CN116676002B - Self-repairing super-hydrophobic anti-reflection coating and coating - Google Patents
Self-repairing super-hydrophobic anti-reflection coating and coating Download PDFInfo
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- CN116676002B CN116676002B CN202310967474.2A CN202310967474A CN116676002B CN 116676002 B CN116676002 B CN 116676002B CN 202310967474 A CN202310967474 A CN 202310967474A CN 116676002 B CN116676002 B CN 116676002B
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- 238000000576 coating method Methods 0.000 title claims abstract description 136
- 239000011248 coating agent Substances 0.000 title claims abstract description 135
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000002987 primer (paints) Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000011859 microparticle Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 42
- -1 polytetrafluoroethylene Polymers 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002344 surface layer Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 31
- 238000002834 transmittance Methods 0.000 abstract description 27
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 46
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000007921 spray Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 238000001132 ultrasonic dispersion Methods 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 10
- 244000137852 Petrea volubilis Species 0.000 description 8
- 238000006748 scratching Methods 0.000 description 8
- 230000002393 scratching effect Effects 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000000422 nocturnal effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The application provides a self-repairing super-hydrophobic anti-reflection coating and a coating, comprising a bottom coating and a surface coating, wherein the bottom coating comprises microparticles, a dispersing agent, a high polymer, polyborosiloxane, a curing agent and a coupling agent, and the surface coating comprises nanoparticles, a dispersing agent, a high polymer, a curing agent and a coupling agent. The self-repairing super-hydrophobic anti-reflection coating and the coating adopt a double-layer design thought, namely a primer coating and a surface coating, wherein the primer coating is composed of large-size microparticles, high-molecular polymers and polyborosiloxane, the microparticles are more easily and firmly adhered to the surfaces of carriers such as glass and the like than the nanoparticles, the surface coating is composed of the nanoparticles and the high-molecular polymers, and the nanoparticles are adhered to a bottom micrometer structure, so that the self-repairing coating has high adhesive force, high light transmittance, easiness in repairing and self-repairing performance.
Description
Technical Field
The application belongs to the field of coatings, and particularly relates to a self-repairing super-hydrophobic anti-reflection coating and a coating.
Background
Through research and study on plant leaves with superhydrophobicity in nature, two conditions are required to be provided for preparing the superhydrophobic surface: firstly, the surface of the material has very low surface energy; secondly, a double structure with a certain roughness and micron and nanometer is constructed on the surface of the solid material. Through a bionic technology, the super-hydrophobic coating can form a micro-nano structure similar to lotus leaves when being coated on the solid surface, so that the solid surface has super-hydrophobic performance.
When light strikes the interface between two media, a portion of the light changes direction of propagation back into the original medium and continues to propagate, a phenomenon known as light reflection. This is due to the abrupt change in refractive index at the discontinuous boundary.
In 1967 Bernhard found that nocturnal moths had an aggregate of micro-hexagons with diameters of about 100n to 200nm, and that the hexagonal surfaces had fine irregularities, and that the evolution characteristics could prevent reflection of light by eyes and prevent natural enemies or prey from finding themselves, and could efficiently collect weak light at night for four weeks.
The study surface, the reflection of light and the surface structure of the material have the following relation:
1. if the unit scale of the array of structures is greater than a wavelength, incident light can identify individual structures as matter and be absorbed, reflected, and scattered by individual structure portions.
2. If the depth scale and spacing between individual structures is similar to the wavelength of the incident light, the light may be trapped between the individual structures, resulting in multiple internal reflections.
3. If the incident light is insensitive to individual structures when the unit scale of the array of structures is smaller than the wavelength, the incident light will tend to bend gradually.
4. When the material has multiple layers of coating on its surface, and the refractive index of these layers is between that of glass and air, a gradient is formed that gradually decreases from glass to air, and the incident light is also gradually curved.
