CN109592908B - Preparation method of modified porous silicon dioxide moisture-proof anti-reflection coating - Google Patents
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Abstract
The invention discloses a preparation method of a modified porous silicon dioxide moisture-proof anti-reflection coating, which comprises the steps of firstly synthesizing multi-arm silane by using siloxane containing epoxy groups and siloxane containing primary amine or secondary amine through ring-opening addition reaction, then preparing precursor solution of polysiloxane sol under the acid catalysis condition by using the multi-arm silane and the silane monomer containing the siloxane as common silicon source monomers, then preparing pore-forming agent solution, then preparing modified silicon dioxide sol, and finally forming a film on a transparent substrate by using the modified silicon dioxide sol through a dip-draw method to prepare the modified porous silicon dioxide moisture-proof anti-reflection coating. The coating has a broad spectrum anti-reflection effect, the surface is flat and smooth, the particles are tightly stacked, the coating has good wear resistance and weather resistance, the thickness of the coating is 100-200 nm, the section pore size is 5-10 nm, the surface pore size is 10-40 nm, the coating is favorable for reversible absorption and desorption of water vapor, and the coating has an excellent moisture-proof function.
Description
Technical Field
The invention belongs to the technical field of inorganic thin film material modification, and particularly relates to a preparation method of a modified porous silicon dioxide moistureproof anti-reflection coating.
Background
The silica anti-reflection coating prepared based on the sol-gel method has excellent optical performance, and is widely applied due to the advantages of good weather resistance, adjustable refractive index, simple preparation method, large-area preparation and the like. However, when the coating is applied to anti-reflection coatings of solar cells, building glass and optical lenses, the coating is easily affected by external environmental factors, mainly including moisture adsorption, dust pollution, surface abrasion and the like, so that the optical performance of the coating is reduced, the service life of the coating is shortened, and the maintenance cost of components is increased.
At present, a silicon dioxide anti-reflection coating prepared based on a sol-gel method is subjected to sol synthesis modification and chemical modification post-treatment to obtain a coating surface with a self-cleaning function preliminarily, so that the performances of wear resistance, moisture resistance, pollution resistance and the like of the coating are realized. Patent CN106892574A discloses a super-hydrophilic self-cleaning porous silica antireflection film and a preparation method thereof, wherein tetraethoxysilane is used as a silicon source, silica particle glue solution a is prepared under the alkali catalysis condition, tetraethoxysilane is added into the glue solution a without the alkali catalyst, and acid catalysis hybridization treatment is carried out to obtain glue solution B. And annealing the prepared film at 250-600 ℃, and soaking the annealed film in hydrochloric acid and placing the film under steam. Controlling the dosage of the alkali catalyst and the aging time to obtain a film with the aperture of 5-8 nm; by controlling the amount of the acid catalyst, the water contact angle of the film is less than 5 degrees under the post-treatment conditions of hydrochloric acid and water vapor. The invention improves the wear resistance and super hydrophilicity of the film through hybridization and hydrochloric acid post-treatment, but the aperture of the film is smaller, and the film is easy to adsorb water vapor in the air, thereby causing the reduction of the optical performance.
Patent CN107674463 discloses that organic silicon source methyl triethoxysilane and ethyl orthosilicate are used as a common silicon source precursor, alcohol and water are used as solvents, silane coupling agents KH560 and KH570, a flexibilizer, N-methyl pyrrolidone, a crosslinking agent and a flatting agent are added, and SiO with a core-shell structure is formed under the condition of acid catalysis2Silica sol of particles of which SiO is2The particle size is 25 to 30 nm. And (3) tempering the prepared film at the high temperature of 680-720 ℃ to remove organic groups to obtain the superhard antireflection film. The anti-reflection coating has a compact structure and good weather resistance and wear resistance. However, the preparation method has complex raw materials, the average transmittance of the film in a 380-1100 nm waveband is 94.10%, and the single-side broad-spectrum antireflection performance is low.
Patent CN107188425A discloses a method for modifying a silicon dioxide antireflection film, which is to prepare the silicon dioxide antireflection film by taking ethyl orthosilicate, methyl trimethylsilane and N, N-dimethylformamide as precursors under the condition of acid catalysis, solve the problems of film formation cracking and film layer nonuniformity through material proportioning and heating temperature control, and improve the scratch resistance and aging resistance of the film layer. Compared with an acid-catalyzed silicon dioxide antireflection film taking an ethyl orthosilicate single silicon source as a precursor in the patent CN107629419, the film layer can be tightly stacked by simple heat treatment, so that the modification method of the patent does not play an obvious modification role, the obtained film layer has low optical performance and weak refractive index adjustability, and the influence of introducing a large amount of methyl on the condensation efficiency of silicon hydroxyl and the film-substrate combination is unknown.
Patent CN108455872A proposes a scratch-resistant hydrophobic antireflection film. Hydrophobic modified hollow ball SiO2And mixing the nano particle solution with the hydrophilic inorganic nano adhesive precursor solution to obtain the hybrid sol. After coating on a glass substrate, carrying out heat treatment at 400 ℃ for 1h to obtain the hydrophobic anti-reflection film. Although the hydrophilic inorganic nano binder can form a certain bonding with a substrate, the disordered accumulation of the nano particles in the film forming process leads to larger surface roughness and more external pores of the film, and reduces the weather resistance and the mechanical wear resistance of the film.
