CN109592908A - A kind of preparation method of modified porous silica moistureproof antireflecting coating - Google Patents
A kind of preparation method of modified porous silica moistureproof antireflecting coating Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of modified porous silica moistureproof antireflecting coating, multi-arm silane is synthesized by opening by the siloxanes containing epoxy group and the siloxanes containing primary amine or secondary amine first, again using multi-arm silane with contain the silane monomer of siloxanes as common silicon source monomer, the precursor solution of polysiloxanes colloidal sol is prepared under acid catalysed conditions, then pore-creating agent solution is prepared, modified silicon dioxide sol is prepared later, modified silicon dioxide sol is finally passed through into dip-coating method one-pass film-forming on a transparent substrate, modified porous silica moistureproof antireflecting coating is prepared.The coating has wide spectrum anti-reflection effect, smooth surface, it is tightly packed between particle, with good wearability and weatherability, it is 5~10nm with a thickness of 100~200nm, section pore-size, and surface pore is having a size of 10~40nm, be conducive to the reversible adsorption desorption of steam, there is excellent moisture-proof function.
Description
Technical field
The invention belongs to inorganic thin film material technical field of modification, in particular to a kind of moisture-proof increasing of modified porous silica
The preparation method of antireflective coating layer.
Background technique
Based on the silica antireflecting coating excellent in optical properties of sol-gel method preparation, because having, weather resistance is good, rolls over
Penetrate rate is adjustable, preparation method is simple, the advantages that being prepared with large area and be widely used.But be applied to solar battery and
It mainly include aqueous vapor absorption, grey dustiness vulnerable to the influence of outside environmental elements when the antireflecting coating of building glass and optical lens
Dye and surface abrasion etc. cause its optical property to decline, and reduced service life, component maintenance cost rises.
Currently, the silica antireflecting coating based on sol-gel method preparation, passes through colloidal sol synthesis modification and chemical modification
Post-processing tentatively obtains the coating surface with self-cleaning function, realizes the performances such as wear-resisting, the moisture-proof and anti-pollution of coating.
Patent CN106892574A discloses a kind of superhydrophilic self-cleaning porous silica antireflective film and preparation method thereof, with positive silicic acid
Ethyl ester is silicon source, and silica dioxide granule glue A is prepared under the conditions of base catalysis, and the glue A of removal base catalyst is added just
Silester, and acid catalysis hydridization processing is carried out, obtain glue liquid B.The film of preparation carries out at annealing between 250~600 DEG C
Reason, the film after annealing carry out hydrochloric acid immersion treatment and the placement processing under vapor.By control base catalyst dosage and
Digestion time, the membrane pore size of acquisition is between 5~8nm；By controlling the dosage of acid catalyst, after hydrochloric acid and vapor
Under the conditions of reason, the water contact angle of film is less than 5 °.The invention improves the wearability of film by hydridization and hydrochloric acid post-processing
And Superhydrophilic, but membrane pore size is smaller, easily adsorbs the steam in air, causes the decline of optical property.
Patent CN107674463 discloses organic silicon source methyltriethoxysilane and ethyl orthosilicate as common silicon source
Presoma, alcohol and water are solvent, and silane coupling agent KH560 and KH570 and soft agent, N-Methyl pyrrolidone, crosslinking is added
Agent, levelling agent, under acid catalysed conditions, being formed has core-shell structure SiO2The silicon dioxide gel of particle, wherein SiO2Particle ruler
Very little is 25~30nm.The film of preparation tempering processing removal organic group under 680 DEG C~720 DEG C high temperature, obtains superhard anti-reflection
Penetrate film.The antireflecting coating compact structure has preferable weatherability and wearability.But the preparation method raw material is complicated, film
It is 94.10% in 380~1100nm wave band mean transmissivity, single side wide spectrum anti-reflection performance is lower.
Patent CN107188425A discloses a kind of method of improved silica anti-reflection film, with ethyl orthosilicate, methyl
Trimethyl silane, n,N-Dimethylformamide are the anti-reflection film that presoma prepares silica under acid catalysed conditions, pass through object
Matter proportion and heating temperature control improve film forming cracking and the non-uniform problem of film layer, improve film layer damage resistant and anti-aging property.It is right
Than in patent CN107629419 using ethyl orthosilicate list silicon source as the acid catalysis antireflecting silicon dioxide film of presoma, simple heat
Processing can be realized that film layer is tightly packed, thus the method for modifying of this patent does not play apparent modifying function, and gained film
Layer optical property is lower, and thin-film refractive index adjustability is weaker, and a large amount of methyl that introduce close silicone hydroxyl condensation efficiency and film base junction
Influence not known to.
Patent CN108455872A proposes a kind of hydrophobic antireflective film of scratch resistance.By the hollow sphere SiO of hydrophobically modified2Nanoparticle
Sub- solution is mixed with hydrophilic inorganic nanometer adhesive precursor solution, obtains hybrid collosol.On the glass substrate after plated film,
400 DEG C of heat treatment 1h, obtain hydrophobic antireflective film.Although the addition of hydrophilic inorganic nanometer binder can be formed centainly with substrate
Bonding, but unordered accumulation of the nanoparticle in film forming procedure keeps roughness of film larger, and external pores are more, drop
The weatherability and mechanical endurance of low film.
In addition, for the ordered mesoporous silica dioxide system under acid catalysed conditions, Xu Yao et al. (Contamination-
Resistant silica antireflective coating with closed ordered mesopores, RSC
Phys.Chem.Chem.Phys, 2014,16,16684-16693) with silicon fluoride, orderly Jie that acid-catalyzed sol is prepared
Hole silicon dioxide antireflective film is post-processed, and using the mesoporous hole of fluorine-based modification film surface, obtains having certain hydrophobicity
The surface of energy makes film layer have certain moisture-proof functions, but its functionalization timeliness is short.In addition,
(Superhydrophilic Antireflective Periodic Mesoporous OrganosilicaCoating on
Flexible Polyimide Substrate with Strong Abrasion-Resistance, ACS Appl Mater
Interfaces 2017,9 (6), 5468-5476.) document also reported using r- (2,3 the third oxygen of epoxy) propyl trimethoxy silicon
Alkane (GPTMS) is reacted with ethylenediamine (EDA), is prepared for a kind of organosilan (EG-BSQ) of chiasma type.Organosilan with
Ethyl orthosilicate is template as common silicon source presoma, F127, and modified titanium dioxide is prepared for using acid catalyzed method
Silica solution.Prepare film on flexible substrates, 250 DEG C of annealings, obtained Superhydrophilic, have with flexible substrate it is relatively strong
The mesoporous silicon oxide antireflective film of binding force.Fine and close film layer structure is obtained by this method, improves film layer and flexibility
The binding force of substrate, but film surface 5nm or so mesoporous hole, outdoors in environment, due to capillary condensation act on,
There are still the potential problems of the irreversible moisture absorption.
