CN117263523A - Self-repairable glass surface anti-fog and anti-reflection coating and preparation method thereof - Google Patents
Self-repairable glass surface anti-fog and anti-reflection coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 239000011521 glass Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 44
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- -1 amino organosilane Chemical class 0.000 claims abstract description 26
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001282 organosilanes Chemical class 0.000 claims description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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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
- C03C17/006—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
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/478—Silica
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
-
- 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
-
- 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
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to the technical field of glass surface coating structures, in particular to an IPC C03C17, and more particularly relates to a self-repairable glass surface anti-fog and anti-reflection coating and a preparation method thereof. The invention firstly prepares SiO with polyacrylic acid nucleus 2 A nanoparticle; then, an SiO containing N-vinylamide polymer and having a polyacrylic acid core is prepared 2 Coating liquid of nano particles and amino organosilane; coating the coating liquid on the cleaned glass by adopting a spin coating method; finally, the glass is heated and annealed to finish the preparation of the coating. The glass coating has excellent anti-reflection, anti-fog and self-repairing functions.
Description
Technical Field
The invention relates to the technical field of glass surface coating structures, in particular to an IPC C03C17, and more particularly relates to a self-repairable glass surface anti-fog and anti-reflection coating and a preparation method thereof.
Background
When light enters the glass from air, the light is reflected more strongly at the interface between the glass and air due to the larger refractive index difference between the two. For ordinary glass, more than 4% of the incident light will be reflected at the glass/air interface, which is detrimental in some applications. For example, the surface of a photovoltaic system is typically covered by tempered photovoltaic glass, and strong light reflection can reduce the photoelectric conversion efficiency of the solar cell.
In environments with high relative humidity, the surface of hydrophobic or insufficiently hydrophilic objects can form a large number of non-interconnected droplets, causing strong scattering of light, affecting the application of some transparent objects (e.g. spectacles, vehicle windshields/mirrors, solar cells, camera lenses, etc.). The use of various super-moist materials to form an anti-fog coating on the surface of such transparent objects has raised visual clarity, driving safety or device-related performance, and has attracted increasing attention.
The formation of a specific coating on the surface of the glass can realize the functions of antireflection and/or antifogging. However, these coatings often lack sufficient mechanical strength to cause scratching of the coating during outdoor use due to abrasion by sand and other natural factors, which can immediately and permanently lose the coating's function.
The prior patent CN201410564019.9 discloses a silica sol antireflection film glass and a preparation method thereof, and provides a silica sol antireflection film glass which is compounded with a silica sol antireflection film layer and has low reflectivity, but the antifogging property and the abrasion resistance of the silica sol antireflection film glass are still to be improved.
Therefore, the development of the self-repairing function of the coating has important significance for improving the weather resistance and the service life of the actual application of the coating.
Disclosure of Invention
In order to solve the problems in the prior art, the first aspect of the invention provides a self-repairable glass surface anti-fog and anti-reflection coating and a preparation method thereof, comprising the following steps:
alkaline hydrolysis and acidic hydrolysis of alkoxy silane are carried out in the presence of polyacrylic acid to obtain SiO with polyacrylic acid core 2 Dispersing the nano particles into water, adding amino organosilane and N-vinyl amide polymer to prepare coating liquid, coating the coating liquid on the surface of clean glass, and annealing to form a coating.
Preferably, the specific preparation method of the self-repairable glass surface anti-fog and anti-reflection coating comprises the following steps:
s1: dissolving polyacrylic acid in ammonia water, adding ethanol to dilute the ammonia water containing polyacrylic acid, then dropwise adding alkoxy silane, and finally stirring at room temperature for reaction, and carrying out alkali hydrolysis;
s2: condensing and refluxing the solution after alkali hydrolysis, removing ammonia water, adding hydrochloric acid solution, adjusting the pH value of the solution after the condensation and refluxing to be 1.5-2.5, then dropwise adding alkoxy silane, stirring and aging at room temperature, centrifuging, and drying to obtain precipitate, thereby obtaining SiO with polyacrylic acid core 2 A nanoparticle;
s3: siO with polyacrylic acid core 2 The nano particles are ultrasonically stirred and dispersed into water to form transparent solution;
s4: dissolving amino organosilane in water, adding the water into the transparent solution obtained in the step S3, and stirring and mixing;
s5: slowly adding N-vinylamide polymers into the solution obtained in the step S4 in batches, and performing ultrasonic treatment to obtain a dissolved solution;
s6: sequentially placing the glass substrate into washing powder solution, deionized water, acetone and ethanol for ultrasonic cleaning for 15 minutes, and then drying by nitrogen gas flow to obtain clean glass;
s7: spin-coating the solution prepared in the step S5 on a clean glass substrate, and then annealing to obtain a coating.
