CN115231835B - Preparation method of UV (ultraviolet) curing super-hydrophobic material - Google Patents

Preparation method of UV (ultraviolet) curing super-hydrophobic material Download PDF

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CN115231835B
CN115231835B CN202211134016.2A CN202211134016A CN115231835B CN 115231835 B CN115231835 B CN 115231835B CN 202211134016 A CN202211134016 A CN 202211134016A CN 115231835 B CN115231835 B CN 115231835B
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CN115231835A (en
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汪少灿
罗小凤
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Jiangsu Zhongxinrui Optical Materials Co ltd
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    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C2217/76—Hydrophobic and oleophobic 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

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Abstract

The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a UV (ultraviolet) cured super-hydrophobic materialThe preparation method comprises the following steps: the preparation of the bottom resin solution comprises nano SiO 2 Cyclohexanone, UV curing resin and an initiator; preparation of A1: coating the bottom substrate, spin-coating the substrate by a spin coater, vacuum adsorbing, spreading a bottom resin solution on the surface of the substrate, and carrying out surface drying UV light irradiation to obtain a bottom substrate A1 with a coating; preparation of A2: preparation of SiO on the surface layer of A1 by liquid phase deposition 2 Film formation: preparing a growth solution; immersing A1 in growth solution for deposition to make the surface of A1 coated with SiO 2 Film forming to obtain A2; and (3) performing hydrophobic modification on the surface of the A2 to ensure that the A2 is covered with a UV-cured super-hydrophobic coating, thereby obtaining a UV-cured super-hydrophobic material A3. The super-hydrophobic material has the functions of absorbing UV groups and hydrophobicity, and simultaneously has the advantages of self-cleaning function, friction resistance, high hardness, high durability, good UV aging resistance, simple and efficient preparation process, energy conservation and environmental friendliness.

Description

Preparation method of UV (ultraviolet) curing super-hydrophobic material
Technical Field
The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a preparation method of a UV (ultraviolet) curing super-hydrophobic material.
Background
The hydrophobic material has a plurality of unique surface properties such as corrosion resistance, self-cleaning, hydrophobicity, good visual effect and the like due to the existence of micro-nano structure mastoid similar to lotus leaf surface and wax on the surface of the hydrophobic material. The characteristics endow the super-hydrophobic material with unique performance, so that the super-hydrophobic material has wide application prospects in national defense, industrial and agricultural production and daily life.
With the gradual attention of people on environmental protection and energy utilization, the sustainable development concept is carried out, and high-efficiency and environment-friendly novel green coating is competitively researched in all countries in the world. The Ultraviolet (UV) curing material adopts a radiation curing method, the radiation curing technology has the characteristic of '5E' (high efficiency, energy conservation, wide adaptability, economy and environmental protection), and the Ultraviolet (UV) curing material becomes a 'green coating' variety which develops rapidly in recent years.
For example, patent application with publication number CN102675941a discloses a UV-cured super-hydrophobic fingerprint-resistant coating and a preparation method thereof, the coating is prepared into a UV-cured coating by adopting high-activity PUA oligomer, a reactive diluent, a photoinitiator and the like, and a monomer with a special structure is added to achieve the fingerprint-resistant effect; on the basis, active fluorine monomer, silicone resin and the like are introduced to form self-layering hydrophobic varnish with a compact and stable surface so as to achieve a self-cleaning effect; finally by changing toNano SiO2 2 And constructing a surface micro-nano structure by adopting a self-assembly technology.
The patent application with publication number CN108587381A discloses a processing technology of a UV-cured fluorine-containing wear-resistant hydrophobic coating, wherein the hydrophobic coating is formed by matching a bottom hydrophobic coating and a surface hydrophobic coating in a double-layer manner, so that the coating has hydrophobic and oleophobic properties while the adhesion of the waterproof coating and a target material is ensured. The bottom coating is prepared from organosilicon fluorine-containing acrylate emulsion and nano SiO modified by all (heptadecafluorodecyl trimethoxy silane 2 /TiO 2 The mixed solution of the dispersion liquid is coated by adopting a spraying process; the surface coating is prepared by adding perfluoroheptadecane trimethyl oxysilane as hydrophobic agent into isopropanol solution, stirring, and adding nanometer SiO 2 /TiO 2 And mixing and stirring the dispersion liquid, dibutyltin dilaurate and dimethyl silicon oil to obtain a mixed solution, and coating by adopting a spraying process. The acrylic ester is used for curing the hydrophobic coating at the bottom layer, so that the strength and the compactness of the waterproof coating can be improved; the fluorine-containing silane and the fluorine-containing acrylate improve the hydrophobic performance of the hydrophobic coating on the surface layer.