Patent publication No. CN105565678A discloses a reflection-reducing reflection-increasing super-hydrophobic self-cleaning SiO 2 Nanocoating consisting of a bilayer nanoparticle system, the first layer being a solid SiO with small dimensions 2 Particle-structured anti-reflection coating, the second layer is formed by dendritic SiO 2 The super-hydrophobic coating constructed by the nano particles has excellent super-hydrophobic self-cleaning performance and anti-reflection performance, but because the preparation method involves high temperature, when the coating is damaged, the coating is difficult to repair; patent publication No. CN106629793A discloses a hollow rod-like MgF 2 Preparation method of particles and application of particles in self-cleaning antireflection film, and hollow rod-shaped MgF is utilized 2 Particles and SiO 2 After the particles are compounded, a layer of thin film is plated by a lifting-dipping methodThe film is dried at 250 ℃ to obtain the self-cleaning antireflection film which has superhydrophobicity and has the highest light transmittance of more than 97% in the visible light range, but the film is directly coated on the surface of glass, cannot obtain higher adhesive force and is easy to fall off.
Disclosure of Invention
In view of the above, the application aims to provide a self-repairing super-hydrophobic anti-reflection coating and a coating, which are used for improving the hydrophobic anti-reflection performance of the coating, enhancing the adhesive force with a carrier and improving the self-repairing capability.
In order to achieve the above purpose, the technical scheme of the application is realized as follows:
the self-repairing super-hydrophobic anti-reflection coating comprises a primer and a surface coating, wherein the primer comprises microparticles, a dispersing agent, a high molecular polymer, polyborosiloxane, a curing agent and a coupling agent, the surface coating comprises nanoparticles, a dispersing agent, a high molecular polymer, a curing agent and a coupling agent, the microparticles comprise one or more of micrometer silicon dioxide, micrometer titanium dioxide, micrometer calcium carbonate, micrometer diatomite, kaolin, nylon powder, polytetrafluoroethylene powder, ferric oxide, chromium powder, boron oxide, boron nitride and boron carbide, the high molecular polymer comprises one or more of polydimethylsiloxane, MQ resin, polyethylene, polystyrene, polyurethane, epoxy resin, alkyd resin and acrylic resin, and the nanoparticles comprise one or more of nanometer silicon dioxide, nanometer titanium dioxide, nanometer vinylidene fluoride microspheres, nanometer ferric oxide, carbon nanotubes, nanometer silver, nanometer tin oxide, nanometer zirconium oxide, nanometer antimony oxide, nanometer boron nitride, nanometer boron carbide and nanometer silicon carbide.
Further, the dispersing agent may be xylene, toluene, tetrahydrofuran, ethyl acetate, etc., and any dispersing agent used in the art for dispersing the microparticles and nanoparticles as described above is suitable for the present application.
Further, the microparticles have a particle size of 0.1 to 100 μm.
Further, the particle size of the nanoparticle is 5-100nm.
Further, the mass ratio of the microparticles, the dispersing agent, the high molecular polymer, the polyborosiloxane and the coupling agent in the primer is 1:10-500:0.01-10:0.01-10:0.01-1, and the mass ratio of the high molecular polymer to the curing agent is 10:1.
Further, the mass ratio of the nano particles, the dispersing agent, the high molecular polymer and the coupling agent in the surface coating is 1:20-500:0.01-10:0.01-1, and the mass ratio of the high molecular polymer to the curing agent is 10:1.
The self-repairing super-hydrophobic anti-reflection coating is applied, and the preparation method of the coating comprises the following steps:
s1, uniformly dispersing the microparticles and a dispersing agent by ultrasonic, adding a high molecular polymer, polyborosiloxane, a curing agent and a coupling agent, and uniformly stirring to obtain a primer;
s2, spraying the primer on the surface of the carrier, and drying to obtain a primer coating;
s3, uniformly dispersing the nano particles and the dispersing agent by ultrasonic, adding the high molecular polymer, the curing agent and the coupling agent, and uniformly stirring to obtain the surface coating;
s4, spraying the surface coating on the bottom coating, and drying to form the surface coating.
Further, the primer coating has a thickness of 0.1 to 500 μm.
Further, the thickness of the surface coating is 10-500nm.
Further, the drying temperature in step S2 and step S4 was 80℃and the drying time was 2 hours.