Preferably, the alkoxy silane comprises one or more of tetraethyl orthosilicate, tetramethoxy silane and tetrabutoxy silane.
Preferably, the molecular weight of the polyacrylic acid is 1000-5000; further preferably, it is 3000.
Preferably, the polyacrylic acid is purchased from aladine, P104270.
Preferably, the mass volume ratio of the acrylic acid, the alkoxysilane in the S1 and the ammonia water is 0.1-1 g:1.0 to 5.0mL:14mL; further preferably, 0.2g:1.5mL:14mL or 0.6g:2mL:14mL.
Preferably, the mass percentage concentration of the ammonia water is 25-28%, and the ammonia water is commercially available.
Preferably, the stirring time at room temperature in the step S1 is 1-5 h; more preferably, the time is 2 to 3 hours.
Preferably, the mass concentration of the substances of the hydrochloric acid solution in the S2 is 0.5-2 mol/L; further preferably, the concentration is 1mol/L.
Preferably, the volume ratio of the alkoxysilane in the S1 to the alkoxysilane in the S2 is (1-5): (0.1-2); further preferably, 1.5:1.2 or 2:0.8.
preferably, the stirring time at room temperature in the step S2 is 1-5 hours, and the aging time is 2-8 days; further preferably, the stirring time is 2 to 3 hours and the aging time is 5 to 7 days.
Preferably, the transparent solution in S3 contains SiO of polyacrylic acid core 2 The concentration of the nano particles is 1-5wt%; further preferably, 1.5 to 3wt%.
Preferably, the amino organosilane comprises a diamino-terminated organosilane.
Preferably, the mass percentage of the amino organosilane aqueous solution formed by dissolving the amino organosilane in water in the S4 is 0.1-10wt%; further preferably, the content is 0.5 to 2wt%.
Preferably, the volume ratio of the aqueous solution of the amino organosilane in the S4 to the transparent solution in the S3 is (0.5-1.5): 1, a step of; further preferred is 1:1.
preferably, the diamino-terminated organosilane comprises 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane.
Preferably, the 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane has a CAS number of 2469-55-8 and is commercially available.
The invention improves the waterproof and antifogging performances of the glass coating by adding the amino-terminated organosilane. The inventors have found that amino-terminated organosilanes interpenetrate polyvinylpyrrolidone and SiO with polyacrylic acid core in the coating structure 2 In the network structure of the nano particles, the waterproof and anti-fog performances of the glass coated film can be improved, the glass coated film is obtained and is dried after being soaked in water for 30min, and the coated film cannot fall off.
Preferably, the N-vinyl amide polymer comprises one or more of polyvinylpyrrolidone, poly N-vinyl caprolactam and poly N-vinyl formamide.
Preferably, the molecular weight of the polyvinylpyrrolidone is 50-60 k; further preferably, 55k.
Preferably, the polyvinylpyrrolidone is purchased from aladine, P434442.
Preferably, in S5, the N-vinylamide polymer and the SiO of the polyacrylic acid core 2 The mass ratio of the nanometer is 1/10-1/2.
In the present invention, the organosilane, polyvinylpyrrolidone and SiO having polyacrylic acid core are blocked by diamino groups 2 The nano particles are combined to provide the glass coating with the functions of anti-reflection, anti-fog and self-repairing. The inventors found that polyvinylpyrrolidone molecular chain and SiO having polyacrylic acid core 2 The surfaces of the nano particles all have certain negative charges, so that the double-amino-terminated organosilane can be used for crosslinking, and the mechanical strength of the coating film is improved.
In the invention, by adding polyvinylpyrrolidone and SiO with polyacrylic acid nucleus 2 The nano particles and the amino-terminated organosilane improve the anti-fog function of the glass coating. The inventors have found that polyvinylpyrrolidone, siO with polyacrylic acid core 2 The nanoparticle and the amino-terminated organosilane are combined in a specific structure, so that the respective hydrophilic moisture absorption effect is exerted to the maximum extent, and the coating has an anti-fog function. When only two substances are crosslinked to form a film layer, the antifogging effect is poor and the antifogging is easy to generate.