However, although the preparation method and the processing technology enable the super-hydrophobic material to have the functions of absorbing UV groups and hydrophobicity, the super-hydrophobic material is complex, single in performance, low in hardness, low in durability and general in UV aging resistance, and the super-hydrophobic material using the fluorine-containing polymer as the raw material is toxic and not beneficial to environmental protection.
Disclosure of Invention
The invention aims to provide a preparation method of a UV-cured super-hydrophobic material, so that the super-hydrophobic material has the functions of absorbing UV groups and hydrophobicity, and simultaneously has the advantages of self-cleaning function, friction resistance, high hardness, high durability, good UV aging resistance, simple and efficient preparation process, energy conservation and contribution to environmental protection.
A preparation method of a UV-cured super-hydrophobic material comprises the following preparation steps:
A. preparation of bottom resin solution: mixing nano SiO 2 Mixing with cyclohexanone, ultrasonic crushing, cooling to room temperature, adding UV curable resin and initiator, stirring at room temperature to obtain mixed solution,the mixed solution is a bottom resin solution;
B. preparation of the coated base substrate A1: coating the bottom substrate, namely spin-coating the bottom substrate by a spin coater, performing vacuum adsorption, spreading the bottom resin solution on the surface of the bottom substrate, drying the surface after the spin coating is finished, and irradiating by UV light to completely cure the coating to obtain the bottom substrate A1 with the coating;
by adopting the technical scheme, the bottom layer is made of UV curing resin and nano SiO 2 The mixed solution is subjected to a spin coating process, so that a resin substrate with certain strong hardness and a micro-nano structure on the surface can be constructed.
C. Preparing A2, wherein the preparation of A2 is to prepare SiO on the surface layer of A1 by a liquid phase deposition method 2 Film formation:
1) Preparation of growth solution: measuring H 2 SiF 6 The solution is poured into a container and fed to H 2 SiF 6 Adding silicic acid powder into the solution, and magnetically stirring until SiO in the solution 2 Filtering out solid particles by using filter cloth when the saturated state is reached to obtain a clarified liquid;
weighing a clear solution, pouring the clear solution into a container, adding deionized water, and stirring at normal temperature to enable the solution to reach a supersaturated state to obtain a supersaturated solution;
by adopting the technical scheme, H in the solution 2 SiF 6 Is adjusted to a suitable range, and the concentration of SiO grows too low 2 The crystal can not form a film shape, HF can be generated faster when the concentration is too high, the formed film is corroded, and the film deposition rate is reduced.
Adding a boric acid solution or aluminum into the supersaturated solution, and stirring at normal temperature to obtain a growth solution;
by adopting the technical scheme, not only can HF generated in the solution be consumed, but also SiO can be promoted 2 The subsequent film forming is convenient.
2) Vertically putting the bottom substrate A1 with the coating into the growth solution, completely immersing for deposition, washing with deionized water after deposition, and drying at normal temperature to ensure that the surface layer of the A1 is covered with SiO 2 Film, obtaining A2;
by adopting the technical scheme, the surface layer is used for preparing SiO by adopting a liquid phase deposition method 2 The film can further improve the strong hardness of the micro-nano structure on the surface of the film layer.
D. Adding a catalyst into hydrogen-containing silicone oil, soaking A2 into a hydrogen-containing silicone oil solution containing the catalyst after magnetic stirring to perform hydrophobic modification on the surface of A2, taking out A2, and washing with absolute ethyl alcohol to enable the A2 to be coated with a UV-cured super-hydrophobic coating, thereby obtaining a UV-cured super-hydrophobic material A3.
By adopting the technical scheme, the hydrogen-containing silicone oil is finally used for treating SiO 2 The film is modified to make the film super-hydrophobic, thereby solving the problem that the super-hydrophobic disappears after the traditional super-hydrophobic coating is wiped, and simultaneously making the coating have good hardness.
