound solution and 0.5 part of isopropanol, ultrasonically dispersing for 30min, and filtering by using 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
ultrasonically cleaning and drying the glass surface by using an ethanol aqueous solution, placing the glass surface in a plasma machine for processing for 360s, spraying the hydrophobic and oleophobic coating on the glass surface by using a spray gun, and then placing the glass surface in a 60 ℃ drying oven for drying for 30min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has no obvious particles and has a contact angle to water of 112 degrees.
Comparative example 1
Stirring 2 parts of heptadecafluorodecyltrimethoxysilane and 98 parts of an ethanol aqueous solution (90 parts of ethanol and 8 parts of water) at 40 ℃ for 60min to obtain a fluorine-containing compound solution;
uniformly mixing 10 parts of tetraethoxysilane, 1 part of 3-glycidyl ether oxypropyltrimethoxysilane and 90 parts of ethanol aqueous solution (81 parts of ethanol and 9 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L hydrochloric acid aqueous solution to adjust the pH of the system to 3, heating to 40 ℃, then cooling for 20 hours to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 52nm;
taking 10 parts of nano silica sol solution, adding 100 parts of ethanol, stirring for 30min, adding 2 parts of fluorine-containing compound solution and 0.5 part of n-butyl alcohol, ultrasonically dispersing for 15min, and filtering by adopting 400-mesh filter cloth to obtain a hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass for 120s by using a plasma machine, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in a 60 ℃ drying oven for 30min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has obvious particle aggregates, and the contact angle to water is 112 degrees.
Comparative example 2
Uniformly mixing 10 parts of ethyl orthosilicate, 2 parts of heptadecafluorodecyltrimethoxysilane and 188 parts of an ethanol aqueous solution (171 parts of ethanol and 17 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L hydrochloric acid aqueous solution to adjust the pH of the system to 3, heating to 40 ℃, reacting for 8 hours, adding 1 part of 3-glycidoxypropyltrimethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 12 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 103nm;
taking 10 parts of nano silica sol solution, adding 0.5 part of n-butyl alcohol, performing ultrasonic dispersion for 15min, and filtering by adopting 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass for 120s by using a plasma machine, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in a 60 ℃ oven for 30min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has obvious particle aggregates, and the contact angle to water is 114 degrees.
Comparative example 3
Stirring 2 parts of heptadecafluorodecyltrimethoxysilane and 98 parts of an ethanol aqueous solution (90 parts of ethanol and 8 parts of water) at 40 ℃ for 60min to obtain a fluorine-containing compound solution;
uniformly mixing 10 parts of tetraethoxysilane and 90 parts of ethanol aqueous solution (81 parts of ethanol and 9 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L hydrochloric acid aqueous solution to adjust the pH of the system to 3, heating to 40 ℃, reacting for 8 hours, adding 1 part of 3-glycidyl ether oxypropyltrimethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 12 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 16nm;
taking 10 parts of nano silica sol solution, adding 2 parts of fluorine-containing compound solution and 0.5 part of n-butyl alcohol, ultrasonically dispersing for 15min, and filtering by adopting 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass for 120s by using a plasma machine, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in a 60 ℃ oven for 30min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has no obvious particle aggregate and has a water contact angle of 108 degrees.
Comparative example 4
Stirring 2 parts of heptadecafluorodecyltrimethoxysilane and 98 parts of an aqueous ethanol solution (90 parts of ethanol and 8 parts of water) at 40 ℃ for 60min to obtain a fluorine-containing compound solution;
uniformly mixing 10 parts of tetraethoxysilane and 90 parts of ethanol aqueous solution (81 parts of ethanol and 9 parts of water), stirring to obtain a uniform transparent solution, then dropwise adding 1mol/L hydrochloric acid aqueous solution to adjust the pH of the system to 3, heating to 40 ℃, reacting for 8 hours, adding 1 part of 3-glycidyl ether oxypropyltrimethoxysilane, maintaining the temperature at 40 ℃, continuing to react for 12 hours, cooling to obtain a nano silica sol solution, wherein the particle size of nano silica in the silica sol is 16nm;
taking 10 parts of nano silica sol solution, adding 100 parts of ethanol, stirring for 30min, adding 2 parts of fluorine-containing compound solution and 0.5 part of n-butyl alcohol, ultrasonically dispersing for 15min, and filtering by using 400-mesh filter cloth to obtain a stable and high-transparent hydrophobic and oleophobic coating;
and ultrasonically cleaning and drying the surface of the glass by using an ethanol aqueous solution, treating the glass for 120s by using a plasma machine, then soaking the glass into the hydrophobic and oleophobic coating, slowly lifting the glass, and drying the glass in a 60 ℃ oven for 30min to obtain the hydrophobic and oleophobic glass. The obtained hydrophobic and oleophobic glass surface has obvious flow marks, and the contact angle to water is 107 degrees.
Performance testing
(1) Stability test
The prepared hydrophobic and oleophobic coating is placed in a transparent glass ware for sealing, and is moved to a constant temperature and humidity box (25 ℃,50 percent of relative humidity) for placing, and the time of the coating for sedimentation or gelation is observed.
(2) Contact Angle testing
The contact angle of the surface to water was measured using a contact angle measuring instrument. The water droplet size was 5 μ L, and each sample was measured 5 times and averaged.