Junhui He et al. (Afacile hybrid approach to high-performance broadband
antireflective thin films with humidity resistance as well as mechanical
Robustness, Journal of Materials Chemistry C 2016,4,5342--5348.) utilize methyl trimethoxy oxygen
Base silane (MTMS) and ethyl orthosilicate are silicon source, and Surfactant CTAB is added, is prepared for the two of hydrophobically modified under acid catalysis
Silica sol, 600 DEG C of annealings obtain the hydrophobicity ultra-smooth anti-reflection with certain porosity and methyl modification after plated film
Film.Similarly, patent CN102757055A uses methyltriethoxysilane as organic silicon source, is prepared for dredging with same method
Aqueous mesoporous silicon dioxde film.Humidity resistance, this method are obtained by hydrophobic post-processing compared to mesoporous silicon dioxde film layer
The film of preparation has certain mechanical stability and relatively long-acting hydrophobic property, but due to the hydrophobicity of colloidal sol entirety,
The binding force site of film layer and substrate greatly reduces, and the film-substrate cohesion and mechanical endurance of film are not known.
It is existing based on sol-gel modified and chemical modification post-processing technology silica antireflecting coating, mainly include hydridization with
And mesoporous silicon oxide coating surface, just have self-cleaning function by the method for chemical modification.Wherein hybrid silica is adopted more
Modification sol is obtained with two or multistep processes, operating procedure is more complex, and preparation method controllability is poor, and gained coating surface has
While self-cleaning function, roughness is larger, and there are a large amount of external pores；And coating a large amount of functional groups introducing after, silicon hydroxyl
Effective condensing site of base is greatly reduced, degree of cross linking decline, for known to the research not of coating stability and mechanical endurance energy.
In contrast, existing mesoporous silicon oxide antireflecting coating (its surface SEM figure is shown in Fig. 1), unique high intensity under the premise of acid catalysis
Orderly mesopore network, stable structure, film layer is fine and close, and surface is smooth, has stronger mechanical endurance and weatherability, but because of table
Mesoporous hole existing for face can carry out irreversible chemical/physical absorption under capillary condensation effect with the steam in air, cause
Mesopore orbit structure swells simultaneously change, and after hole is filled by steam, refractive index rises, and the decline of anti-reflection performance is serious；In view of
This, after mostly use chemical modification to post-process, " closing " surface mesoporous hole will be surface-hydrophobicized, inhibit the moisture absorption.Though the method is shown in
Effect is fast, but timeliness is short, once hydrophobic effect fails, the mesoporous coating surface of script will the moisture absorption again.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of modified porous titanium dioxide
The preparation method of silicon moistureproof antireflecting coating, the coating of preparation have a wide spectrum anti-reflection effect, smooth surface, tight between particle
Closs packing has good wearability and weatherability, and with a thickness of 100~200nm, section pore-size is 5~10nm, surface
Pore-size is 10~40nm, is conducive to the reversible adsorption desorption of steam, has excellent moisture-proof function.
The technical scheme of the invention to solve the technical problem is: a kind of modified porous silica moistureproof antireflecting
The preparation method of coating, comprising the following steps:
(1) synthesis of multi-arm silane precursor
Siloxanes containing epoxy group and the siloxanes containing primary amine or secondary amine are added in three-necked flask by a certain percentage,
Using alcoholic solvent as reaction dissolvent, under inert gas protection, heating reaction a period of time, after reaction, reaction solution is shifted
Into beaker, it is concentrated by evaporation, multi-arm silane precursor is prepared；
(2) preparation of the precursor solution of polysiloxanes colloidal sol
Silane monomer containing siloxanes is mixed in a certain ratio with the multi-arm silane precursor synthesized in step (1),
And a certain proportion of alcoholic solvent, deionized water and acid catalyst is added, it is heated to reflux and is stirred to react rear cooled to room temperature, obtain
To the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
Alcoholic solvent, deionized water and acid catalyst are mixed in a certain ratio, mixed liquor is obtained, weighs a certain amount of pore-creating
Agent adds in the mixed liquor, and stir thoroughly at room temperature makes pore creating material be uniformly dispersed, and pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is added in the precursor solution of the polysiloxanes colloidal sol of step (2) preparation,
After reacting a period of time at a certain temperature, room temperature seal aging adjusts sol pH, obtains modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
Dip-coating method is passed through under certain temperature and humidity using modified silicon dioxide sol prepared by step (4)
Two-sided modified coating is prepared on a transparent substrate, is then made annealing treatment, i.e., obtains modified porous dioxy on a transparent substrate
SiClx moistureproof antireflecting coating.
The present invention provides a kind of preparation methods of modified porous silica moistureproof antireflecting coating, and this method is first by containing
There are the siloxanes of epoxy group and the siloxanes containing primary amine or secondary amine to synthesize multi-arm silane by opening, then with multi-arm
Silane precursor with contain the silane monomer of siloxanes as common silicon source monomer, and be added a certain proportion of alcoholic solvent, go from
The precursor solution of polysiloxanes colloidal sol is prepared in sub- water and acid catalyst under acid catalysed conditions；Then by alcoholic solvent, go
Ionized water, acid catalyst and pore creating material uniformly mix by a certain percentage, and pore-creating agent solution is prepared；Later by pore-creating agent solution
It is mixed with the precursor solution of polysiloxanes colloidal sol, modified silicon dioxide sol is prepared；It is finally that improved silica is molten
Glue passes through dip-coating method one-pass film-forming on a transparent substrate, and by annealing high temperature induction method, pore creating material is removed, thus saturating
Surface is obtained on bright substrate and section is respectively provided with the modified porous silica moistureproof antireflecting coating of specific mesoporous hole, and is applied
The mesoporous hole of layer surface is greater than the mesoporous hole of coating section, and the mesoporous hole of coating surface and coating section has gradual change ruler
Very little gradient forms multistage pore structure.The section of coating prepared by the present invention has small-size meso-porous duct (6~9nm), passes through
SEM figure is it can be seen that the larger surface pore-size for accumulating formation between coating surface particle is 10~40nm.