Preferably, in the preparation of the bottom resin solution, the nano SiO 2 The addition amount of the (1) is 0.4 to 0.5g, the addition amount of the cyclohexanone is 10 to 15g, the ultrasonic crushing time is 5 to 15min, the addition amount of the UV curing resin is 2 to 5g, the stirring time at room temperature is 30 to 120min, and the volume of the mixed solution is 15 to 25ml.
Preferably, in the preparation of the bottom resin solution, the initiator is 5 to 10 percent of the content of the UV curing resin.
Preferably, in the preparation of the bottom base material A1 with the coating, 2 to 5ml of bottom resin solution is sucked by a dropper to be spread on the surface of the base material, the rotating speed of a glue spreader is 500 to 3000r, the spin coating time is 10 to 30s, after the spin coating is finished, the surface is dried at 120 to 150 ℃ for 30min, and the UV light is irradiated for 60 to 90s, so that the coating is completely cured.
Preferably, said amount of H is taken during the preparation of the growth solution 2 SiF 6 The concentration of the solution is 30 to 32 percent, and the purity of the silicic acid powder>99 percent, magnetically stirring for 8 to 10 hours;
weighing the clear liquid, pouring the clear liquid into a container, adding deionized water, and stirring at normal temperature for 25 to 35 min;
and (3) stirring the aluminum with the concentration of more than 99% at normal temperature for 25-35 min to obtain a growth solution.
Preferably, the bottom layer substrate with the coating is vertically placed into the growth solution and is completely immersed for deposition, and the deposition temperature is lowThe temperature is 25-40 ℃, the deposition time is 4-6h, the deposition is finished, the deposition is washed by deionized water, the air is dried at normal temperature, the air drying time is more than or equal to 30min, and the surface layer of A1 is covered with SiO 2 Film, A2 was obtained.
Preferably, 0.5-1ml of catalyst is added into 20-40ml of hydrogen-containing silicone oil, A2 is immersed into the hydrogen-containing silicone oil solution containing the catalyst after magnetic stirring to carry out hydrophobic modification on the surface of A2, and A2 is taken out after 4 hours;
the catalyst comprises at least one of dibutyltin dilaurate and dioctyltin mercaptide.
Preferably, the A2 is covered with a UV-cured super-hydrophobic coating to obtain a UV-cured super-hydrophobic material A3, and the UV-cured super-hydrophobic coating can finally reach 6H hardness through a pencil hardness test.
The invention has the beneficial effects that:
firstly, the super-hydrophobic material has the functions of absorbing UV groups and dewatering, and simultaneously has the advantages of self-cleaning function, friction resistance, high hardness, high durability, good UV aging resistance, simple and efficient preparation process and energy conservation;
the water contact angle can reach more than 140 degrees, and the hardness can reach 5H to 6H; in particular to a method for preparing SiO with a micro-nano structure by adopting a double-layer coating process 2 Film, and hydrogen-containing silicone oil is used for treating SiO 2 Performing hydrophobic modification on the film to finally obtain a UV-cured super-hydrophobic coating film with certain strong hardness; the bottom layer is UV curing resin and nano SiO 2 The mixed solution is subjected to a spin coating process to construct a resin substrate with certain strength and hardness and a micro-nano structure on the surface; the surface layer is prepared into the silicon dioxide film by adopting a liquid phase deposition method, so that the strength and hardness of the micro-nano structure on the surface of the film layer are further improved; finally, hydrogen-containing silicone oil is used for treating SiO 2 The film is modified to make the film super-hydrophobic, so that the problem that the super-hydrophobic disappears after the traditional super-hydrophobic coating is wiped is solved, and meanwhile, the coating has good hardness.
Secondly, the super-hydrophobic material is a fluorine-free UV curing super-hydrophobic coating, and is beneficial to environmental protection.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic drawing of the 151.59 ° coated water drop angle of example 1 of the present invention;
FIG. 2 is a schematic drawing of the 144.09 ° coated water drop angle of example 2 of the present invention;
FIG. 3 is a schematic drawing of the 149.43 ° coating water drop angle of example 3 of this invention;
FIG. 4 is a schematic drawing of the 139.77 ° coating water drop angle of comparative example 1 of the present invention;
FIG. 5 is a schematic drawing of the water drop angle of the 145.03 ° coating of comparative example 2 of the present invention.