(3) Light transmittance test
And (3) placing the material coated with the hydrophobic and oleophobic coating in an ultraviolet visible spectrophotometer, and testing the light transmittance of the material, wherein the testing wavelength range of the light is 300-800nm.
(4) Adhesion test
Adhesion test adopts a hundred-grid knife test method, specifically referring to 'adhesion test of colored paint and varnish by grid cutting method' (GB/T9286-1998), firstly, hydrophobic glass is placed on a flat table, a hundred-grid knife is used for uniformly applying force to the surface of a sample plate perpendicularly, at least 6 parallel cutting lines are stably cut, then the parallel cutting lines are vertically crossed with the first cutting lines at an angle of 90 degrees to form a grid pattern, an adhesive tape is applied to the center of the grid, and the adhesive tape is ensured to be completely contacted with a paint film. And lifting the adhesive tape to form an angle of about 60 degrees with the sample plate, continuously and stably removing the adhesive tape, and then observing the falling condition of the paint film in the grid. The adhesive force grades corresponding to the number of the falling grids of 0, less than 5%, 5% -15%, 15% -35%, 35% -65% and more than 65% are respectively 1-5 grades.
Table 1 results of performance test of examples and comparative examples
As can be seen from the performance tests of the examples and comparative examples in Table 1, the hydrophobic and oleophobic coatings obtained in examples 1-6 have good light transmittance and high adhesion, and good storage stability.
Compared with the example 1, the storage stability of the paint of the comparative example 1 and the paint of the comparative example 2 is poor, and the glass surface has particle aggregates after the paint is coated, so that the light transmittance is low; while comparative example 3 has good light transmittance and hydrophobic property, it is inferior in storage stability compared to example 1; the coating obtained in comparative example 4 was hydrophobic and stable, but showed significant flow marks when applied to the glass surface, affecting light transmittance. Therefore, the hydrophobic and oleophobic coating obtained by the invention has good storage stability, solves the defect of poor storage stability of the common silica sol hydrophobic and oleophobic coating, and has good surface hydrophobicity and adhesive force and high light transmittance after being coated with glass.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The hydrophobic and oleophobic coating is characterized by consisting of a nano silica sol solution, a fluorine-containing compound solution and a leveling agent; the grain diameter of the silicon dioxide in the nano silica sol solution is 1-30 nm.
2. The hydrophobic and oleophobic coating of claim 1, wherein the nanosilicon sol solution is prepared by the following method: uniformly mixing ethyl orthosilicate and an ethanol aqueous solution, stirring to obtain a uniform transparent solution, then dropwise adding an acid catalyst to adjust the pH value of the system, heating the system to 30-60 ℃, reacting for 6-12 h, adding a molecular weight regulator, continuously reacting for 6-12 h, cooling to obtain a nano silica sol solution;
the molecular weight regulator is one of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane and 3-glycidyl ether oxypropyl trimethoxy silane;
the acid catalyst is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
the mass ratio of ethanol to water in the ethanol water solution is 60-95;
the mass ratio of the ethyl orthosilicate to the ethanol aqueous solution is 40-5;
the pH is 1-5.
3. The hydrophobic and oleophobic coating according to claim 2, characterized in that the mass ratio of the ethyl orthosilicate to the molecular weight regulator is 90.
4. The hydrophobic and oleophobic coating of claim 1, wherein the fluorochemical solution is tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane.
5. The hydrophobic and oleophobic coating according to claim 4, characterized in that the fluorine-containing compound solution is obtained by stirring a fluorine-containing compound and an ethanol aqueous solution at 20-60 ℃ for 10-120 min.
6. The hydrophobic and oleophobic coating according to claim 5, characterized in that the mass ratio of the fluorine-containing compound to the aqueous ethanol solution is 0.5-20.
7. The hydrophobic and oleophobic coating according to claim 1, wherein the leveling agent is one or more of ethylene glycol dimethyl ether, isopropanol, N-butanol, ethylene glycol monomethyl ether, and N, N-dimethylformamide.
8. A preparation method of a hydrophobic and oleophobic coating is characterized by comprising the following steps: diluting the nano silica sol solution with ethanol, stirring for 20-50 min, adding a fluorine-containing compound solution and a flatting agent, ultrasonically dispersing for 5-30 min, and filtering to obtain a stable and high-transparency hydrophobic and oleophobic coating;
the mass ratio of the nano silica sol solution to the ethanol is 1:1-1;
the mass ratio of the nano silica sol solution to the fluorine-containing compound solution is 1:1-20;
the mass ratio of the nano silica sol solution to the flatting agent is (100).
9. The application of the hydrophobic and oleophobic coating is characterized in that a glass substrate is cleaned, then treated by a plasma machine, the hydrophobic and oleophobic coating prepared by the preparation method of claim 8 is coated on the surface of the glass substrate by spraying, dip coating, roll coating, spin coating and brush coating, and the glass containing the hydrophobic and oleophobic coating can be obtained after a solvent is dried and volatilized.
10. The use of a hydrophobic and oleophobic coating according to claim 9, characterized in that the hydrophobic and oleophobic coating is dried at room temperature or by heating.
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| CN116715984A (en) * | 2023-05-11 | 2023-09-08 | 淄博国创中心先进车用材料技术创新中心 | Antifreezing paint, antifreezing coating, preparation method and application thereof |
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