In addition, aiming at an ordered mesoporous silica system under the acid catalysis condition, people (pollution-resistant silicon anti-reflective coating with closed ordered mesopores, RSC Phys. chem. Phys,2014,16,16684-16693) use fluorosilane to carry out post-treatment on the ordered mesoporous silica anti-reflective film prepared by the acid catalysis sol, and utilize fluorine base to modify mesoporous pores on the surface of the film layer to obtain the surface with certain hydrophobic property, so that the film layer has certain moisture-proof and anti-fouling functions, but the functional timeliness is short. In addition, (Superhydrophobic organic silane functionalized silicon Polyimide Substrate with structure inhibition-Resistance, ACS applied materials Interfaces 2017,9(6), 5468-5476) also reports that a cross-type organosilane (EG-BSQ) is prepared by reacting r- (2, 3-Glycidoxy) Propyltrimethoxysilane (GPTMS) with Ethylenediamine (EDA). Organosilane and tetraethoxysilane are used as a common silicon source precursor, F127 is used as a template agent, and the modified silicon dioxide sol is prepared by adopting an acid catalysis method. Preparing a film on a flexible substrate, and carrying out annealing treatment at 250 ℃ to obtain the mesoporous silica anti-reflection film which is super-hydrophilic and has stronger binding force with the flexible substrate. The compact film structure is obtained by the method, the bonding force between the film and the flexible substrate is improved, but the potential problem of irreversible moisture absorption still exists in the outdoor environment due to the capillary condensation effect of mesoporous pores on the surface of the film of about 5 nm.
Junhui He et al (affinity hybrid acid to high-performance hybrid anti-reflection thin films with high sensitivity as mechanical properties, Journal of Materials Chemistry C2016, 4, 5342-5348.) utilize methyltrimethoxysilane (MTMS) and ethyl orthosilicate as silicon sources, surfactant CTAB is added, hydrophobic modified silica sol is prepared under the catalysis of acid, and after coating, annealing treatment is carried out at 600 ℃ to obtain the hydrophobic ultra-smooth anti-reflection film with certain porosity and methyl modification. Similarly, patent CN102757055A uses methyltriethoxysilane as the organic silicon source to prepare hydrophobic mesoporous silica membrane by the same method. Compared with a mesoporous silicon dioxide film layer, the moisture resistance is obtained through hydrophobic post-treatment, the film prepared by the method has certain mechanical stability and relatively long-acting hydrophobic characteristic, but due to the integral hydrophobicity of the sol, the bonding force sites of the film layer and the substrate are greatly reduced, and the film-substrate bonding force and the mechanical wear resistance of the film are unknown.
The existing silica anti-reflection coating based on sol modification and chemical modification post-treatment technology mainly comprises a hybrid and mesoporous silica coating surface, and has a self-cleaning function through a chemical modification method. The hybrid silica is mainly prepared into modified sol by adopting a two-step or multi-step method, the operation steps are complex, the controllability of the preparation method is poor, the surface of the obtained coating has a self-cleaning function, the roughness is high, and a large number of external pores exist; after a large number of functional groups are introduced into the coating, the effective condensation sites of silicon hydroxyl are greatly reduced, the crosslinking degree is reduced, and the research on the stability and the mechanical wear resistance of the coating is unknown. In contrast, the conventional mesoporous silica anti-reflection coating (the surface SEM image of which is shown in fig. 1) has a high-strength ordered mesoporous network under the acid catalysis, and has the advantages of stable structure, compact film layer, smooth surface, and strong mechanical wear resistance and weather resistance, but due to the existence of mesoporous pores on the surface, irreversible chemical/physical adsorption with water vapor in the air is performed under the capillary condensation effect, so that the mesoporous pore structure is swelled and changed, the pores are filled with water vapor, the refractive index is increased, and the anti-reflection performance is seriously reduced; therefore, the surface is usually "closed" by chemical modification post-treatment to hydrophobize the surface and inhibit moisture absorption. The method has quick response but short timeliness, and once the hydrophobic effect fails, the surface of the original mesoporous coating absorbs moisture again.
Disclosure of Invention
The invention aims to solve the technical problem that the prepared coating has a broad-spectrum antireflection effect, is flat and smooth in surface, is tightly stacked among particles, has good wear resistance and weather resistance, is 100-200 nm thick, 5-10 nm in section pore size and 10-40 nm in surface pore size, is beneficial to reversible absorption and desorption of water vapor, and has an excellent moistureproof function.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a modified porous silicon dioxide moisture-proof anti-reflection coating comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding siloxane containing epoxy groups and siloxane containing primary amine or secondary amine into a three-neck flask according to a certain proportion, heating and reacting for a period of time under the protection of inert gas by taking an alcohol solvent as a reaction solvent, transferring a reaction solution into a beaker after the reaction is finished, and evaporating and concentrating to prepare a multi-arm silane precursor;
(2) preparation of precursor solution of polysiloxane sol
Mixing a siloxane-containing silane monomer with the multi-arm silane precursor synthesized in the step (1) according to a certain proportion, adding a certain proportion of alcohol solvent, deionized water and acid catalyst, heating, refluxing, stirring, reacting, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Mixing an alcohol solvent, deionized water and an acid catalyst according to a certain proportion to obtain a mixed solution, weighing a certain amount of a pore-forming agent, adding the pore-forming agent into the mixed solution, and fully stirring at room temperature to uniformly disperse the pore-forming agent to prepare a pore-forming agent solution;
(4) preparation of modified silica sols
Adding the pore-forming agent solution prepared in the step (3) into the precursor solution of the polysiloxane sol prepared in the step (2), reacting for a period of time at a certain temperature, sealing and aging at normal temperature, and adjusting the pH value of the sol to obtain modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
And (3) preparing a double-sided modified coating on the transparent substrate by adopting the modified silica sol prepared in the step (4) through a dip-coating method at a certain temperature and humidity, and then annealing to obtain the modified porous silica moisture-proof anti-reflection coating on the transparent substrate.