Detailed Description
Example 1
Referring to fig. 1, a method for preparing a UV-curable superhydrophobic material:
TABLE 1
Primer resin solution formulation Addition amount (g)
Nano SiO2 0.45
Cyclohexanone 14.45
UV curable resin 2
Initiator 0.1
A. Preparation of bottom resin solution: referring to the above Table 1, nano SiO 2 Mixing with cyclohexanone, carrying out ultrasonic crushing for 5min, cooling to room temperature, adding UV curing resin and an initiator, and stirring at room temperature for 30min to obtain 18ml of mixed solution, wherein the mixed solution is a bottom resin solution;
B. preparation of the coated base substrate A1: coating and coating a bottom substrate by using a spin coating process of a spin coater, wherein the bottom substrate is preferably a glass substrate, the glass substrate is placed on a sample table in the spin coater, vacuum adsorption is carried out, 2ml of bottom resin solution is absorbed by a dropper to be paved on the surface of the substrate, the rotation speed of the spin coater is set to be 1000r, the spin coating time is 10s, the surface drying is carried out for 30min at 150 ℃ after the spin coating is finished, and the UV light irradiates for 60s to completely cure the coating, so that the bottom substrate A1 with the coating is obtained;
C. preparation of A2: preparation of SiO on the surface layer of A1 by liquid phase deposition 2 Film formation:
1) Preparation of growth solution: measuring 20ml of H with the concentration of 30% -32% 2 SiF 6 Pouring the solution into a container, preferably a plastic container, into a vessel, and introducing hydrogen 2 SiF 6 Adding 2g of silicic acid powder with purity of more than 99% into the solution, and magnetically stirring for 8h until SiO in the solution 2 Filtering out solid particles by using filter cloth when the saturated state is reached to obtain a clarified liquid;
weighing 18ml of clarified liquid, pouring into a container, preferably a plastic container, adding 9ml of deionized water, and stirring at normal temperature for 30min to enable the solution to reach a supersaturated state, thereby obtaining a supersaturated solution; at this point in the solution H 2 SiF 6 Is adjusted to 1.5M, the concentration of SiO grows too low 2 The crystal can not form a film form, HF can be generated quickly when the concentration is too high, the formed film is corroded, and the film deposition rate is reduced;
TABLE 2
Boric acid solutionFormulation of Amount of addition
Boric acid 0.0223g
Water (W) 9ml
Referring to the above table 2, 0.01M boric acid solution was added to the supersaturated solution, and stirred at room temperature for 30min to obtain 36ml growth solution; this not only consumes HF formed in the solution, but also promotes SiO 2 The subsequent film forming is convenient;
2) Vertically putting the bottom substrate A1 with the coating into a growth solution, completely immersing for deposition, wherein the deposition temperature is 40 ℃, the deposition time is 4h, washing with deionized water after deposition, and airing at normal temperature for 30min to ensure that the surface layer of the A1 is covered with SiO 2 Film, obtaining A2;
D. adding 0.5ml of dibutyltin dilaurate into 20ml of hydrogen-containing silicone oil, soaking A2 into a hydrogen-containing silicone oil solution containing dibutyltin dilaurate after magnetic stirring to perform hydrophobic modification on the surface of A2, taking out A2 after 4 hours, washing with absolute ethyl alcohol to ensure that the A2 is covered with a UV-cured super-hydrophobic coating to obtain a UV-cured super-hydrophobic material A3, and finally reaching 6H hardness of the UV-cured super-hydrophobic coating through pencil hardness test, wherein the results refer to Table 7 and figure 1.