The preparation method of modified porous silica moistureproof antireflecting coating of the present invention synthesizes and uses multi-arm silane, firstly,
While directly introducing functional group, a large amount of silicone hydroxyl has also been introduced, is the precursor solution of polysiloxanes colloidal sol
Dehydration condensation provides a large amount of crosslink sites；Secondly as the multi-arm silane of synthesis contains a large amount of silicone hydroxyls, and contain
Silicone hydroxyl is in alkalescent in alcoholic solution, can make the silane monomer containing siloxanes under acid catalysed conditions rapidly with its core,
It is crosslinked therewith and assembles the particle for being grown to tens nanometers (10~40nm), it can be achieved that subsequent film gradual change cellular structure is constructed
And surface pore regulation.In this way, both having overcome in conventional method after functional group introducing, the disadvantage of silicone hydroxyl condensing site reduction
End, and prior art intermediary hole coating surface is improved because of moisture absorption problem caused by lesser mesoporous hole (5~10nm).This
The coating of invention preparation can be realized wide spectrum anti-reflection, and performance is significantly improved in terms of the functionalization such as moisture-proof, wear-resisting.
The preparation condition of the method for the present invention is mild, easy to operate, can be prepared by modified silicon dioxide sol one-pass film-forming
Modified porous silica moistureproof antireflecting coating is obtained, and the pore structure of obtained coating is flexibly controllable, in the association of each step
Tightly packed with achievable small size nano particle under regulation, forming surface and section has the coating of gradual change cellular structure.This
Inventive method can solve the problems, such as the coating moisture absorption while preparing high-intensitive order mesoporous antireflecting coating, and it is weather-proof to promote coating
Performance extends the service life of mesoporous silicon oxide antireflecting coating environment outdoors, is suitable for including ultra-clear glasses, quartz glass
Etc. it is various transparent including the flexible substrates such as rigid substrates and ultra-thin glass, polyimides, polyethylene terephthalate
Substrate, industrial production and application prospect with scale.
Preferably, in step (1), the molar ratio of the siloxanes containing epoxy group and the siloxanes containing primary amine or secondary amine
For 0.5~5:0.25~2.5, wherein the dosage of the siloxanes containing epoxy group is 4~40mL, the silicon containing primary amine or secondary amine
The dosage of oxygen alkane is 2~20mL, and the dosage of alcoholic solvent is 150~3000mL；Heating temperature is 40~80 DEG C, the reaction time 24
~72h is concentrated by evaporation after reaction, removes alcoholic solvent.
Preferably, the siloxanes containing epoxy group is 3- (2,3- the third oxygen of epoxy) propyl front three in step (1)
Oxysilane (i.e. GPTMS), 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane (i.e. GPTES), 3- (the third oxygen of 2,3- epoxy)
Hydroxypropyl methyl diethoxy silane is (i.e. by hydroxypropyl methyl dimethoxysilane (i.e. GPMDMS) and 3- (the third oxygen of 2,3- epoxy)
One of GPMDES)；The siloxanes containing primary amine or secondary amine is bis- [3- (triethoxysilane) propyl] amine, double
[3- (trimethoxy silane) propyl] amine, N, N- is bis--[(3- triethoxysilylpropyl) amino carbonyl] poly- ethoxy alkane, N, and N- is bis--
[(3- trimethoxy silicon substrate) propyl] ethylenediamine, N, N- is bis--[(3- triethoxy silicon substrate) propyl] ethylenediamine, three second of 3- aminopropyl
One of oxysilane, 3- aminopropyl trimethoxysilane.
Preferably, in step (2), the molar ratio of the silane monomer containing siloxanes and multi-arm silane precursor is 10~
The sum of mole dosage of 100:0.1~1.4, the silane monomer containing siloxanes and multi-arm silane precursor, alcoholic solvent, deionization
Water, acid catalyst molar ratio be 1~10:3~40:1~10:0.00005~0.0005, wherein the silane containing siloxanes
The dosage of monomer is 88~880mmol, and the dosage of multi-arm silane precursor is 1~12mmol, the dosage of alcoholic solvent is 22~
220mL, the dosage of deionized water are 1.8~18mL, and the dosage of acid catalyst is 0.005~0.05mmol；Heating temperature is 40
~70 DEG C, the reaction time is 1.5~3h.
Preferably, the silane monomer containing siloxanes is tetramethoxy-silicane (also known as positive silicon in step (2)
Sour methyl esters, i.e. TMOS), one of tetraethoxysilane (also known as ethyl orthosilicate, i.e. TEOS) and methyltriethoxysilane.
Preferably, in step (3), alcoholic solvent, deionized water, the molar ratio of acid catalyst and pore creating material be 18.2~
182:4~40:0.00395~0.0395:0.008~0.12, wherein the dosage of alcoholic solvent is 100~1000mL, deionized water
Dosage be 7.2~72mL, the dosage of acid catalyst is 0.4~4mmol, and the dosage of pore creating material is 0.8~12mmol.
Preferably, in step (3), the pore creating material be amphiphilic diblock copolymer, ionic surfactant or
Nonionic surface active agent, the amphiphilic diblock copolymer are polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers
Object (i.e. F127 or P123), the ionic surfactant are cetyl trimethylammonium bromide (i.e. CTAB) or hexadecane
Base trimethyl ammonium chloride (i.e. CATC), the nonionic surface active agent are polyacrylic acid (i.e. PAA).CTAB, CATC and
PAA belongs to surfactant scope, removes temperature T > 400 DEG C；Amphiphilic diblock copolymer have lower thermal stability or
Thermal decomposition temperature, decomposition temperature Td<250℃.By being made annealing treatment to the two-sided modified coating prepared in transparent substrates,
Pore creating material can be made to be effectively removed, to obtain surface on a transparent substrate and section is respectively provided with changing for specific mesoporous hole
Property porous silica moistureproof antireflecting coating.