In the invention, the mass or the volume of polyacrylic acid, alkoxy silane, amino organosilane and N-vinyl amide polymer in the preparation process is controlled so that SiO with polyacrylic acid nucleus 2 The refractive index of the nano particle adjustable coating is lower than that of the glass substrate, so that the nano particle adjustable coating has the functions of antireflection and reflection resistance.
Preferably, the spin-coating parameter in the step S7 is 1000-2000 rpm and 8-12S; further preferably 1000rpm, 10s and 2000rpm, 10s.
Preferably, the annealing temperature is 80-150 ℃ and the annealing time is 0.5-1.0 h; further preferably, the temperature is 100℃and the annealing time is 1h.
According to the invention, the glass coating is prepared by controlling the quality or volume of polyacrylic acid, alkoxy silane, amino organosilane and N-vinyl amide polymers through a specific preparation method, and has a certain self-repairing function. The inventors have found that too high a degree of crosslinking results in reduced flowability of the polyvinylpyrrolidone molecular chain in a high humidity environment, resulting in reduced self-repairing properties of the coating, by a specific preparation method and addition of a specific range of bisamino-terminated organosilane, polyvinylpyrrolidone and SiO with polyacrylic acid core 2 The nano particles control proper crosslinking degree in the system, and improve the fluidity of polyvinylpyrrolidone molecular chains in a high humidity environment, thereby improving the self-repairing performance of the coating. When the coating absorbs moisture in a high humidity environment, the molecular chain of polyvinylpyrrolidone has certain fluidity. Properly crosslinking polyvinylpyrrolidone and SiO with polyacrylic acid core in diamino terminated organosilane 2 After nano-particles, siO can be prepared 2 The nano particles flow along with the molecular chain of polyvinylpyrrolidone, so that the damage (such as scratch) of the coating is repaired, and the performance of the coating before being damaged is basically recovered.
The invention provides a self-repairable glass surface anti-fog and anti-reflection coating and a coating prepared by the preparation method thereof.
The schematic diagram of the coating structure is shown in figure 1.
Advantageous effects
1. In the present invention, the organosilane, polyvinylpyrrolidone and SiO having polyacrylic acid core are blocked by diamino groups 2 The nano particles are combined to provide the glass coating with the functions of anti-reflection, anti-fog and self-repairing.
2. In the invention, by adding polyvinylpyrrolidone and SiO with polyacrylic acid nucleus 2 The nano particles and the amino-terminated organosilane improve the anti-fog function of the glass coating.
3. The invention improves the waterproof and antifogging performances of the glass coating by adding the amino-terminated organosilane.
4. In the invention, the mass or the volume of polyacrylic acid, alkoxy silane, amino organosilane and N-vinyl amide polymer in the preparation process is controlled so that SiO with polyacrylic acid nucleus 2 The refractive index of the nano particle adjustable coating is lower than that of the glass substrate, so that the nano particle adjustable coating has the functions of antireflection and reflection resistance.
5. According to the invention, the glass coating is prepared by controlling the quality or volume of polyacrylic acid, alkoxy silane, amino organosilane and N-vinyl amide polymers through a specific preparation method, and has a certain self-repairing function.
Drawings
FIG. 1 is a schematic view of the structure of a coating prepared according to the present invention.
FIG. 2 is a graph showing the transmittance spectra of the glass coated samples prepared in example 1, comparative example 1 and comparative example 2 after the surgical knife is scratched and repaired; comparative example 1 is comparative example 1, and comparative example 2 is comparative example 2.
Detailed Description
Example 1
S1: 0.2g of polyacrylic acid (Mw-3000, commercially available) was dissolved in 14mL of aqueous ammonia (AR, commercially available), followed by dilution of the aqueous ammonia solution with 300mL of ethanol, followed by dropwise addition of 1.5mL of tetraethyl orthosilicate (AR, commercially available), and finally stirring at 25℃for 3 hours;
s2: removing most of ammonia water in the solution prepared by S1 by using a condensation reflux method, then using 1mol/L hydrochloric acid aqueous solution, regulating the pH value of the solution obtained by the condensation reflux method to 2, then dropwise adding 1.2mL of tetraethyl orthosilicate, stirring at 25 ℃ for 2h and aging for 5 days, and finally centrifuging and drying to obtain the SiO with polyacrylic acid core 2 A nanoparticle;
s3: siO with polyacrylic acid core 2 The nano particles are ultrasonically and stirred and dispersed into 50mL of water to form transparent solution, and SiO with polyacrylic acid core in the transparent solution 2 The mass percentage of the nano particles is 3wt%;
s4: the bis-amino-terminated organosilane (1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane) was dissolved in 50mL of water, and the mass percentage of the aqueous bis-amino-terminated organosilane solution was controlled to be 0.5wt%. Then adding the aqueous solution of the diamino end-capped organosilane into the S3 transparent solution, and stirring and mixing;
s5: 3g of polyvinylpyrrolidone powder was added to the solution formed by S4 in portions slowly and the dissolution was accelerated by ultrasound.