Example 2
Referring to fig. 2, a method for preparing a UV-curable superhydrophobic material:
TABLE 3
Primer resin solution formulation Addition amount (g)
Nano SiO2 0.45
Cyclohexanone 10.3
UV curable resin 2
Initiator 0.1
A. Preparation of bottom resin solution: referring to the above Table 3, the nano SiO 2 Mixing with cyclohexanone, carrying out ultrasonic crushing for 5min, cooling to room temperature, adding UV curing resin and an initiator, and stirring at room temperature for 30min to obtain 14ml of mixed solution, wherein the mixed solution is a bottom resin solution;
B. preparation of the coated base substrate A1: coating and coating a bottom substrate by using a spin coating process of a spin coater, wherein the bottom substrate is preferably a glass substrate, the glass substrate is placed on a sample table in the spin coater, vacuum adsorption is carried out, 2ml of bottom resin solution is absorbed by a dropper to be paved on the surface of the substrate, the rotation speed of the spin coater is set to be 1000r, the spin coating time is 10s, the surface drying is carried out for 30min at 150 ℃ after the spin coating is finished, and the UV light irradiates for 60s to completely cure the coating, so that the bottom substrate A1 with the coating is obtained;
C. preparation of A2: preparation of SiO on the surface layer of A1 by liquid phase deposition 2 Film formation:
1) Preparation of growth solution: measuring 30ml of H with the concentration of 30% -32% 2 SiF 6 Pouring the solution into a container, preferably a plastic container, into H 2 SiF 6 Adding 3g of silicic acid powder with purity of more than 99% into the solution, and magnetically stirring for 10h until SiO in the solution 2 Reaching saturation state, filtering out solid particles with filter cloth to obtain clear solutionLiquid;
weighing 25ml of clear solution, pouring the clear solution into a container, preferably a plastic container, adding 12-13ml of deionized water, and stirring at normal temperature for 30min to enable the solution to reach a supersaturated state, thereby obtaining a supersaturated solution; at this point in the solution H 2 SiF 6 Is adjusted to 1.5M, the concentration of SiO grows too low 2 The crystal can not form a film form, HF can be generated quickly when the concentration is too high, and the formed film is corroded, so that the film deposition rate is reduced;
adding 0.4g of aluminum into the supersaturated solution, and stirring at normal temperature for 30min to obtain 36ml of growth solution; this not only consumes HF formed in the solution, but also promotes SiO 2 The subsequent film forming is convenient;
2) Vertically putting the bottom substrate A1 with the coating into a growth solution, completely immersing for deposition, wherein the deposition temperature is 40 ℃, the deposition time is 4h, washing with deionized water after deposition, and airing at normal temperature for 30min to ensure that the surface layer of the A1 is covered with SiO 2 Film, obtaining A2;
D. adding 0.5ml of dibutyltin dilaurate into 20ml of hydrogen-containing silicone oil, soaking A2 into a hydrogen-containing silicone oil solution containing dibutyltin dilaurate after magnetic stirring to perform hydrophobic modification on the surface of A2, taking out A2 after 4 hours, washing with absolute ethyl alcohol to ensure that the A2 is covered with a UV-cured super-hydrophobic coating to obtain a UV-cured super-hydrophobic material A3, and finally reaching 5H hardness of the UV-cured super-hydrophobic coating through pencil hardness test, wherein the results refer to Table 7 and figure 2.
Example 3
Referring to fig. 3, a method for preparing a UV-curable superhydrophobic material:
TABLE 4
Primer resin solution formulation Addition amount (g)
Nano SiO2 0.45
Cyclohexanone 14.45
UV curable resin 2
Initiator 0.1
A. Preparation of bottom resin solution: referring to Table 4 above, the nano SiO 2 Mixing with cyclohexanone, carrying out ultrasonic crushing for 5min, cooling to room temperature, adding UV curing resin and an initiator, and stirring at room temperature for 30min to obtain 18ml of mixed solution, wherein the mixed solution is a bottom resin solution;
B. preparation of the coated base substrate A1: coating and coating a bottom substrate by using a spin coating process of a spin coater, wherein the bottom substrate is preferably a glass substrate, the glass substrate is placed on a sample table in the spin coater, vacuum adsorption is carried out, 2ml of bottom resin solution is absorbed by a dropper to be paved on the surface of the substrate, the rotation speed of the spin coater is set to be 1000r, the spin coating time is 10s, the surface drying is carried out for 30min at 150 ℃ after the spin coating is finished, and the UV light irradiates for 60s to completely cure the coating, so that the bottom substrate A1 with the coating is obtained;
C. preparation of A2: preparation of SiO on the surface layer of A1 by liquid phase deposition 2 Film formation:
1) Preparation of growth solution: measuring 20ml of H with the concentration of 30% -32% 2 SiF 6 Pouring the solution into a container, preferably a plastic container, into a vessel, and introducing hydrogen 2 SiF 6 Adding 2g of silicic acid powder with purity of more than 99% into the solution, and magnetically stirring for 10h until SiO in the solution 2 Filtering out solid particles by using filter cloth when the saturated state is reached to obtain a clarified liquid;
measuring 18ml of clear liquid, and pouring into a container, preferably plasticAdding 9ml of deionized water into a material container, and stirring at normal temperature for 30min to enable the solution to reach a supersaturated state to obtain a supersaturated solution; at this point in the solution H 2 SiF 6 Is adjusted to 1.5M, the concentration of SiO grows too low 2 The crystal can not form a film form, HF can be generated quickly when the concentration is too high, the formed film is corroded, and the film deposition rate is reduced;
TABLE 5
Boric acid solution formula Amount of addition
Boric acid 0.0223g
Water (W) 9ml
Referring to table 5 above, 0.01M boric acid solution was added to the supersaturated solution, and stirred at room temperature for 30min to obtain 36ml growth solution; this not only consumes HF formed in the solution, but also promotes SiO 2 The subsequent film forming is convenient;
2) Vertically putting the bottom substrate A1 with the coating into a growth solution, completely immersing for deposition, wherein the deposition temperature is 40 ℃, the deposition time is 4h, washing with deionized water after deposition, and airing at normal temperature for 30min to ensure that the surface layer of the A1 is covered with SiO 2 Film, obtaining A2;
D. adding 1ml of dioctyl tin mercaptide into 20ml of hydrogen-containing silicone oil, after magnetic stirring, immersing A2 into a hydrogen-containing silicone oil solution containing dioctyl tin mercaptide to perform hydrophobic modification on the surface of A2, taking out A2 after 4 hours, washing with absolute ethyl alcohol to ensure that the A2 is covered with a UV-cured super-hydrophobic coating, obtaining a UV-cured super-hydrophobic material A3, and finally achieving 6H hardness of the UV-cured super-hydrophobic coating through pencil hardness test, wherein the results refer to Table 7 and figure 3.
Comparative example 1
Referring to fig. 4, a method for preparing a UV-curable superhydrophobic material specifically includes:
preparing 5% nano SiO 2 Adjusting the pH value of the ethyl acetate solution to 4-5, and stirring and reacting under the water bath condition of 40-50 ℃ to obtain 100g of active nano particle dispersion liquid; 50g of the dispersion was added with 0.5g of methyl 2-fluoroacrylate, 1g of dipentaerythritol hexaacrylate, and 0.5g of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide, and stirred and mixed uniformly to prepare a dipping solution. And (3) putting the transparent glass into the dipping solution for soaking for 10min, airing for 30min at 60 ℃, and carrying out UV curing for 60s to form a UV-cured super-hydrophobic coating to obtain the UV-cured super-hydrophobic material, wherein the UV-cured super-hydrophobic coating reaches HB hardness through a pencil hardness test, and the results refer to Table 7 and figure 4.
Comparative example 2
Referring to fig. 5, a method for preparing a UV-curable superhydrophobic material includes the following steps:
1) Taking 100mg of graphene oxide in 60 ml absolute ethyl alcohol, ultrasonically dispersing 1 h to form uniform dispersion liquid, adding hydrochloric acid to adjust the pH of the dispersion liquid to 3-4, slowly adding 10ml of 95% ethyl alcohol containing 0.3 g KH-570 into the dispersion liquid under stirring, continuously reacting for 24 hours at 60 ℃, centrifugally separating the obtained product, and then washing the product with absolute ethyl alcohol and deionized water to obtain modified graphene oxide, so that unreacted silane coupling agent KH-570 can be completely removed, and the washing liquid is neutral;
2) Stirring the urethane acrylate, the cross-linking agent and the modified graphene oxide at 40 ℃ and performing ultrasonic oscillation for 30min to obtain a mixed solution B1; wherein the addition amount of the modified graphene oxide is 0.2-5% of the mass of the monomer polyurethane acrylate;
3) Mixing nano SiO 2 Adding the mixture into an ethanol solution, stirring and mixing uniformly, adding the mixture into the mixed solution B1, and stirring and mixing uniformly to obtain a mixed solution B2; wherein, the nano SiO 2 The mass ratio of the alcohol to the ethanol is 1: 15;
4) Adding a photoinitiator into the mixed solution B2, spraying the mixed solution B2 containing the photoinitiator on a substrate by using a spray gun, placing the substrate under an ultraviolet lamp for illumination and curing, and forming a UV-cured super-hydrophobic coating after curing to obtain a UV-cured super-hydrophobic material; wherein the addition amount of the photoinitiator is 5 percent of the mass of the monomer polyurethane acrylate; the UV cured superhydrophobic coating finally reached a 2B hardness by pencil hardness testing, with the results referring to table 7 and fig. 5.