The invention provides a preparation method of a modified porous silicon dioxide moisture-proof anti-reflection coating, which comprises the steps of firstly synthesizing multi-arm silane by using siloxane containing epoxy groups and siloxane containing primary amine or secondary amine through ring-opening addition reaction, then taking a multi-arm silane precursor and a silane monomer containing siloxane as a common silicon source monomer, adding a certain proportion of alcohol solvent, deionized water and acid catalyst, and preparing precursor solution of polysiloxane sol under the acid catalysis condition; then, uniformly mixing an alcohol solvent, deionized water, an acid catalyst and a pore-forming agent according to a certain proportion to prepare a pore-forming agent solution; then mixing the pore-forming agent solution with a precursor solution of the polysiloxane sol to prepare modified silica sol; finally, the modified silica sol is subjected to one-time film formation on a transparent substrate through a dip-coating method, and a pore-forming agent is removed through an annealing high-temperature induction method, so that a modified porous silica moisture-proof anti-reflection coating with specific mesoporous pores on the surface and the cross section of the coating is obtained on the transparent substrate, the mesoporous pores on the surface of the coating are larger than the mesoporous pores on the cross section of the coating, and the surface of the coating and the mesoporous pores on the cross section of the coating have gradient size, so that a multi-stage pore structure is formed. The section of the coating prepared by the method has small-size mesoporous channels (6-9 nm), and the size of larger surface pores formed by accumulation of particles on the surface of the coating can be seen to be 10-40 nm through an SEM image.
According to the preparation method of the modified porous silicon dioxide moistureproof anti-reflection coating, multi-arm silane is synthesized and used, firstly, functional groups are directly introduced, and simultaneously, a large number of silicon hydroxyl groups are introduced, so that a large number of crosslinking sites are provided for the dehydration condensation reaction of a precursor solution of polysiloxane sol; secondly, because the synthesized multi-arm silane contains a large amount of silicon hydroxyl, and the silicon hydroxyl is alkalescent in an alcohol solution, the silane monomer containing siloxane can be quickly used as a core under the acid catalysis condition, is crosslinked with the core and is assembled to grow dozens of nanometer (10-40 nm) particles, and the construction of a subsequent film layer gradient pore structure and the regulation and control of surface pores can be realized. Therefore, the defect that after functional groups are introduced in the traditional method, silicon hydroxyl condensation sites are reduced is overcome, and the problem of moisture absorption caused by smaller mesoporous pores (5-10 nm) on the surface of the mesoporous coating in the prior art is solved. The coating prepared by the invention can realize broad-spectrum antireflection, and the performances of the coating in the aspects of functionalization such as moisture resistance, wear resistance and the like are obviously improved.
The preparation method disclosed by the invention is mild in preparation conditions and simple in operation, the modified porous silica moisture-proof anti-reflection coating can be prepared by one-step film formation of the modified silica sol, the pore structure of the obtained coating is flexible and controllable, and the tight packing of small-size nano particles can be realized under the synergistic regulation and control of each step, so that the coating with the gradually-changed pore channel structure on the surface and the cross section is formed. The method can solve the problem of moisture absorption of the coating, improve the weather resistance of the coating and prolong the service life of the mesoporous silica anti-reflection coating in outdoor environment while preparing the high-strength ordered mesoporous anti-reflection coating, is suitable for various transparent substrates including rigid substrates such as ultra-white glass and quartz glass and flexible substrates such as ultra-thin glass, polyimide, polyethylene glycol terephthalate and the like, and has large-scale industrial production and application prospects.
Preferably, in the step (1), the molar ratio of the siloxane containing the epoxy group to the siloxane containing the primary amine or the secondary amine is 0.5-5: 0.25-2.5, wherein the dosage of the siloxane containing the epoxy group is 4-40 mL, the dosage of the siloxane containing the primary amine or the secondary amine is 2-20 mL, and the dosage of the alcohol solvent is 150-3000 mL; heating at 40-80 ℃, reacting for 24-72 h, and after the reaction is finished, evaporating and concentrating to remove the alcohol solvent.
Preferably, in the step (1), the siloxane containing an epoxy group is one of 3- (2, 3-glycidoxy) propyltrimethoxysilane (i.e., GPTMS), 3- (2, 3-glycidoxy) propyltriethoxysilane (i.e., GPTES), 3- (2, 3-glycidoxy) propylmethyldimethoxysilane (i.e., GPMDMS), and 3- (2, 3-glycidoxy) propylmethyldiethoxysilane (i.e., GPMDES); the siloxane containing primary amine or secondary amine is one of bis [3- (triethoxysilane) propyl ] amine, bis [3- (trimethoxy silane) propyl ] amine, N-bis- [ (3-triethoxysilylpropyl) aminocarbonyl ] polysiloxane, N-bis- [ (3-trimethoxysilyl) propyl ] ethylenediamine, N-bis- [ (3-triethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxy silane.
Preferably, in the step (2), the molar ratio of the siloxane-containing silane monomer to the multi-arm silane precursor is 10-100: 0.1-1.4, the molar ratio of the sum of the molar amount of the siloxane-containing silane monomer and the multi-arm silane precursor to the alcohol solvent, the deionized water and the acid catalyst is 1-10: 3-40: 1-10: 0.00005-0.0005, wherein the amount of the siloxane-containing silane monomer is 88-880 mmol, the amount of the multi-arm silane precursor is 1-12 mmol, the amount of the alcohol solvent is 22-220 mL, the amount of the deionized water is 1.8-18 mL, and the amount of the acid catalyst is 0.005-0.05 mmol; the heating temperature is 40-70 ℃, and the reaction time is 1.5-3 h.
Preferably, in the step (2), the siloxane-containing silane monomer is one of tetramethoxysilane (also called methyl orthosilicate, i.e. TMOS), tetraethoxysilane (also called tetraethoxysilane, i.e. TEOS) and methyltriethoxysilane.