Further, the spraying in step S2 and step S4 may be replaced by brushing, dipping or classical spraying.
The self-repairing super-hydrophobic anti-reflection coating or the self-repairing super-hydrophobic anti-reflection coating can be applied to the field of high light transmission materials, such as solar panels, display panels, camera lenses and the like.
Compared with the prior art, the self-repairing super-hydrophobic anti-reflection coating and the coating have the following advantages:
(1) The self-repairing superhydrophobic anti-reflection coating and the coating adopt a double-layer design thought, namely a primer coating and a surface coating respectively, wherein the primer coating is composed of large-size microparticles, high-molecular polymers and polyborosiloxane, the microparticles are more easily and firmly adhered to the surfaces of carriers such as glass and the like than the nanoparticles, the surface coating is composed of the nanoparticles and the high-molecular polymers, the nanoparticles are adhered to a bottom micrometer structure, and the adhesion force of the micrometer concave-convex structure to the surface layer is better than that of the surface layer directly adhered to smooth glass because the micrometer concave-convex structure plays a role in protecting the surface layer;
(2) The self-repairing super-hydrophobic anti-reflection coating and the coating are constructed by separating the micro structure from the nano structure, and compared with the construction of a layer of coating, the self-repairing super-hydrophobic anti-reflection coating and the coating are easier to control the regularity of the structure, so that the light transmittance of the super-hydrophobic anti-reflection coating is better;
(3) According to the self-repairing superhydrophobic anti-reflection coating and the coating bottom layer, the polyborosiloxane is added, oxygen atoms and boron atoms in the polyborosiloxane can form coordination bonds, and when the surface of the coating is damaged, the damage can be healed due to the generation of the coordination bonds;
(4) The self-repairing super-hydrophobic anti-reflection coating and the coating provided by the application can be used for simply spraying the surface nano material after the surface nano material fails, and have a good recovery effect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a schematic view of a primer coating according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a self-repairing superhydrophobic anti-reflection coating according to an embodiment of the application.
Reference numerals illustrate:
1. glass; 2. a primer coating; 3. and (5) surface coating.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The application will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
Preparing a bottom layer: 1 g of silicon dioxide particles with the particle size of 10 microns are added into 100 g of dimethylbenzene, ultrasonic dispersion is carried out for 10 minutes, 0.2 g of dimethyl siloxane, 0.4 g of polyborosiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.05 g of coupling agent KH-570 are added and stirred uniformly, the mixture is sprayed on glass by a spray gun, a sample is placed in an oven at 80 ℃ for drying for 2 hours and then taken out, and a 20 mu m-thick bottom coating is formed;
preparing a surface layer: 1 g of nano hydrophobic silica (AEROSIL R202) with the particle size of 14nm is added into 100 g of dimethylbenzene, ultrasonic dispersion is carried out for 10 minutes, 0.1 g of polydimethylsiloxane, 0.01 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570 are added and stirred uniformly, a spray gun is used for spraying the mixture on the bottom coating, a sample is placed in an 80 ℃ oven for drying for 2 hours, and then the self-repairing super-hydrophobic anti-reflection coating is obtained, wherein the thickness of the surface coating is 200nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 160 ° using a 10 microliter water test;
roll angle: the roll angle was 5 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90 percent, and the light transmittance after coating is 92 percent;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, and after one-time circulating movement is carried out for 20cm and 25 times of friction, the contact angle is 155 degrees, and the rolling angle is 7 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for four hours at room temperature, with a contact angle of 157 °, and a roll angle of 6 °.
And (3) easy repair test: after the coating is polished 60 times by a method for testing adhesion, the contact angle is 140 degrees, the rolling angle is 20 degrees, and after the surface layer is sprayed, the contact angle is restored to 160 degrees, and the rolling angle is 5 degrees.