S6: ultrasonically cleaning glass (2×2.5cm, thickness 1mm, commercially available) with washing powder solution, deionized water, acetone and ethanol for 15 min, and blow-drying with nitrogen gas flow;
s7: the solution prepared in S5 was spin-coated (1000 rpm, 10S and 2000rpm, 10S) onto a clean glass substrate, followed by annealing at 100℃for 1h.
The polyacrylic acid was purchased from aladine, P104270; the polyvinylpyrrolidone was purchased from aladine, P434442.
Example 2
The embodiment of example 2 is the same as example 1, except that,
s1: 0.6g of polyacrylic acid (Mw-3000, commercially available) was dissolved in 14mL of aqueous ammonia (AR, commercially available), followed by dilution of the aqueous ammonia solution with 300mL of ethanol, followed by dropwise addition of 2mL of tetraethyl orthosilicate (AR, commercially available), and finally stirring at 25℃for 2h;
s2: removing most of ammonia water in the solution prepared by S1 by using a condensation reflux method, then using 1mol/L hydrochloric acid aqueous solution, regulating the pH value of the solution obtained by the condensation reflux method to 2, then dropwise adding 0.8mL of tetraethyl orthosilicate, stirring at 25 ℃ for 3h and aging for 7 days, and finally centrifuging and drying to obtain the SiO with polyacrylic acid core 2 A nanoparticle;
s3: siO with polyacrylic acid core 2 The nano particles are ultrasonically and stirred and dispersed into 50mL of water to form transparent solution, and SiO with polyacrylic acid core in the transparent solution 2 The mass percentage of the nano particles is 1.5wt%;
s4: the bis-amino-terminated organosilane (1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane) was dissolved in 50mL of water, and the mass percentage of the aqueous bis-amino-terminated organosilane solution was controlled to be 2wt%. Next, the aqueous solution of the diamino-terminated organosilane was added to the S3 clear solution and mixed with stirring.
Comparative example 1
The embodiment of comparative example 1 is the same as example 1 except that no diamino-blocked organosilane is added during the preparation.
Comparative example 2
The embodiment of comparative example 2 is the same as example 1 except that no alkoxysilane is added during the preparation of S1, S2, and the same as example 1 is started from step 4.
Comparative example 3
The embodiment of comparative example 3 is the same as example 1, except that the glass is cleaned only and no spin coating is applied to the glass.
Performance testing
1. The glass coated samples prepared in examples 1 to 2 and comparative examples 1 to 3 were tested for average reflectance and average transmittance in the range of 400 to 800nm, and the results are reported in Table 1.
2. The glass coated samples prepared in examples 1 to 2 and comparative examples 1 to 3 were placed 10cm above the water surface at 80℃with the coating facing the water surface, and after 30 seconds, the surface of the coating was observed for fogging. The results are reported in Table 1.
TABLE 1
| Average reflectance | Average transmittance | Whether or not to fog | |
| Example 1 | 3.1％ | 94.2％ | Whether or not |
| Example 2 | 3.0％ | 93.1％ | Whether or not |
| Comparative example 1 | 3.0％ | 94.1％ | Whether or not |
| Comparative example 2 | 4.9％ | 91.1％ | 10s fogging |
| Comparative example 3 | 8.2％ | 86.3％ | Immediately foggy |
3. The glass coated samples prepared in examples 1 to 2 and comparative examples 1 to 2 were subjected to a surgical knife to form a plurality of scratches (the interval between scratches is about 0.5 cm) on the coated layer, the samples were placed in an environment with a humidity of about 80% for 3 hours, and the samples were visually observed to see whether the scratches disappeared, and the transmittance of the scratched areas was characterized, specifically, see fig. 2, and the average transmittance in the wavelength range of 400 to 800nm was measured. The glass coated samples prepared in examples 1 to 2 and comparative examples 1 to 3 were placed 10cm above the water surface at 80℃with the coating facing the water surface, and after 30 seconds, the surface of the coating was observed for fogging. The results are reported in Table 2.