Preferably, in the step (3), the molar ratio of the alcohol solvent, the deionized water, the acid catalyst and the pore-forming agent is 18.2-182: 4-40: 0.00395-0.0395: 0.008-0.12, wherein the dosage of the alcohol solvent is 100-1000 mL, the dosage of the deionized water is 7.2-72 mL, the dosage of the acid catalyst is 0.4-4 mmol, and the dosage of the pore-forming agent is 0.8-12 mmol.
Preferably, in step (3), the pore-forming agent is an amphiphilic block copolymer, an ionic surfactant or a nonionic surfactant, the amphiphilic block copolymer is a polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymer (i.e., F127 or P123), the ionic surfactant is cetyltrimethylammonium bromide (i.e., CTAB) or cetyltrimethylammonium chloride (i.e., CATC), and the nonionic surfactant is polyacrylic acid (i.e., PAA). Category of surfactants of the CTAB, CATC and PAA families, the removal temperature T of which>400 ℃; the amphiphilic block copolymer has a low thermal stability or thermal decomposition temperature, Td<At 250 ℃ to obtain a mixture. The pore-forming agent can be effectively removed by annealing the double-sided modified coating prepared on the transparent substrate, so that the modified porous silica moisture-proof anti-reflection coating with the surface and the cross section respectively provided with specific mesoporous pores is obtained on the transparent substrate.
Preferably, in the step (4), the reaction temperature is 20-50 ℃, the reaction time is 1-5 hours, the pH value of the sol is adjusted to 1.5-5, the modified silica sol is prepared, and the modified silica sol is stored in a transparent glass container for later use. The modified silica sol is placed on a black substrate and becomes light blue sol under illumination.
Preferably, in the step (5), the environment temperature for preparing the double-sided modified coating on the transparent substrate is 15-35 ℃, the environment relative humidity is 20-40%, the pulling speed of the dip-coating method is 800-2000 μm/s, the annealing temperature is 200-500 ℃, and the annealing time is 1-2 h.
Preferably, in the step (1) to the step (3), the alcohol solvent is one of methanol, ethanol and isopropanol; in the steps (2) to (3), the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid and phosphoric acid.
Compared with the prior art, the invention has the following advantages:
the coating prepared by the invention has a broad-spectrum antireflection effect, and the average transmittance of the double-sided modified coating prepared on the transparent substrate in the range of 400-1100 nm is more than or equal to 97 percent;
secondly, the coating prepared by the method has a smooth surface, the average roughness is about 1nm, the particles are tightly packed, the coating has good wear resistance, and the optical transmittance is reduced by less than 0.3 percent after the coating is dry-wiped for 80 times;
thirdly, the coating prepared by the invention has good weather resistance, and after 24h of high accelerated aging test (the 24h of high accelerated aging test is equivalent to 1000h of traditional double 85 test), the transmittance of the coating is reduced by less than 0.5%;
and fourthly, through modification of the synthesized multi-arm silane, the coating prepared by the method is tightly stacked, the thickness is 100-200 nm, the pore size of the cross section is 5-10 nm, and the pore size of the surface is 10-40 nm, so that the method is favorable for reversible absorption and desorption of water vapor and has an excellent moisture-proof function.
Drawings
FIG. 1 is a surface SEM image of a conventional mesoporous silica antireflective coating;
FIG. 2 is an optical transmittance curve of a multi-arm silane-modified porous silica moisture-proof anti-reflection coating prepared on an ultra-white glass substrate in example 1 at an ambient temperature of 20 ℃ and an ambient relative humidity of 20% after annealing at 400 ℃;
FIG. 3 is an optical transmittance curve of a multi-arm silane-modified porous silica moisture-resistant anti-reflection coating prepared on an ultra-white glass substrate in example 3 at an ambient temperature of 26 ℃ and an ambient relative humidity of 30% after annealing at 400 ℃;
FIG. 4 is a surface SEM image of a multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 4;
FIG. 5 is a surface SEM image of a multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 5;
FIG. 6 is a sectional SEM image of a multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 6;
FIG. 7 is a SEM cross-section of a multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 7.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 1 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 10mL of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 4.45mL of N, N-bis- [ (3-triethoxysilylpropyl) aminocarbonyl ] polyethoxy alkane into a three-neck flask, adding 300mL of ethanol as a reaction solvent, stirring and reacting for 48 hours at 60 ℃ under the protection of nitrogen, transferring the reaction liquid into the beaker after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a four-arm silane precursor TS-1, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
Adding 88mmol of tetraethoxysilane and 12mmol of quadriarm silane precursor TS-1 into a three-neck round-bottom flask, adding 22.19mL of absolute ethyl alcohol, 1.8mL of deionized water and 0.005mmol of hydrochloric acid, refluxing and stirring at 60 ℃, reacting for 1.5h, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 100mL of absolute ethyl alcohol, 7.2mL of deionized water and 0.4mmol of hydrochloric acid into a beaker to obtain a mixed solution, weighing 0.8mmol of polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymer F127, adding the mixed solution into the mixed solution, fully stirring at room temperature to uniformly disperse the F127, and preparing a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 2 hours at 30 ℃, sealing and aging for 2 days at normal temperature, and adjusting the pH value of the sol to be about 2 to obtain tetra-arm silane TS-1 and tetraethoxysilane as double-silicon-source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of absolute ethyl alcohol to dilute the sol to obtain a glue solution, preparing a double-sided modified coating on the ultra-white glass substrate at the pulling speed of 1200 mu m/s by a dipping and pulling method under the conditions that the ambient temperature is 20 ℃ and the ambient relative humidity is 20%, and then carrying out annealing treatment at the speed of 400 ℃/1h in a muffle furnace, namely obtaining the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 118nm and the refractive index of 1.21 on the ultra-white glass substrate.