Preferably, reaction temperature is 20~50 DEG C in step (4), the reaction time is 1~5h, adjusts sol pH and is
1.5~5, modified silicon dioxide sol is prepared, and modified silicon dioxide sol is stored in transparent glass container, it is standby
With.The modified silicon dioxide sol is placed on black substrate, is light blue colloidal sol under illumination.
Preferably, the environment temperature for preparing two-sided modified coating on a transparent substrate is 15~35 DEG C in step (5),
Envionmental humidity is 20~40%, and the pull rate of dip-coating method is 800~2000 μm/s, and annealing temperature is 200~500
DEG C, annealing time is 1~2h.
Preferably, the alcoholic solvent is one of methanol, ethyl alcohol and isopropanol in step (1)~step (3)；
In step (2)~step (3), the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid and phosphoric acid.
Compared with prior art, the present invention has the advantage that
One, coating prepared by the present invention is with wide spectrum anti-reflection effect, the two-sided modified coating prepared on a transparent substrate,
In 400~1100nm range mean transmissivity >=97%；
Two, coating surface prepared by the present invention is flat and smooth, and mean roughness is about 1nm or so, compact reactor between particle
Product has good wearability, and after xerotripsis 80 times, optical transmittance reduces < 0.3%；
Three, coating prepared by the present invention has good weatherability, by high accelerated aging test (height for 24 hours for 24 hours
Accelerated aging test is equivalent to double 85 tests of tradition of 1000h) after, transmitance reduces < 0.5%；
Four, silane-modified by the multi-arm of synthesis, coating prepared by the present invention is tightly packed, with a thickness of 100~200nm,
Section pore-size is 5~10nm, and surface pore is conducive to the reversible adsorption desorption of steam having a size of 10~40nm, is had excellent
Moisture-proof function.
Detailed description of the invention
Fig. 1 is that the surface SEM of existing mesoporous silicon oxide antireflecting coating schemes；
Fig. 2 is to make in ultra-clear glasses substrate under the conditions of 20 DEG C of environment temperature, envionmental humidity 20% in embodiment 1
Optical transmittance curve of the silane-modified porous silica moistureproof antireflecting coating of standby multi-arm after 400 DEG C of annealing；
Fig. 3 is to make in ultra-clear glasses substrate under the conditions of 26 DEG C of environment temperature, envionmental humidity 30% in embodiment 3
Optical transmittance curve of the silane-modified porous silica moistureproof antireflecting coating of standby multi-arm after 400 DEG C of annealing；
Fig. 4 is the surface SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 4；
Fig. 5 is the surface SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 5；
Fig. 6 is the section SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 6；
Fig. 7 is the section SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 7.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 1, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 10mL 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane and 4.45mL N, N- it is bis--[(3- triethoxysilicane
Propyl) amino carbonyl] poly- ethoxy alkane is added in three-necked flask, 300mL ethyl alcohol is added as reaction dissolvent, in nitrogen protection
Under, 60 DEG C are stirred to react 48h, and after reaction, reaction solution is transferred in beaker, are concentrated by evaporation, and remove alcohol solvent, preparation
Obtain four arm silane precursor TS-1, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
88mmol tetraethoxysilane and tetra- arm silane precursor TS-1 of 12mmol are added in three neck round bottom flask, and added
Enter 22.19mL dehydrated alcohol, 1.8mL deionized water and 0.005mmol hydrochloric acid, natural cooling after 60 DEG C of return stirring reaction 1.5h
To room temperature, the precursor solution of polysiloxanes colloidal sol is obtained；
(3) preparation of pore-creating agent solution
It is separately added into the hydrochloric acid of 100mL dehydrated alcohol, 7.2mL deionized water and 0.4mmol into beaker, is mixed
Liquid weighs 0.8mmol polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers F127 and adds in the mixed liquor, and room temperature is abundant
Stirring, makes F127 be uniformly dispersed, pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 30 DEG C of reaction 2h, room temperature seal aging 2 days, adjusting sol pH was 2 or so, obtained four arm silane TS-1 and tetraethoxy-silicane
The alkane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL dehydrated alcohol is added and dilutes to obtain glue, in environment
Under the conditions of temperature is 20 DEG C, envionmental humidity is 20%, by dip-coating method, with the pull rate of 1200 μm/s in ultrawhite
Two-sided modified coating is prepared in substrate of glass, the annealing of 400 DEG C/1h is then carried out in Muffle furnace, i.e., in ultra-clear glasses
Single side is obtained in substrate with a thickness of 118nm, the modified porous silica moistureproof antireflecting coating that refractive index is 1.21.
It is prepared in ultra-clear glasses substrate under the conditions of 20 DEG C of environment temperature, envionmental humidity 20% in embodiment 1
Optical transmittance curve of the silane-modified porous silica moistureproof antireflecting coating of multi-arm after 400 DEG C of annealing is shown in Fig. 2.From Fig. 2
As it can be seen that being 97.60% in 400~1100nm range mean transmissivity.Whole more flat and smooth, the mean roughness of coating surface
About 1.23nm or so, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optics is penetrated
Rate reduces < 0.2%；By high accelerated aging test for 24 hours, (tradition that the high accelerated aging test for 24 hours is equivalent to 1000h is double
85 tests) after, transmitance reduces < 0.4%.Coating section pore-size is 6~9nm or so, and surface pore is having a size of 30nm
Left and right, is conducive to the reversible adsorption desorption of steam, has excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 2, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 20mL3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane and 10mLN, N- it is bis--[(3- triethoxy silicon substrate)
Propyl] ethylenediamine is added in three-necked flask, add 600mL ethyl alcohol as reaction dissolvent, under nitrogen protection, 70 DEG C of stirrings are instead
It answers 72h, after reaction, reaction solution is transferred in beaker, is concentrated by evaporation, remove alcohol solvent, four arm silane are prepared
Presoma TS-2, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
Three neck round bottom flask is added in 197.37mmol tetraethoxysilane and tetra- arm silane precursor TS-2 of 2.63mmol
In, and 44.38mL dehydrated alcohol, 3.6mL deionized water and 0.01mmol nitric acid is added, it is natural after 70 DEG C of return stirring reaction 2h
It is cooled to room temperature, obtains the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
It is separately added into 212.54mL dehydrated alcohol, 14.4mL deionized water and 0.8mmol nitric acid into beaker, is mixed
Liquid takes 2.4mmol polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers F127 to add in the mixed liquor, and room temperature is sufficiently stirred
It mixes, F127 is made to be uniformly dispersed, pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 40 DEG C of reaction 3h, room temperature seal aging 2 days, adjusting sol pH was 4 or so, obtained four arm silane TS-2 and tetraethoxy-silicane
The alkane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL dehydrated alcohol is added and dilutes to obtain glue, in environment
Under the conditions of temperature is 35 DEG C, envionmental humidity is 40%, by dip-coating method, with the pull rate of 800 μm/s ultra-thin
Two-sided modified coating is prepared in substrate of glass, the annealing of 300 DEG C/1.5h is then carried out in Muffle furnace, i.e., in ultra-thin glass
Obtained in glass substrate single side with a thickness of between 130nm, refractive index be 1.30 modified porous silica moistureproof antireflecting coating.