Example two
Preparing a bottom layer: adding 0.5g of silica particles with the particle size of 5 microns into 100 g of dimethylbenzene, carrying out ultrasonic dispersion for 10 minutes, adding 0.2 g of dimethyl siloxane, 0.2 g of polyborosiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 10 microns;
preparing a surface layer: adding 0.5g of nano hydrophobic silica (AEROSIL R202) with the particle size of 14nm into 100 g of dimethylbenzene, carrying out ultrasonic dispersion for 10 minutes, adding 0.1 g of polydimethylsiloxane, 0.01 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, uniformly stirring, spraying on the bottom coating by using a spray gun, and drying a sample in an oven at 80 ℃ for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 150nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 155 ° using a 10 microliter water test;
roll angle: the roll angle was 7 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after the coating is coated is 96%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 156 degrees after one-time circulating movement is 20cm and 15 times of friction, and the rolling angle is 8 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for six hours at room temperature, with a test contact angle of 157 ° and a roll angle of 6 °.
Example III
Preparing a bottom layer: adding 1 g of diatomite particles with the particle size of 60 micrometers into 100 g of dimethylbenzene, carrying out ultrasonic dispersion for 10 minutes, adding 0.3 g of dimethyl siloxane, 0.4 g of polyborosiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 100 micrometers;
preparing a surface layer: 1 g of hydrophobic polyvinylidene fluoride microsphere with the particle size of 60nm is added into 100 g of dimethylbenzene, ultrasonic dispersion is carried out for 10 minutes, 0.2 g of polydimethylsiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570 are added and stirred uniformly, a spray gun is used for spraying on the bottom coating, a sample is placed in an 80 ℃ oven for drying for 2 hours, and then the self-repairing super-hydrophobic anti-reflection coating is obtained, wherein the thickness of the surface coating is 300nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 153 ° using a 10 microliter water test;
roll angle: the roll angle was 7 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after the coating is coated is 91%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 156 degrees after one-time circulating movement is carried out for 20cm and 30 times of friction, and the rolling angle is 9 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for four hours at room temperature, with a test contact angle of 154 ° and a roll angle of 8 °.
Example IV
Preparing a bottom layer: adding 100 g of tetrahydrofuran into 1 g of titanium dioxide particles with the particle size of 20 microns, performing ultrasonic dispersion for 10 minutes, adding 0.3 g of MQ silicone resin, 0.4 g of polyborosiloxane and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 50 microns;
preparing a surface layer: adding 100 g of ethyl acetate into 1 g of titanium dioxide with the particle size of 10nm, dispersing for 10 minutes by ultrasonic, adding 0.05 g of polydimethylsiloxane, 0.005 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, stirring uniformly, spraying on the bottom coating by using a spray gun, and placing a sample in an 80 ℃ oven for drying for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 160nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 156 ° using a 10 microliter water test;
roll angle: the roll angle was 6 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after the coating is coated is 93%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 155 degrees and the rolling angle is 8 degrees after the self-repairing super-hydrophobic anti-reflection coating is circularly moved for 20cm for 10 times.
Self-repair test: after scratching the coating with a knife, the scratch healed five hours at room temperature, with a test contact angle of 155 ° and a roll angle of 8 °.
Example five
Preparing a bottom layer: adding 1 g of calcium carbonate particles with the particle size of 26 microns into 100 g of tetrahydrofuran, performing ultrasonic dispersion for 10 minutes, adding 0.2 g of polyurethane, 0.3 g of polyborosiloxane and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 70 mu m;
preparing a surface layer: adding 0.5g of nano hydrophobic silica (AEROSIL R202) with the particle size of 14nm into 100 g of dimethylbenzene, carrying out ultrasonic dispersion for 10 minutes, adding 0.05 g of polydimethylsiloxane, 0.005 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, uniformly stirring, spraying on the bottom coating by using a spray gun, and drying a sample in an oven at 80 ℃ for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 130nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 157 ° using a 10 microliter water test;
roll angle: the roll angle was 6 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after the coating is coated is 93%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 156 degrees after one-time circulating movement is 20cm and 15 times of friction, and the rolling angle is 8 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for six hours at room temperature, with a test contact angle of 155 ° and a roll angle of 7 °.