The optical transmittance curve of the multi-arm silane-modified porous silica moisture-proof anti-reflection coating prepared on the ultra-white glass substrate in example 1 after annealing at 400 ℃ under the conditions of the ambient temperature of 20 ℃ and the ambient relative humidity of 20% is shown in fig. 2. As can be seen from FIG. 2, the average transmittance in the range of 400 to 1100nm was 97.60%. The surface of the coating is flat and smooth as a whole, the average roughness is about 1.23nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.2 percent after the coating is dry-wiped for 80 times; after 24h of highly accelerated ageing tests (which 24h of highly accelerated ageing tests correspond to 1000h of the conventional double 85 test), the transmission is reduced by < 0.4%. The size of pores on the section of the coating is about 6-9 nm, and the size of pores on the surface is about 30nm, so that reversible absorption and desorption of water vapor are facilitated, and the coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 2 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 3- (2, 3-epoxypropoxy) propyl triethoxysilane and 10mLN, N-bis- [ (3-triethoxysilyl) propyl ] ethylenediamine into a three-neck flask, adding 600mL ethanol as a reaction solvent, stirring and reacting for 72 hours at 70 ℃ under the protection of nitrogen, transferring the reaction liquid into the flask after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a four-arm silane precursor TS-2, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
Adding 197.37mmol of tetraethoxysilane and 2.63mmol of four-arm silane precursor TS-2 into a three-neck round-bottom flask, adding 44.38mL of absolute ethyl alcohol, 3.6mL of deionized water and 0.01mmol of nitric acid, refluxing and stirring at 70 ℃, reacting for 2 hours, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 212.54mL of absolute ethyl alcohol, 14.4mL of deionized water and 0.8mmol of nitric acid into a beaker to obtain a mixed solution, adding 2.4mmol of polyoxypropylene-polyoxyethylene-polyoxypropylene segmented copolymer F127 into the mixed solution, and fully stirring at room temperature to uniformly disperse the F127 to prepare a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 3 hours at 40 ℃, sealing and aging at normal temperature for 2 days, and adjusting the pH value of the sol to be about 4 to obtain four-arm silane TS-2 and tetraethoxysilane as double-silicon-source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of absolute ethyl alcohol to dilute the sol to obtain a glue solution, preparing a double-sided modified coating on the ultrathin glass substrate at the pulling speed of 800 mu m/s by a dipping and pulling method under the conditions that the ambient temperature is 35 ℃ and the ambient relative humidity is 40%, and then carrying out annealing treatment at the temperature of 300 ℃/1.5h in a muffle furnace, namely obtaining the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 130nm and the refractive index of 1.30 on the ultrathin glass substrate.
Example 2 the modified porous silica moisture barrier antireflective coating prepared on an ultrathin glass substrate has an average transmittance of 97.01% over the range of 400-1100 nm. The surface of the coating is flat and smooth as a whole, the average roughness is about 1.07nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.2 percent after the coating is dry-wiped for 80 times; after 24h of highly accelerated ageing tests (which 24h of highly accelerated ageing tests correspond to 1000h of the conventional double 85 test), the transmission is reduced by < 0.4%. The size of pores on the section of the coating is 5-8 nm, the size of pores on the surface is about 25nm, reversible absorption and desorption of water vapor are facilitated, and the moisture-proof coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 3 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane 4.42mL and aminopropyl triethoxy silane 3.43 mL into a three-neck flask, adding ethanol 150mL serving as a reaction solvent, stirring and reacting at 60 ℃ for 24h under the protection of argon, transferring the reaction solution into the beaker after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a three-arm silane precursor GATS-1, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
Adding 485mmol of tetraethoxysilane and 6mmol of three-arm silane precursor GATS-1 into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, 9.2mL of deionized water and 0.028mmol of acetic acid, refluxing and stirring at 65 ℃, reacting for 2.5h, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 550mL of absolute ethyl alcohol, 39.5mL of deionized water and 2.2mmol of acetic acid into a beaker to obtain a mixed solution, adding 6.4mmol of polyoxypropylene-polyoxyethylene-polyoxypropylene segmented copolymer F127 into the mixed solution, and fully stirring at room temperature to uniformly disperse the F127 to prepare a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 1h at 20 ℃, sealing and aging at normal temperature for 2 days, and adjusting the pH value of the sol to about 1.5 to obtain three-arm silane GATS-1 and tetraethoxysilane as double-silicon-source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of absolute ethyl alcohol to dilute the sol to obtain a glue solution, preparing a double-sided modified coating on the ultra-white glass substrate at a pulling speed of 1600 mu m/s by a dip-coating method under the conditions that the ambient temperature is 26 ℃ and the ambient relative humidity is 30%, and then carrying out annealing treatment at 400 ℃/1h in a muffle furnace, namely obtaining the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 115nm and the refractive index of 1.20 on the ultra-white glass substrate.