The modified porous silica moistureproof antireflecting coating that embodiment 2 is prepared in ultra-thin glass substrate 400~
1100nm range mean transmissivity is 97.01%.Coating surface is whole more flat and smooth, and mean roughness is about the left side 1.07nm
The right side, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optical transmittance reduces < 0.2%；
After high accelerated aging test (double 85 tests of tradition that the high accelerated aging test for 24 hours is equivalent to 1000h) for 24 hours,
Transmitance reduces < 0.4%.Coating section pore-size is 5~8nm, and surface pore is conducive to steam having a size of 25nm or so
Reversible adsorption desorption has excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 3, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 4.42mL3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and 2.43mL3- aminopropyl triethoxysilane
It is added in three-necked flask, adds 150mL ethyl alcohol as reaction dissolvent, under protection of argon gas, 60 DEG C are stirred to react for 24 hours, reaction
After, reaction solution is transferred in beaker, is concentrated by evaporation, alcohol solvent is removed, three arm silane precursor GATS- is prepared
1, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
485mmol tetraethoxysilane and tri- arm silane precursor GATS-1 of 6mmol are added in three neck round bottom flask, and
120mL dehydrated alcohol, 9.2mL deionized water and 0.028mmol acetic acid, natural cooling after 65 DEG C of return stirring reaction 2.5h is added
To room temperature, the precursor solution of polysiloxanes colloidal sol is obtained；
(3) preparation of pore-creating agent solution
It is separately added into 550mL dehydrated alcohol, 39.5mL deionized water and 2.2mmol acetic acid into beaker, obtains mixed liquor,
6.4mmol polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers F127 is taken to add in the mixed liquor, stir thoroughly at room temperature,
So that F127 is uniformly dispersed, pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 20 DEG C of reaction 1h, room temperature seal aging 2 days, adjusting sol pH was 1.5 or so, obtained three arm silane GATS-1 and four ethoxies
The base silane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL dehydrated alcohol is added and dilutes to obtain glue, in environment
Under the conditions of temperature is 26 DEG C, envionmental humidity is 30%, by dip-coating method, with the pull rate of 1600 μm/s in ultrawhite
Two-sided modified coating is prepared in substrate of glass, the annealing of 400 DEG C/1h is then carried out in Muffle furnace, i.e., in ultra-clear glasses
Obtained in substrate single side with a thickness of between 115nm, refractive index be 1.20 modified porous silica moistureproof antireflecting coating.
It is prepared in ultra-clear glasses substrate under the conditions of 26 DEG C of environment temperature, envionmental humidity 30% in embodiment 3
Optical transmittance curve of the silane-modified porous silica moistureproof antireflecting coating of multi-arm after 400 DEG C of annealing is shown in Fig. 3.From Fig. 3
As it can be seen that being 97.58% in 400~1100nm range mean transmissivity.Whole more flat and smooth, the mean roughness of coating surface
About 2.20nm or so, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optics is penetrated
Rate reduces < 0.1%；By high accelerated aging test for 24 hours, (tradition that the high accelerated aging test for 24 hours is equivalent to 1000h is double
85 tests) after, transmitance reduces < 0.3%.Coating section pore-size is 6~8nm or so, and surface pore is having a size of 20nm
Left and right, is conducive to the reversible adsorption desorption of steam, has excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 4, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 40mL3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane and 20mL3- aminopropyl triethoxysilane
It is added in three-necked flask, adds 1800mL ethyl alcohol as reaction dissolvent, under nitrogen protection, 80 DEG C are stirred to react 72h, reaction
After, reaction solution is transferred in beaker, is concentrated by evaporation, alcohol solvent is removed, three arm silane precursor GATS- is prepared
2, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
880mmol tetramethoxy-silicane and tri- arm silane precursor GATS-2 of 10mmol are added in three neck round bottom flask,
And 220ml isopropanol, 18mL deionized water and 0.05mmol hydrochloric acid is added, room is naturally cooled to after 70 DEG C of return stirring reaction 3h
Temperature obtains the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
It is separately added into 1000ml isopropanol, 72mL deionized water and 4mmol hydrochloric acid into beaker, obtains mixed liquor, takes
12mmol polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers P123 is added in the mixed liquor, and stir thoroughly at room temperature makes
P123 is uniformly dispersed, and pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 50 DEG C of reaction 5h, room temperature seal aging 2 days, adjusting sol pH was 3 or so, obtained three arm silane GATS-2 and tetramethoxy
The silane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；·
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL isopropanol is added and obtains glue, in environment temperature
Under the conditions of degree is 25 DEG C, envionmental humidity is 35%, by dip-coating method, with the pull rate of 2000 μm/s in ultra-thin glass
Two-sided modified coating is prepared in glass substrate, the annealing of 400 DEG C/1h is then carried out in Muffle furnace, i.e., in ultra-thin glass base
Single side is obtained on bottom with a thickness of 170nm, the modified porous silica moistureproof antireflecting coating that refractive index is 1.18.