Example six
Preparing a bottom layer: adding 0.5g of nylon powder particles with the particle size of 10 microns and 0.5g of boron nitride particles with the particle size of 10 microns into 100 g of xylene, performing ultrasonic dispersion for 10 minutes, adding 0.2 g of epoxy resin, 0.4 g of polyborosiloxane, 0.02 g of polyepoxide curing agent and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a 20-mu m-thick bottom coating;
preparing a surface layer: adding 1 g of nano boron nitride with the particle size of 10nm into 100 g of dimethylbenzene, carrying out ultrasonic dispersion for 10 minutes, adding 0.1 g of polydimethylsiloxane, 0.01 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, uniformly stirring, spraying on the bottom coating by using a spray gun, and placing a sample in an 80 ℃ oven for drying for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 200nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 155 ° using a 10 microliter water test;
roll angle: the roll angle was 8 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after coating is 93%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 150 degrees after one-time circulating movement is carried out for 20cm and 25 times of friction, and the rolling angle is 10 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for four hours at room temperature with a contact angle of 153 ° and a roll angle of 8 °.
Example seven
Preparing a bottom layer: adding 0.5g of boron oxide particles with the particle size of 20 microns and 0.5g of boron carbide with the particle size of 20 microns into 100 g of dimethylbenzene, performing ultrasonic dispersion for 10 minutes, adding 0.2 g of acrylic resin, 0.4 g of polyborosiloxane and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 50 microns;
preparing a surface layer: adding 0.5g of carbon nano tube with the particle size of 20nm and 0.5g of nano silicon carbide with the particle size of 20nm into 100 g of dimethylbenzene, performing ultrasonic dispersion for 10 minutes, adding 0.1 g of polydimethylsiloxane, 0.01 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, uniformly stirring, spraying on the bottom coating by using a spray gun, and placing a sample on an 80 ℃ oven for drying for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 300nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 153 ° using a 10 microliter water test;
roll angle: the roll angle was 7 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90%, and the light transmittance after coating is 93%;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, the contact angle is 150 degrees after one-time circulating movement is carried out for 20cm and 25 times of friction, and the rolling angle is 10 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for four hours at room temperature with a contact angle of 153 ° and a roll angle of 8 °.
Example eight
Preparing a bottom layer: adding 0.5g of ferric oxide with the particle size of 20 microns and particles and 0.5g of chromium powder with the particle size of 20 microns into 100 g of dimethylbenzene, performing ultrasonic dispersion for 10 minutes, adding 0.2 g of dimethyl siloxane, 0.4 g of polyborosiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.05 g of coupling agent KH-570, uniformly stirring, spraying on glass by using a spray gun, placing a sample in an oven at 80 ℃ for drying for 2 hours, and taking out to form a bottom coating with the thickness of 50 microns;
preparing a surface layer: adding 0.5g of nano silver with the particle size of 20nm and 0.5g of boron carbide with the particle size of 20nm into 100 g of dimethylbenzene, performing ultrasonic dispersion for 10 minutes, adding 0.2 g of polydimethylsiloxane, 0.02 g of polydimethylsiloxane curing agent and 0.01 g of coupling agent KH-570, uniformly stirring, spraying on the bottom coating by using a spray gun, and placing a sample on an 80 ℃ oven for drying for 2 hours to obtain the self-repairing super-hydrophobic anti-reflection coating, wherein the thickness of the surface coating is 300nm.
The test results were as follows:
measuring the water contact angle: the contact angle was 155 ° using a 10 microliter water test;
roll angle: the roll angle was 8 ° using a 10 microliter water test;
transmittance: the light transmittance of the bare glass is 90 percent, and the light transmittance after coating is 91 percent;
adhesion test: the self-repairing super-hydrophobic anti-reflection coating on the glass sheet is pressed on 600-mesh sand paper by a 50g weight to be polished, and after one-time circulating movement is carried out for 20cm and 25 times of friction, the contact angle is 150 degrees, and the rolling angle is 9 degrees.
Self-repair test: after scratching the coating with a knife, the scratch healed for four hours at room temperature with a contact angle of 153 ° and a roll angle of 8 °.