The optical transmittance curve of the multi-arm silane-modified porous silica moisture-proof anti-reflection coating prepared on the ultra-white glass substrate in example 3 at the ambient temperature of 26 ℃ and the ambient relative humidity of 30% after annealing at 400 ℃ is shown in fig. 3. As can be seen from FIG. 3, the average transmittance was 97.58% in the range of 400 to 1100 nm. The surface of the coating is flat and smooth as a whole, the average roughness is about 2.20nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.1 percent after the coating is dry-wiped for 80 times; after 24h of high accelerated ageing test (this 24h of high accelerated ageing test corresponds to 1000h of conventional double 85 test), the transmittance decreases by < 0.3%. The size of pores on the section of the coating is about 6-8 nm, and the size of pores on the surface is about 20nm, so that reversible absorption and desorption of water vapor are facilitated, and the coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 4 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 40mL of 3- (2, 3-epoxypropoxy) propyl methyldimethoxysilane and 20mL of 3-aminopropyltriethoxysilane into a three-neck flask, adding 1800mL of ethanol as a reaction solvent, stirring and reacting for 72 hours at 80 ℃ under the protection of nitrogen, transferring the reaction solution into a beaker after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a three-arm silane precursor GATS-2, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
880mmol of tetramethoxysilane and 10mmol of three-arm silane precursor GATS-2 are added into a three-neck round-bottom flask, 220mL of isopropanol, 18mL of deionized water and 0.05mmol of hydrochloric acid are added, reflux stirring is carried out at 70 ℃ for reaction for 3 hours, and then natural cooling is carried out to room temperature, so as to obtain precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 1000mL of isopropanol, 72mL of deionized water and 4mmol of hydrochloric acid into a beaker to obtain a mixed solution, adding 12mmol of polyoxypropylene-polyoxyethylene-polyoxypropylene segmented copolymer P123 into the mixed solution, fully stirring at room temperature to uniformly disperse the P123, and preparing a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 5 hours at 50 ℃, sealing and aging for 2 days at normal temperature, and adjusting the pH value of the sol to be about 3 to obtain three-arm silane GATS-2 and tetramethoxysilane as double-silicon-source modified acid sol, namely modified silica sol; a
(5) Preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of isopropanol to dilute to obtain a glue solution, preparing a double-sided modified coating on the ultrathin glass substrate at the pulling speed of 2000 mu m/s by a dip-pulling method under the conditions that the ambient temperature is 25 ℃ and the ambient relative humidity is 35%, and then carrying out annealing treatment at 400 ℃/1h in a muffle furnace to obtain the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 170nm and the refractive index of 1.18 on the ultrathin glass substrate.
The surface SEM image of the multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 4 is shown in FIG. 4.
Example 4 the modified porous silica moisture barrier antireflective coating prepared on an ultrathin glass substrate has an average transmittance of 97.31% over the range of 400-1100 nm. The surface of the coating is flat and smooth as a whole, the average roughness is about 2.11nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.3 percent after the coating is dry-wiped for 80 times; after 24h of highly accelerated ageing tests (which 24h of highly accelerated ageing tests correspond to 1000h of the conventional double 85 test), the transmission is reduced by < 0.5%. The size of pores on the section of the coating is 7-9 nm, the size of pores on the surface is about 20nm, reversible absorption and desorption of water vapor are facilitated, and the moisture-proof coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 5 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 15mL of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and 6.7mL of N, N-bis- [ (3-trimethoxysilyl) propyl ] ethylenediamine into a three-neck flask, adding 450mL of methanol as a reaction solvent, stirring and reacting for 72h at 40 ℃ under the protection of nitrogen, transferring the reaction solution into the flask after the reaction is finished, and distilling off the methanol solvent to prepare a four-arm silane precursor TS-3, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
Adding 98mmol of methyltriethoxysilane and 1mmol of quadriarm silane precursor TS-3 into a three-neck round-bottom flask, adding 22mL of methanol, 1.8mL of deionized water and 0.005mmol of phosphoric acid, refluxing at 40 ℃, stirring, reacting for 1.5h, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 106.27mL of methanol, 7.2mL of deionized water and 0.4mmol of phosphoric acid into a beaker to obtain a mixed solution, adding 0.8mmol of cetyl trimethyl ammonium bromide CTAB into the mixed solution, fully stirring at room temperature to uniformly disperse the cetyl trimethyl ammonium bromide, and preparing a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 1.5h at 35 ℃, sealing and aging for 2 days at normal temperature, and adjusting the pH value of the sol to be about 2 to obtain a four-arm silane precursor TS-3 and methyl triethoxysilane as a double-silicon-source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of prepared modified silica sol, adding 25mL of methanol for dilution to obtain a glue solution, preparing a double-sided modified coating on the ultrathin glass substrate at the pulling speed of 1200 mu m/s by a dipping and pulling method under the conditions that the ambient temperature is 24 ℃ and the ambient relative humidity is 28%, and then carrying out annealing treatment at 500 ℃/1h in a muffle furnace to obtain the modified porous silica moisture-proof anti-reflection coating with the thickness of 160nm and the refractive index of 1.25 on the ultrathin glass substrate.
The surface SEM image of the multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 5 is shown in FIG. 5.
Example 5 the modified porous silica moisture barrier antireflective coating prepared on an ultrathin glass substrate has an average transmittance of 97.14% over the range of 400-1100 nm. The surface of the coating is flat and smooth as a whole, the average roughness is about 0.96nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.25 percent after the coating is dry-wiped for 80 times; after 24h of high accelerated ageing test (this 24h of high accelerated ageing test corresponds to 1000h of conventional double 85 test), the transmittance decreases by < 0.3%. The size of pores on the section of the coating is 5-8 nm, the size of pores on the surface of the coating is about 15nm, reversible absorption and desorption of water vapor are facilitated, and the coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 6 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 3- (2, 3-epoxypropoxy) propyltriethoxysilane and 15mL bis [3- (triethoxysilane) propyl ] amine into a three-neck flask, adding 1200mL ethanol as a reaction solvent, stirring at 50 ℃ for reaction for 72h under the protection of nitrogen, transferring the reaction solution into the flask after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a three-arm silane precursor GATS-3, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
Adding 300mmol of tetraethoxysilane and 5mmol of three-arm silane precursor GATS-3 into a three-mouth round-bottom flask, adding 80mL of absolute ethyl alcohol, 6.2mL of deionized water and 0.019mmol of hydrochloric acid, refluxing and stirring at 60 ℃, reacting for 2 hours, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Adding 380mL of absolute ethyl alcohol, 27mL of deionized water and 1.5mmol of hydrochloric acid into a beaker respectively to obtain a mixed solution, adding 4.4mmol of polyacrylic acid PAA into the mixed solution, and fully stirring at room temperature to uniformly disperse the PAA to prepare a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 2h at 30 ℃, sealing and aging at normal temperature for 2 days, and adjusting the pH value of the sol to be about 5 to obtain a three-arm silane precursor GATS-3 and tetraethoxysilane as double-silicon-source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of absolute ethyl alcohol to dilute the sol to obtain a glue solution, preparing a double-sided modified coating on a quartz glass substrate at a pulling speed of 1800 mu m/s by a dipping and pulling method under the conditions that the ambient temperature is 28 ℃ and the ambient relative humidity is 35%, and then carrying out annealing treatment at 500 ℃/1h in a muffle furnace, namely obtaining the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 125nm and the refractive index of 1.22 on the quartz glass substrate.