The test pieces prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for the water drop angle (water contact angle), rolling angle, light transmittance, adhesion stability, hardness, UV aging performance index, wherein the water drop angle is indicative of hydrophobicity, and the instrument and test data are shown in the following tables 6 and 7, respectively:
TABLE 6
Content of test Instrument type
Water drop angle (Water contact angle) RM-J08A type water drop angle tester
Roll angle SCI2000B rolling angle measuring instrument
Light transmittance UV-2600 type light transmittance tester
Stability of adhesion QFH-A type adhesion force tester
Hardness of Model QHQ-A pencil hardness tester
UV aging Performance index MDYA-250 type UV aging tester
TABLE 7
Sample (I) Water drop angle Roll angle Light transmittance Stability of adhesion Hardness of UV aging Performance index
Example 1 151.59° 3° 88.17% By passing 6H Resistance to yellowing
Example 2 144.09° 12° 86.92% By passing 5H Resistance to yellowing
Example 3 149.43° 5° 88.59% By passing 6H Resistance to yellowing
Comparative example 1 139.77° 18° 90.33% By passing HB Is not resistant to yellowing
Comparative example 2 145.03° 42.7° 65% By passing 2B Is not resistant to yellowing
The UV-cured super-hydrophobic coating of the UV-cured super-hydrophobic material has a water contact angle of over 140 degrees, hardness of 5H to 6H, good light transmittance, good adhesion stability and good UV aging resistance.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A preparation method of a UV-cured super-hydrophobic material is characterized by comprising the following preparation steps:
A. preparation of bottom resin solution: mixing nano SiO 2 Mixing the mixture with cyclohexanone, carrying out ultrasonic crushing, cooling to room temperature, adding UV curing resin and an initiator, and stirring at room temperature to obtain a mixed solution, wherein the mixed solution is a bottom resin solution;
B. preparation of the coated base substrate A1: coating the bottom substrate, namely spin-coating the bottom substrate by a spin coater, performing vacuum adsorption, spreading the bottom resin solution on the surface of the bottom substrate, drying the surface after the spin coating is finished, and irradiating by UV light to completely cure the coating to obtain the bottom substrate A1 with the coating;
C. preparing A2, wherein the preparation of A2 is to prepare SiO on the surface layer of A1 by a liquid phase deposition method 2 Film formation:
1) Preparation of growth solution: measuring H 2 SiF 6 The solution is poured into a container and fed to H 2 SiF 6 Adding silicic acid powder into the solution, and magnetically stirring until SiO in the solution 2 Filtering out solid particles by using filter cloth when the saturated state is reached to obtain a clarified liquid;
weighing a clear solution, pouring the clear solution into a container, adding deionized water, and stirring at normal temperature to enable the solution to reach a supersaturated state to obtain a supersaturated solution;
adding boric acid solution or aluminum into the supersaturated solution, and stirring at normal temperature to obtain a growth solution;
2) Vertically putting the bottom substrate A1 with the coating into the growth solution, completely immersing for deposition, washing with deionized water after deposition, and drying at normal temperature to make the surface layer of the substrate A1Coated with SiO 2 Film, obtaining A2;
D. adding a catalyst into hydrogen-containing silicone oil, magnetically stirring, immersing A2 into a hydrogen-containing silicone oil solution containing the catalyst, performing hydrophobic modification on the surface of A2, taking out A2, washing with absolute ethyl alcohol to enable the A2 to be coated with a UV-cured super-hydrophobic coating, and obtaining a UV-cured super-hydrophobic material A3.