4. The glass coating films prepared in examples 1 to 2 and comparative examples 1 to 2 were immersed in water for 30 minutes and then dried, and whether the coating layers were peeled off was observed.
TABLE 2
| Whether or not the scratch disappears | Average transmittance | Whether or not to fog | Whether or not to fall off | |
| Example 1 | Scratch disappearance | 94.1％ | Whether or not | Whether or not |
| Example 2 | Scratch disappearance | 92.8％ | Whether or not | Whether or not |
| Comparative example 1 | Scratch disappearance | 92.2％ | Whether or not | Shedding off |
| Comparative example 2 | Scratches can be observed | 87.5％ | 5s fogging | Whether or not |
Claims (10)
1. A self-repairable glass surface anti-fog and anti-reflection coating and a preparation method thereof comprise the following steps:
alkaline hydrolysis and acidic hydrolysis of alkoxy silane are carried out in the presence of polyacrylic acid to obtain SiO with polyacrylic acid core 2 Dispersing the nano particles into water, adding amino organosilane and N-vinyl amide polymer to prepare coating liquid, coating the coating liquid on the surface of clean glass, and annealing to form a coating.
2. The self-repairable glass surface anti-fog, anti-reflection coating and the preparation method thereof as claimed in claim 1, comprising the following specific steps:
s1: dissolving polyacrylic acid in ammonia water, adding ethanol to dilute the ammonia water containing polyacrylic acid, then dropwise adding alkoxy silane, and finally stirring at room temperature for reaction, and carrying out alkali hydrolysis;
s2: condensing and refluxing the solution after alkali hydrolysis, removing ammonia water, adding hydrochloric acid solution, adjusting the pH value of the solution after the condensation and refluxing to be 1.5-2.5, then dropwise adding alkoxy silane, stirring and aging at room temperature, centrifuging, and drying to obtain precipitate, thereby obtaining SiO with polyacrylic acid core 2 A nanoparticle;
s3: siO with polyacrylic acid core 2 The nano particles are ultrasonically stirred and dispersed into water to form transparent solution;
s4: dissolving amino organosilane in water, adding the water into the transparent solution obtained in the step S3, and stirring and mixing;
s5: slowly adding N-vinylamide polymers into the solution obtained in the step S4 in batches, and performing ultrasonic treatment to obtain a dissolved solution;
s6: sequentially placing the glass substrate into washing powder solution, deionized water, acetone and ethanol for ultrasonic cleaning for 15 minutes, and then drying by nitrogen gas flow to obtain clean glass;
s7: spin-coating the solution prepared in the step S5 on a clean glass substrate, and then annealing to obtain a coating.
3. The method for preparing an anti-fog and anti-reflection coating on a self-repairable glass surface according to claim 2, wherein the alkoxy silane comprises one or more of tetraethyl orthosilicate, tetramethoxy silane and tetrabutoxy silane.
4. The self-repairable glass surface anti-fog and anti-reflection coating and the preparation method thereof according to claim 2, wherein the mass volume ratio of the alkoxysilane to the ammonia water in the polyacrylic acid and the S1 is 0.1-1 g:1.0 to 5.0mL:14mL.
5. The self-repairable glass surface anti-fog and anti-reflection coating and the preparation method thereof according to claim 2, wherein the volume ratio of the alkoxysilane in the S1 to the alkoxysilane in the S2 is (1-5): (0.1-2).
6. The self-repairable glass surface anti-fog and anti-reflection coating and the preparation method thereof according to claim 2, wherein the stirring time at room temperature in the S2 is 1-5 h, and the aging time is 2-8 days.
7. The self-healing glass surface anti-fog, anti-reflection coating and method of making same according to claim 2, wherein the amino organosilane comprises a diamino-terminated organosilane.
8. The self-healing glass surface anti-fog, anti-reflection coating and the preparation method thereof according to claim 2, wherein the N-vinyl amide polymer comprises one or more of polyvinylpyrrolidone, poly-N-vinyl caprolactam and poly-N-vinyl formamide.
9. The method for preparing an anti-fog and anti-reflection coating on a self-repairable glass surface according to claim 2, wherein in the step S5, the N-vinylamide polymer and the polyacrylic acid core are formed of SiO 2 The mass ratio of the nanometer is 1/10-1/2.
10. A glass coating prepared from the self-repairable glass surface anti-fog and anti-reflection coating and a preparation method thereof according to any one of claims 1 to 9.
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