A cross-sectional SEM image of the multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 6 is shown in fig. 6.
Example 6 the modified porous silica moisture barrier antireflective coating prepared on a quartz glass substrate has an average transmittance of 98.10% over the range of 400-1100 nm. The surface of the coating is flat and smooth as a whole, the average roughness is about 1.87nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.25 percent after the coating is dry-wiped for 80 times; after 24h of highly accelerated ageing tests (which 24h of highly accelerated ageing tests correspond to 1000h of the conventional double 85 test), the transmission is reduced by < 0.2%. The size of pores on the section of the coating is 5-7 nm, the size of pores on the surface is about 20nm, reversible absorption and desorption of water vapor are facilitated, and the moisture-proof coating has an excellent moisture-proof function.
The preparation method of the modified porous silica moisture-proof antireflection coating in the embodiment 7 comprises the following steps:
(1) synthesis of multi-arm silane precursor
Adding 3- (2, 3-epoxypropoxy) propyltriethoxysilane and 20mLN, N-bis- [ (3-triethoxysilylpropyl) aminocarbonyl ] polyethoxyalkyl into a three-neck flask, adding 3000mL ethanol as a reaction solvent, stirring and reacting for 72 hours at 60 ℃ under the protection of argon, transferring the reaction solution into a beaker after the reaction is finished, evaporating and concentrating, and removing the ethanol solvent to prepare a four-arm silane precursor TS-4, wherein the chemical reaction formula is as follows:
(2) preparation of precursor solution of polysiloxane sol
880mmol of tetramethoxysilane and 12mmol of four-arm silane precursor TS-4 are added into a three-neck round-bottom flask, 220mL of ethanol, 18mL of deionized water and 0.05mmol of hydrochloric acid are added, reflux stirring is carried out at 60 ℃ for reaction for 2.5h, and then natural cooling is carried out to room temperature, so as to obtain precursor solution of polysiloxane sol;
(3) preparation of pore-forming agent solution
Respectively adding 1000mL of ethanol, 72mL of deionized water and 4mmol of hydrochloric acid into a beaker to obtain a mixed solution, adding 12mmol of polyoxypropylene-polyoxyethylene-polyoxypropylene segmented copolymer F127 into the mixed solution, fully stirring at room temperature to uniformly disperse the F127, and preparing a pore-forming agent solution;
(4) preparation of modified silica sols
Slowly dripping the pore-forming agent solution prepared in the step (3) into a precursor solution of polysiloxane sol by using a dropper, reacting for 2 hours at 30 ℃, sealing and aging for 2 days at normal temperature, and adjusting the pH value of the sol to be about 2 to obtain quadriarm silane TS-4 and tetramethoxysilane as double silicon source modified acid sol, namely modified silica sol;
(5) preparation of moisture-proof anti-reflection coating
Taking 25mL of the prepared modified silica sol, adding 25mL of absolute ethyl alcohol to dilute the sol to obtain a glue solution, preparing a double-sided modified coating on a quartz glass substrate at the pulling speed of 1200 mu m/s by a dipping and pulling method under the conditions that the ambient temperature is 22 ℃ and the ambient relative humidity is 22%, and then carrying out annealing treatment at 400 ℃/1h in a muffle furnace, namely obtaining the modified porous silica moisture-proof anti-reflection coating with the single-sided thickness of 128nm and the refractive index of 1.19 on the quartz glass substrate.
A cross-sectional SEM image of the multi-arm silane-modified porous silica moisture barrier antireflective coating prepared in example 7 is shown in fig. 7.
Example 7 the modified porous silica moisture-resistant antireflective coating prepared on a quartz glass substrate has an average transmittance of 98.05% over a 400-1100 nm range. The surface of the coating is flat and smooth as a whole, the average roughness is about 0.87nm, the particles are tightly stacked, the coating has good wear resistance and weather resistance, and the optical transmittance is reduced by less than 0.2 percent after the coating is dry-wiped for 80 times; after 24h of highly accelerated ageing tests (which 24h of highly accelerated ageing tests correspond to 1000h of the conventional double 85 test), the transmission is reduced by < 0.2%. The size of pores on the section of the coating is about 8-10 nm, the size of pores on the surface is about 25nm, reversible absorption and desorption of water vapor are facilitated, and the moisture-proof coating has an excellent moisture-proof function.