The surface SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 4 is shown in Fig. 4.
The modified porous silica moistureproof antireflecting coating that embodiment 4 is prepared in ultra-thin glass substrate, 400~
1100nm range mean transmissivity is 97.31%.Coating surface is whole more flat and smooth, and mean roughness is about the left side 2.11nm
The right side, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optical transmittance reduces < 0.3%；
After high accelerated aging test (double 85 tests of tradition that the high accelerated aging test for 24 hours is equivalent to 1000h) for 24 hours,
Transmitance reduces < 0.5%.Coating section pore-size is 7~9nm, and surface pore is conducive to steam having a size of 20nm or so
Reversible adsorption desorption has excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 5, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 15mL3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and 6.7mLN, N- it is bis--[(3- trimethoxy silicon substrate)
Propyl] ethylenediamine is added in three-necked flask, add 450mL methanol as reaction dissolvent, under nitrogen protection, 40 DEG C of stirrings are instead
It answers 72h, after reaction, reaction solution is transferred in beaker, steams methanol solvate, four arm silane precursor TS- are prepared
3, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
98mmol methyltriethoxysilane and tetra- arm silane precursor TS-3 of 1mmol are added in three neck round bottom flask,
And 22mL methanol, 1.8mL deionized water and 0.005mmol phosphoric acid is added, it is naturally cooled to after 40 DEG C of return stirring reaction 1.5h
Room temperature obtains the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
It is separately added into 106.27mL methanol, 7.2mL deionized water and 0.4mmol phosphoric acid into beaker, obtains mixed liquor, takes
0.8mmol cetyl trimethylammonium bromide CTAB is added in the mixed liquor, and stir thoroughly at room temperature makes cetyl trimethyl bromine
Change ammonium to be uniformly dispersed, pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 35 DEG C of reaction 1.5h, room temperature seal aging 2 days, adjusting sol pH was 2 or so, obtained four arm silane precursor TS-3 and first
The ethyl triethoxy silicane alkane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL methanol dilution is added and obtains glue, in environment temperature
Under the conditions of being 28% for 24 DEG C, envionmental humidity, by dip-coating method, with the pull rate of 1200 μm/s in ultra-thin glass
Two-sided modified coating is prepared in substrate, the annealing of 500 DEG C/1h is then carried out in Muffle furnace, i.e., in ultra-thin glass substrate
On obtain with a thickness of 160nm, refractive index be 1.25 modified porous silica moistureproof antireflecting coating.
The surface SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 5 is shown in Fig. 5.
The modified porous silica moistureproof antireflecting coating that embodiment 5 is prepared in ultra-thin glass substrate, 400~
1100nm range mean transmissivity is 97.14%.Coating surface is whole more flat and smooth, and mean roughness is about the left side 0.96nm
The right side, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optical transmittance reduced <
0.25%；By high accelerated aging test for 24 hours, (the high accelerated aging test for 24 hours is equivalent to double 85 examinations of tradition of 1000h
Test) after, transmitance reduces < 0.3%.Coating section pore-size is 5~8nm, and surface pore is having a size of 15nm or so, favorably
In the reversible adsorption desorption of steam, there is excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 6, comprising the following steps:
(1) synthesis of multi-arm silane precursor
25mL3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane and 15mL is bis- [3- (triethoxysilane) propyl]
Amine is added in three-necked flask, adds 1200mL ethyl alcohol as reaction dissolvent, under nitrogen protection, 50 DEG C are stirred to react 72h, instead
After answering, reaction solution is transferred in beaker, is concentrated by evaporation, alcohol solvent is removed, three arm silane precursors is prepared
GATS-3, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
300mmol tetraethoxysilane and tri- arm silane precursor GATS-3 of 5mmol are added in three neck round bottom flask, and
80ml dehydrated alcohol, 6.2mL deionized water and 0.019mmol hydrochloric acid is added, is naturally cooled to after 60 DEG C of return stirring reaction 2h
Room temperature obtains the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
It is separately added into 380mL dehydrated alcohol, 27mL deionized water and 1.5mmol hydrochloric acid into beaker, obtains mixed liquor, takes
4.4mmol polyacrylic acid PAA is added in the mixed liquor, and stir thoroughly at room temperature makes PAA be uniformly dispersed, and it is molten that pore creating material is prepared
Liquid；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 30 DEG C of reaction 2h, room temperature seal aging 2 days, adjusting sol pH was 5 or so, obtained three arm silane precursor GATS-3 and four
The Ethoxysilane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL dehydrated alcohol is added and dilutes to obtain glue, in environment
Under the conditions of temperature is 28 DEG C, envionmental humidity is 35%, by dip-coating method, with the pull rate of 1800 μm/s in quartz
Two-sided modified coating is prepared in substrate of glass, the annealing of 500 DEG C/1h is then carried out in Muffle furnace, i.e., in quartz glass
Single side is obtained in substrate with a thickness of the modified porous silica moistureproof antireflecting coating for being 1.22 for 125nm, refractive index.
The section SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 6 is shown in Fig. 6.
The modified porous silica moistureproof antireflecting coating that embodiment 6 is prepared in quartz glass substrate, 400~
1100nm range mean transmissivity is 98.10%.Coating surface is whole more flat and smooth, and mean roughness is about the left side 1.87nm
The right side, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optical transmittance reduced <
0.25%；By high accelerated aging test for 24 hours, (the high accelerated aging test for 24 hours is equivalent to double 85 examinations of tradition of 1000h
Test) after, transmitance reduces < 0.2%.Coating section pore-size is 5~7nm, and surface pore is having a size of 20nm or so, favorably
In the reversible adsorption desorption of steam, there is excellent moisture-proof function.