2. The method for preparing UV-curable superhydrophobic material of claim 1, wherein the nano SiO is prepared in preparation of the resin solution of the bottom layer 2 The addition amount of the (b) is 0.4 to 0.5g, the addition amount of the cyclohexanone is 10 to 15g, the ultrasonic crushing time is 5 to 15min, the addition amount of the UV curing resin is 2 to 5g, the stirring time at room temperature is 30 to 120min, and the volume of the mixed solution is 15 to 25ml.
3. The method for preparing the UV-curable superhydrophobic material according to claim 1, wherein in preparation of a bottom resin solution, the initiator accounts for 5-10% of the mass of the UV-curable resin.
4. The preparation method of the UV-curable superhydrophobic material according to claim 1, wherein in the preparation of the coated base substrate A1, a dropper is used for sucking 2 to 5ml of base resin solution to be paved on the surface of the base substrate, the rotating speed of a glue homogenizing machine is 500 to 3000r, the spin coating time is 10 to 30s, and after the spin coating is finished, the coating is dried at 120 to 150 ℃ for 30min and is irradiated by UV light for 60 to 90s, so that the coating is completely cured.
5. The method of claim 1, wherein the H is measured during the preparation of the growth solution 2 SiF 6 The concentration of the solution is 30 to 32 percent, and the purity of the silicic acid powder is>99 percent, magnetically stirring for 8 to 10 hours;
weighing the clear liquid, pouring the clear liquid into a container, adding deionized water, and stirring at normal temperature for 25 to 35 min;
and (3) stirring the aluminum with the concentration of more than 99% at normal temperature for 25-35 min to obtain a growth solution.
6. The preparation method of the UV-curable superhydrophobic material according to claim 1, wherein in the step 2), the bottom base material with the coating is vertically placed in the growth solution, completely immersed for deposition, the deposition temperature is 25-40 ℃, the deposition time is 4-6h, the substrate is washed by deionized water after deposition is finished, and the substrate is dried at normal temperature for more than or equal to 30min, so that the SiO is coated on the surface layer of the A1 2 Film, A2 was obtained.
7. The preparation method of the UV-curable superhydrophobic material according to claim 1, wherein in the step D, 0.5 to 1ml of a catalyst is added into 20 to 40ml of hydrogen-containing silicone oil, after magnetic stirring, the A2 is immersed into a hydrogen-containing silicone oil solution containing the catalyst to perform hydrophobic modification on the surface of the A2, and the A2 is taken out after 4 hours;
the catalyst comprises at least one of dibutyltin dilaurate and dioctyltin mercaptide.
8. The method for preparing the UV-curable superhydrophobic material according to claim 1, wherein in step D, A2 is coated with a UV-curable superhydrophobic coating to obtain a UV-curable superhydrophobic material A3, wherein the UV-curable superhydrophobic coating has a hardness of 6H according to a pencil hardness test.
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CN105273586A (en) * 2015-10-20 2016-01-27 宁波大榭开发区综研化学有限公司 Anti-fouling and anti-UV (ultraviolet) coating composition, hard coating film and preparation method
CN106317997A (en) * 2015-06-22 2017-01-11 泰州市华丽塑料有限公司 Nano-TiO2 modified UV coating and production method thereof
CN107555807A (en) * 2017-08-24 2018-01-09 福建农林大学 A kind of method for preparing rub resistance hydrophobic silica anti-reflection film
CN110669363A (en) * 2019-10-18 2020-01-10 东莞深圳清华大学研究院创新中心 Preparation method of transparent super-hydrophobic coating
CN112011266A (en) * 2020-10-29 2020-12-01 宁波富纳新材料科技有限公司 UV (ultraviolet) curing coating, protective film comprising UV curing coating and preparation method of protective film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675941A (en) * 2012-05-29 2012-09-19 江门亿源生化工程有限公司 Ultraviolet (UV) curable super-hydrophobic anti-fingerprint coating and preparation method thereof
CN106317997A (en) * 2015-06-22 2017-01-11 泰州市华丽塑料有限公司 Nano-TiO2 modified UV coating and production method thereof
CN105273586A (en) * 2015-10-20 2016-01-27 宁波大榭开发区综研化学有限公司 Anti-fouling and anti-UV (ultraviolet) coating composition, hard coating film and preparation method
CN107555807A (en) * 2017-08-24 2018-01-09 福建农林大学 A kind of method for preparing rub resistance hydrophobic silica anti-reflection film
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