Claims (5)
1. A preparation method of a modified porous silicon dioxide moistureproof anti-reflection coating is characterized by comprising the following steps:
(1) synthesis of multi-arm silane precursor
Adding siloxane containing epoxy groups and siloxane containing primary amine or secondary amine into a three-neck flask according to a certain proportion, heating and reacting for a period of time under the protection of inert gas by taking an alcohol solvent as a reaction solvent, transferring a reaction solution into a beaker after the reaction is finished, and evaporating and concentrating to prepare a multi-arm silane precursor;
in the step (1), the molar ratio of the siloxane containing the epoxy group to the siloxane containing the primary amine or the secondary amine is 0.5-5: 0.25-2.5, wherein the dosage of the siloxane containing the epoxy group is 4-40 mL, the dosage of the siloxane containing the primary amine or the secondary amine is 2-20 mL, and the dosage of the alcohol solvent is 150-3000 mL; heating at 40-80 ℃, reacting for 24-72 h, and after the reaction is finished, evaporating and concentrating to remove the alcohol solvent;
(2) preparation of precursor solution of polysiloxane sol
Mixing a siloxane-containing silane monomer with the multi-arm silane precursor synthesized in the step (1) according to a certain proportion, adding a certain proportion of alcohol solvent, deionized water and acid catalyst, heating, refluxing, stirring, reacting, and naturally cooling to room temperature to obtain a precursor solution of polysiloxane sol;
in the step (2), the molar ratio of the siloxane-containing silane monomer to the multi-arm silane precursor is 10-100: 0.1-1.4, the molar ratio of the sum of the molar amount of the siloxane-containing silane monomer and the multi-arm silane precursor to the alcohol solvent, deionized water and the acid catalyst is 1-10: 3-40: 1-10: 0.00005-0.0005, wherein the amount of the siloxane-containing silane monomer is 88-880 mmol, the amount of the multi-arm silane precursor is 1-12 mmol, the amount of the alcohol solvent is 22-220 mL, the amount of the deionized water is 1.8-18 mL, and the amount of the acid catalyst is 0.005-0.05 mmol; the heating temperature is 40-70 ℃, and the reaction time is 1.5-3 h;
(3) preparation of pore-forming agent solution
Mixing an alcohol solvent, deionized water and an acid catalyst according to a certain proportion to obtain a mixed solution, weighing a certain amount of a pore-forming agent, adding the pore-forming agent into the mixed solution, and fully stirring at room temperature to uniformly disperse the pore-forming agent to prepare a pore-forming agent solution;
in the step (3), the molar ratio of the alcohol solvent, the deionized water, the acid catalyst and the pore-forming agent is 18.2-182: 4-40: 0.00395-0.0395: 0.008-0.12, wherein the dosage of the alcohol solvent is 100-1000 mL, the dosage of the deionized water is 7.2-72 mL, the dosage of the acid catalyst is 0.4-4 mmol, and the dosage of the pore-forming agent is 0.8-12 mmol;
(4) preparation of modified silica sols
Adding the pore-forming agent solution prepared in the step (3) into the precursor solution of the polysiloxane sol prepared in the step (2), reacting for a period of time at a certain temperature, sealing and aging at normal temperature, and adjusting the pH value of the sol to obtain modified silica sol;
in the step (4), the reaction temperature is 20-50 ℃, the reaction time is 1-5 hours, the pH value of the sol is adjusted to 1.5-5, modified silica sol is prepared, and the modified silica sol is stored in a transparent glass container for later use;
(5) preparation of moisture-proof anti-reflection coating
Preparing a double-sided modified coating on the transparent substrate by adopting the modified silica sol prepared in the step (4) through a dip-coating method at a certain temperature and humidity, and then annealing to obtain the modified porous silica moisture-proof anti-reflection coating on the transparent substrate;
in the step (5), the environment temperature for preparing the double-sided modified coating on the transparent substrate is 15-35 ℃, the environment relative humidity is 20-40%, the pulling speed of the dipping pulling method is 800-2000 mu m/s, the annealing temperature is 200-500 ℃, and the annealing time is 1-2 h.
2. The method for preparing the modified porous silica moisture-proof antireflection coating according to claim 1, wherein in the step (1), the siloxane containing an epoxy group is one of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane and 3- (2, 3-glycidoxy) propylmethyldiethoxysilane; the siloxane containing primary amine or secondary amine is one of bis [3- (triethoxysilane) propyl ] amine, bis [3- (trimethoxy silane) propyl ] amine, N-bis- [ (3-triethoxysilylpropyl) aminocarbonyl ] polysiloxane, N-bis- [ (3-trimethoxysilyl) propyl ] ethylenediamine, N-bis- [ (3-triethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxy silane.
3. The method for preparing the modified porous silica moisture-proof antireflection coating according to claim 1, wherein in the step (2), the siloxane-containing silane monomer is one of tetramethoxysilane, tetraethoxysilane and methyltriethoxysilane.
4. The method for preparing the modified porous silica moisture-proof anti-reflection coating according to claim 1, wherein in the step (3), the pore-forming agent is an amphiphilic block copolymer, an ionic surfactant or a nonionic surfactant, the amphiphilic block copolymer is a polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymer, the ionic surfactant is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride, and the nonionic surfactant is polyacrylic acid.
5. The preparation method of the modified porous silica moisture-proof antireflection coating according to claim 1, wherein in the steps (1) to (3), the alcohol solvent is one of methanol, ethanol and isopropanol; in the steps (2) to (3), the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid and phosphoric acid.
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| CN201910071614.1A CN109592908B (en) | 2019-01-25 | 2019-01-25 | Preparation method of modified porous silicon dioxide moisture-proof anti-reflection coating |
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| CN112760035B (en) * | 2020-12-30 | 2022-04-08 | 中国科学院宁波材料技术与工程研究所 | Photocuring composite flexible anti-reflection coating and preparation method and application thereof |
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| CN115926622B (en) * | 2022-12-02 | 2023-08-22 | 吉林大学 | High-surface-hardness, wear-resistant and super-soft hydrophobic coating taking silicon-doped carbonized polymer dots as construction elements and preparation method thereof |
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