A kind of preparation method of modified porous silica moistureproof antireflecting coating of embodiment 7, comprising the following steps:
(1) synthesis of multi-arm silane precursor
By 40mL3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane and 20mLN, N- it is bis--[(3- triethoxysilicane third
Base) amino carbonyl] poly- ethoxy alkane is added in three-necked flask, add 3000mL ethyl alcohol as reaction dissolvent, under protection of argon gas,
60 DEG C are stirred to react 72h, and after reaction, reaction solution is transferred in beaker, are concentrated by evaporation, and remove alcohol solvent, are prepared into
To four arm silane precursor TS-4, chemical equation are as follows:
(2) preparation of the precursor solution of polysiloxanes colloidal sol
880mmol tetramethoxy-silicane and tetra- arm silane precursor TS-4 of 12mmol are added in three neck round bottom flask, and
220ml ethyl alcohol, 18mL deionized water and 0.05mmol hydrochloric acid is added, naturally cools to room after 60 DEG C of return stirring reaction 2.5h
Temperature obtains the precursor solution of polysiloxanes colloidal sol；
(3) preparation of pore-creating agent solution
It is separately added into 1000ml ethyl alcohol, 72mL deionized water and 4mmol hydrochloric acid into beaker, obtains mixed liquor, takes
12mmol polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers F127 is added in the mixed liquor, and stir thoroughly at room temperature makes
F127 is uniformly dispersed, and pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is slowly dropped in the precursor solution of polysiloxanes colloidal sol with dropper,
After 30 DEG C of reaction 2h, room temperature seal aging 2 days, adjusting sol pH was 2 or so, obtained four arm silane TS-4 and tetramethoxy-silicane
The alkane acid-sol modified as double silicon sources, i.e. modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol that 25mL is prepared is taken, 25mL dehydrated alcohol is added and dilutes to obtain glue, in environment
Under the conditions of temperature is 22 DEG C, envionmental humidity is 22%, by dip-coating method, with the pull rate of 1200 μm/s in quartz
Two-sided modified coating is prepared in substrate of glass, the annealing of 400 DEG C/1h is then carried out in Muffle furnace, i.e., in quartz glass
Single side is obtained in substrate with a thickness of 128nm, the modified porous silica moistureproof antireflecting coating that refractive index is 1.19.
The section SEM figure of the silane-modified porous silica moistureproof antireflecting coating of multi-arm prepared by embodiment 7 is shown in Fig. 7.
The modified porous silica moistureproof antireflecting coating that embodiment 7 is prepared in quartz glass substrate, 400~
1100nm range mean transmissivity is 98.05%.Coating surface is whole more flat and smooth, and mean roughness is about the left side 0.87nm
The right side, it is tightly packed between particle, there is good wearability and weatherability, after xerotripsis 80 times, optical transmittance reduces < 0.2%；
After high accelerated aging test (double 85 tests of tradition that the high accelerated aging test for 24 hours is equivalent to 1000h) for 24 hours,
Transmitance reduces < 0.2%.Coating section pore-size is 8~10nm or so, and surface pore is conducive to having a size of 25nm or so
The reversible adsorption desorption of steam has excellent moisture-proof function.
Claims (10)
1. a kind of preparation method of modified porous silica moistureproof antireflecting coating, which comprises the following steps:
(1) synthesis of multi-arm silane precursor
Siloxanes containing epoxy group and the siloxanes containing primary amine or secondary amine are added in three-necked flask by a certain percentage, with alcohol
Solvent is reaction dissolvent, under inert gas protection, heating reaction a period of time, after reaction, reaction solution is transferred to burning
In cup, it is concentrated by evaporation, multi-arm silane precursor is prepared；
(2) preparation of the precursor solution of polysiloxanes colloidal sol
Silane monomer containing siloxanes is mixed in a certain ratio with the multi-arm silane precursor synthesized in step (1), and is added
Enter a certain proportion of alcoholic solvent, deionized water and acid catalyst, is heated to reflux and is stirred to react rear cooled to room temperature, gathered
The precursor solution of siloxane sol；
(3) preparation of pore-creating agent solution
Alcoholic solvent, deionized water and acid catalyst are mixed in a certain ratio, mixed liquor is obtained, a certain amount of pore creating material is weighed and adds
Into the mixed liquor, stir thoroughly at room temperature makes pore creating material be uniformly dispersed, and pore-creating agent solution is prepared；
(4) preparation of modified silicon dioxide sol
Pore-creating agent solution prepared by step (3) is added in the precursor solution of the polysiloxanes colloidal sol of step (2) preparation, one
Determine after reacting a period of time at temperature, room temperature seal aging adjusts sol pH, obtains modified silicon dioxide sol；
(5) preparation of moistureproof antireflecting coating
The modified silicon dioxide sol prepared using step (4), under certain temperature and humidity, by dip-coating method saturating
Two-sided modified coating is prepared on bright substrate, is then made annealing treatment, i.e., obtains modified porous silica on a transparent substrate
Moistureproof antireflecting coating.
2. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (1), the molar ratio of the siloxanes containing epoxy group and the siloxanes containing primary amine or secondary amine is 0.5~5:0.25
~2.5, wherein the dosage of the siloxanes containing epoxy group is 4~40mL, and the dosage of the siloxanes containing primary amine or secondary amine is 2
~20mL, the dosage of alcoholic solvent are 150~3000mL；Heating temperature is 40~80 DEG C, and the reaction time is 24~72h, reaction knot
Shu Hou is concentrated by evaporation, and removes alcoholic solvent.
3. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In, in step (1), the siloxanes containing epoxy group be 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 3- (2,
The third oxygen of 3- epoxy) propyl-triethoxysilicane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane and 3- (2,3- epoxy
One of third oxygen) hydroxypropyl methyl diethoxy silane；The siloxanes containing primary amine or secondary amine is bis- [3- (three ethoxies
Base silane) propyl] amine, bis- [3- (trimethoxy silane) propyl] amine, N, N- is bis--[(3- triethoxysilylpropyl) amino carbonyl]
Poly- ethoxy alkane, N, N- is bis--[(3- trimethoxy silicon substrate) propyl] ethylenediamine, N, and N- is bis--[(3- triethoxy silicon substrate) propyl] second
One of diamines, 3- aminopropyl triethoxysilane, 3- aminopropyl trimethoxysilane.
4. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In, in step (2), the molar ratio of the silane monomer containing siloxanes and multi-arm silane precursor is 10~100:0.1~1.4,
The sum of mole dosage of silane monomer containing siloxanes and multi-arm silane precursor, alcoholic solvent, deionized water, acid catalyst
Molar ratio is 1~10:3~40:1~10:0.00005~0.0005, wherein the dosage of the silane monomer containing siloxanes is 88
~880mmol, the dosage of multi-arm silane precursor are 1~12mmol, and the dosage of alcoholic solvent is 22~220mL, deionized water
Dosage is 1.8~18mL, and the dosage of acid catalyst is 0.005~0.05mmol；Heating temperature is 40~70 DEG C, and the reaction time is
1.5~3h.
5. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (2), the silane monomer containing siloxanes is three second of tetramethoxy-silicane, tetraethoxysilane and methyl
One of oxysilane.
6. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (3), alcoholic solvent, deionized water, the molar ratio of acid catalyst and pore creating material are 18.2~182:4~40:
0.00395~0.0395:0.008~0.12, wherein the dosage of alcoholic solvent is 100~1000mL, and the dosage of deionized water is
7.2~72mL, the dosage of acid catalyst are 0.4~4mmol, and the dosage of pore creating material is 0.8~12mmol.
7. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (3), the pore creating material is that amphiphilic diblock copolymer, ionic surfactant or non-ionic surface are living
Property agent, the amphiphilic diblock copolymer be polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers, the ion
Type surfactant is cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride, and the non-ionic surface is living
Property agent be polyacrylic acid.
8. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (4), reaction temperature is 20~50 DEG C, and the reaction time is 1~5h, and adjusting sol pH is 1.5~5, is prepared
Modified silicon dioxide sol, and modified silicon dioxide sol is stored in transparent glass container, it is spare.
9. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (5), the environment temperature for preparing two-sided modified coating on a transparent substrate is 15~35 DEG C, and envionmental humidity is
20~40%, the pull rate of dip-coating method is 800~2000 μm/s, and annealing temperature is 200~500 DEG C, annealing time 1
~2h.
10. a kind of preparation method of modified porous silica moistureproof antireflecting coating according to claim 1, feature exist
In in step (1)~step (3), the alcoholic solvent is one of methanol, ethyl alcohol and isopropanol；Step (2)~step
(3) in, the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid and phosphoric acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439936A (en) * | 2020-04-29 | 2020-07-24 | 东莞南玻太阳能玻璃有限公司 | Gradient-refraction high-anti-reflection coated glass and preparation method thereof |
| CN112760035A (en) * | 2020-12-30 | 2021-05-07 | 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 |
| CN112759784A (en) * | 2020-12-30 | 2021-05-07 | 苏州太湖电工新材料股份有限公司 | Wear-resistant polyimide composite film and preparation method thereof |
| WO2022220928A1 (en) * | 2021-04-15 | 2022-10-20 | Cardinal Cg Company | Flexible aerogel, flexible glass technology |
| CN115926622A (en) * | 2022-12-02 | 2023-04-07 | 吉林大学 | High-surface-hardness, wear-resistant and super-soft hydrophobic coating with silicon-doped carbonized polymer dots as building elements and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1313828A1 (en) * | 2000-08-28 | 2003-05-28 | The Procter & Gamble Company | Fabric care compositions comprising cationic silicones and methods employing same |
| CN101238166A (en) * | 2005-07-01 | 2008-08-06 | 金文申有限公司 | Process for production of porous reticulated composite materials |
| WO2009137504A2 (en) * | 2008-05-06 | 2009-11-12 | Millennium Inorganic Chemicals, Inc. | De-polluting and self-cleaning epoxy siloxane coating |
| WO2012058657A2 (en) * | 2010-10-29 | 2012-05-03 | Hardcoat Surfaces Llc | High hardness low surface energy coating |
| CN102757055A (en) * | 2011-04-28 | 2012-10-31 | 昆山智集材料科技有限公司 | Sol-gel preparation method for hydrophobic mesoporous silicon dioxide film |
| CN107629491A (en) * | 2017-05-10 | 2018-01-26 | 中国科学院宁波材料技术与工程研究所 | A kind of mesoporous SiO for flexible substrate2Wear-resisting antireflecting coating and preparation method |
-
2019
- 2019-01-25 CN CN201910071614.1A patent/CN109592908B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1313828A1 (en) * | 2000-08-28 | 2003-05-28 | The Procter & Gamble Company | Fabric care compositions comprising cationic silicones and methods employing same |
| CN101238166A (en) * | 2005-07-01 | 2008-08-06 | 金文申有限公司 | Process for production of porous reticulated composite materials |
| WO2009137504A2 (en) * | 2008-05-06 | 2009-11-12 | Millennium Inorganic Chemicals, Inc. | De-polluting and self-cleaning epoxy siloxane coating |
| WO2012058657A2 (en) * | 2010-10-29 | 2012-05-03 | Hardcoat Surfaces Llc | High hardness low surface energy coating |
| CN102757055A (en) * | 2011-04-28 | 2012-10-31 | 昆山智集材料科技有限公司 | Sol-gel preparation method for hydrophobic mesoporous silicon dioxide film |
| CN107629491A (en) * | 2017-05-10 | 2018-01-26 | 中国科学院宁波材料技术与工程研究所 | A kind of mesoporous SiO for flexible substrate2Wear-resisting antireflecting coating and preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439936A (en) * | 2020-04-29 | 2020-07-24 | 东莞南玻太阳能玻璃有限公司 | Gradient-refraction high-anti-reflection coated glass and preparation method thereof |
| CN112760035A (en) * | 2020-12-30 | 2021-05-07 | 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 |
| CN112759784A (en) * | 2020-12-30 | 2021-05-07 | 苏州太湖电工新材料股份有限公司 | Wear-resistant polyimide composite film and preparation method thereof |
| 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 |
| CN112759784B (en) * | 2020-12-30 | 2023-01-17 | 苏州太湖电工新材料股份有限公司 | Wear-resistant polyimide composite film and preparation method thereof |
| WO2022220928A1 (en) * | 2021-04-15 | 2022-10-20 | Cardinal Cg Company | Flexible aerogel, flexible glass technology |
| CN115926622A (en) * | 2022-12-02 | 2023-04-07 | 吉林大学 | High-surface-hardness, wear-resistant and super-soft hydrophobic coating with silicon-doped carbonized polymer dots as building elements and preparation method thereof |
| 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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