Claims (6)
1. A self-repairing super-hydrophobic anti-reflection coating is characterized in that: the primer comprises a primer and a surface layer coating, wherein the primer consists of one or more of micrometer particles, a dispersing agent, a high molecular polymer, polyborosiloxane, a curing agent and a coupling agent, the surface layer coating consists of one or more of nanometer particles, a dispersing agent, a high molecular polymer, a curing agent and a coupling agent, the micrometer particles are selected from one or more of micrometer silicon dioxide, micrometer titanium dioxide, micrometer calcium carbonate, micrometer diatomite, kaolin, nylon powder, polytetrafluoroethylene powder, ferric oxide, chromium powder, boron oxide, boron nitride and boron carbide, the high molecular polymer is selected from polydimethylsiloxane, MQ silicon resin, polyurethane, epoxy resin and acrylic resin, the nanometer particles are selected from one or more of nanometer silicon dioxide, nanometer titanium dioxide, nanometer vinylidene fluoride microspheres, carbon nanotubes, nanometer silver, nanometer tin oxide, nanometer zirconium oxide, nanometer antimony oxide, nanometer boron nitride, nanometer boron carbide and nanometer silicon carbide, the micrometer particles, the high molecular polymer, the polyborosiloxane and the coupling agent in the primer have a mass ratio of 1:100-200.2:0.4-0.0.05 to 1:0.0, the particle diameter of the surface layer coating is 1:0.0.0.05-0, and the coupling agent has a mass ratio of the nanometer particles to the curing agent is 1:0.0.0.0.0.05-0:0.0.0.0.0.0.0.0.0 to the mass ratio of the surface layer coating to 1:0.0.0.0.0.0.0.02 to the surface layer to 1.
2. The self-repairing super-hydrophobic anti-reflection coating applied with the self-repairing super-hydrophobic anti-reflection coating as claimed in claim 1, wherein the preparation method of the coating comprises the following steps:
s1, uniformly dispersing the microparticles and a dispersing agent by ultrasonic, adding a high molecular polymer, polyborosiloxane, a curing agent and a coupling agent, and uniformly stirring to obtain a primer;
s2, spraying the primer on the surface of the carrier, and drying to obtain a primer coating;
s3, uniformly dispersing the nano particles and the dispersing agent by ultrasonic, adding the high molecular polymer, the curing agent and the coupling agent, and uniformly stirring to obtain the surface coating;
s4, spraying the surface coating on the bottom coating, and drying to form the surface coating.
3. The self-healing superhydrophobic anti-reflection coating of claim 2, wherein: the thickness of the bottom coating is 0.1-500 mu m.
4. The self-healing superhydrophobic anti-reflection coating of claim 2, wherein: the thickness of the surface coating is 10-500nm.
5. The self-healing superhydrophobic anti-reflection coating of claim 2, wherein: the drying temperature in the step S2 and the step S4 is 80 ℃ and the drying time is 2h.
6. The self-repairing superhydrophobic anti-reflection coating of claim 1 or the application of the self-repairing superhydrophobic anti-reflection coating of any one of claims 2-5 in the field of high light transmission materials.
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| US20060269733A1 (en) * | 2003-08-28 | 2006-11-30 | Dai Nippon Printing Co., Ltd. | Antireflection laminate |
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| CN116082678A (en) * | 2022-12-29 | 2023-05-09 | 西安理工大学 | Rapid self-repairing polyborosiloxane film and preparation method thereof |
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| US20060269733A1 (en) * | 2003-08-28 | 2006-11-30 | Dai Nippon Printing Co., Ltd. | Antireflection laminate |
| CN104520392A (en) * | 2012-06-25 | 2015-04-15 | 罗斯科技公司 | Elastomeric coatings having hydrophobic and/or oleophobic properties |
| CN103965673A (en) * | 2014-05-05 | 2014-08-06 | 江南大学 | Preparation method of super-hydrophobic, super-oleophobic and high transparency triple-function coating film |
| WO2018045621A1 (en) * | 2016-09-09 | 2018-03-15 | 东南大学 | Transferable wear-resistant flexible super-hydrophobic film and preparation method therefor |
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