CN103288358A

CN103288358A - Super-hydrophilic self-cleaning antifogging antireflection coating and preparation method thereof

Info

Publication number: CN103288358A
Application number: CN2012100420827A
Authority: CN
Inventors: 贺军辉; 李晓禹
Original assignee: Technical Institute of Physics and Chemistry of CAS
Current assignee: Technical Institute of Physics and Chemistry of CAS
Priority date: 2012-02-22
Filing date: 2012-02-22
Publication date: 2013-09-11
Anticipated expiration: 2032-02-22
Also published as: CN103288358B

Abstract

The invention belongs to the technical field of nano material preparation, and particularly relates to a super-hydrophilic self-cleaning antifogging antireflection coating and a preparation method thereof. The super-hydrophilic self-cleaning antifogging antireflection coating is prepared by electrostatic assembly and a dip-coating method, and the required instruments and equipment are simple and cheap, so that industrialization is expected to be realized. The surface of the super-hydrophilic self-cleaning antifogging antireflection coating has a structure similar to that of a lotus leaf surface in nature, and the antireflection coating is formed by assembling titanium dioxide-silicon dioxide composite nanoparticles and solid silicon dioxide spherical nanoparticles, wherein the appearance of the titanium dioxide-silicon dioxide composite nanoparticles is similar to that of a natural raspberry fruit. The super-hydrophilic self-cleaning antifogging antireflection coating can be used on glass products. The light transmittance of the glass sheet coated with the super-hydrophilic self-cleaning antifogging antireflection coating can be improved from 91.3% to 97.3%, and the super-hydrophilic antifogging coating has an excellent super-hydrophilic antifogging function.

Description

Anti-reflection coating that super hydrophilic automatically cleaning is antifog and preparation method thereof

Technical field

The invention belongs to the nano material preparation technical field, particularly antifog anti-reflection coating of super hydrophilic automatically cleaning and preparation method thereof.

Background technology

The atomizing of glass refers to that moisture or vapor condensation form small water droplet at glass article surface.And automatically cleaning antifog glass (Anti-fogging glass) just refers to that simple glass is after the process special processing, make glass surface have super water-wet behavior, the small water droplet that forms owing to atomizing is paved rapidly, thereby reach the effect of the transmittance that does not influence mirror image, visibility meter and glass, also need not to make cleaning glass through traditional artificial scouring simultaneously.At present, all there is renowned company in developed country in the research and development of specializing in the automatically cleaning antifog glass and making in the world, as Britain Pilkington company, Japanese TOTO company, U.S. PPG company, German GEA company, VTA company, UIC company etc.; The transparent composite self-cleaning antifog glass of people such as U.S. W.L.Tonar development, be to form the photocatalyst Clear coating with photocatalysis on the surface of glass baseplate, form the transparent porous inorganic oxide (SiO of possess hydrophilic property again on the surface of photocatalyst Clear coating ₂And Al ₂O ₃) film.Yet these technology have all been utilized TiO ₂Photocatalysis characteristic impels glass surface to reach super hydrophilic, and applicable elements can be restricted, because need there be the environment of illumination just can carry out katalysis; And the light transmission of these coatings is all bad.

In recent years, scientist has the surface topology of the lotus leaf of self-cleaning function by research, find that the lotus leaf microcosmic surface is very coarse, and formed by the super-hydrophobicity material, so, scientist begins preparation and has the spheroidal particle of uneven surface (namely being similar to the shape of raspberry), and utilizes this spheroidal particle to prepare automatic cleaning coating.Ming etc. assemble preparation raspberry shape particle on the silicon-dioxide macroparticle surface of epoxy group(ing) functionalization by chemical bond with the silicon-dioxide small-particle of amino functional, and utilize this composite particles to construct to have the coarse based superhydrophobic thin films of two yardsticks (W.Ming, D.Wu, R.van Benthem, and G.de With, Nano Letters, 2005,5,2298.), but this method generally needs the finishing process, and this has not only increased experimental procedure, has also improved preparation cost.The present patent application people once utilized two kinds of particle diameter SiO of size ₂Particle assembling raspberry shape spheroidal particle (publication number: CN101168475A) with preparation raspberry shape composite particles (application number 200910092551.4), they have all successfully assembled out the silica dioxide coating of the porous of super hydrophilic and anti-fog performance, though they all have good super hydrophilic antifogging performance, but its self-cleaning performance must rely on precipitation, is not limited to when having seldom area applications of precipitation or precipitation.Therefore it is very necessary and significant developing and develop the automatically cleaning anti-fog function coating with the illumination of taking into account and precipitation restriction.

Summary of the invention

One of purpose of the present invention provides has the anti-reflection coating antifog with the super hydrophilic automatically cleaning of the titania-silica composite nanoparticle of raspberry fruit similar, and the transmittance that scribbles the sheet glass of this coating can bring up to 97% from 91%.

Two of purpose of the present invention provides and adopts the static self-assembling method, with the alternately assembling of nanoparticle and polyelectrolyte, thereby provide preparation method and technology is simple, raw material is cheap, cost is low, applied widely surface to have preparation method with the antifog anti-reflection coating of the super hydrophilic automatically cleaning of the titania-silica composite nanoparticle of raspberry fruit similar.

The present invention has adopted particle diameter to be approximately the solid SiO of 20nm ₂Nano spherical particle is the titania-silica composite nanoparticle of 30～110nm with having with the particle diameter of raspberry fruit similar, utilizes easy Layer-by-Layer (LbL) layer-by-layer in-situ preparing to go out super hydrophilic (water droplet is at contact angle convergence 0 degree that scribbles on the glass surface of this coating) antifog anti-reflection coating of automatically cleaning of coarse structure.The present invention is by regulating solid SiO ₂The assembling number of plies of the titania-silica composite nanoparticle of nano spherical particle and nucleocapsid structure can be prepared the two coarse coatings of stratum of multiple similar lotus leaf surface structure, and hydrophilic contact angle is near zero degree.The transmittance of sheet glass that scribbles the automatically cleaning anti-reflection coating of super hydrophilic antifogging of the present invention can bring up to 97% from 91%.The invention provides a kind ofly at the visible region anti-reflection, have the multi-functional coatings preparation method of super hydrophilic automatically cleaning anti-fog performance simultaneously, technical superiority such as preparation technology is simple, cost is low, effect is obvious, applied widely.

Photochemical catalysis self-cleaning performance and Nano particles of silicon dioxide layer that the antifog anti-reflection coating of super hydrophilic automatically cleaning of the present invention combines the titanium dioxide excellence need not the advantage that ultraviolet lighting just has super hydrophilicity.The antifog anti-reflection coating of super hydrophilic automatically cleaning of the present invention is under the condition of precipitation, thereby drop can be sprawled fast at coatingsurface and take away pollutent, and under the situation of no precipitation, the photocatalysis performance of TiO 2 particles can degradation of contaminant, still can bring into play self-cleaning performance.

The antifog anti-reflection coating of super hydrophilic automatically cleaning of the present invention is to adopt solid SiO ₂The suspension of the titania-silica composite nanoparticle preparation of nano spherical particle and nucleocapsid structure takes the method for dip-coating with solid SiO ₂The titania-silica composite nanoparticle of nano spherical particle and nucleocapsid structure and polyelectrolyte deposit on the substrate (as sheet glass) by the static assembling, prepare described anti-reflection coating finally by crossing calcining.Required plant and instrument is simple, cheap, is easy to industrialization.

The surface of the anti-reflection coating that super hydrophilic automatically cleaning of the present invention is antifog has the structure similar to the lotus leaf surface of occurring in nature, and this anti-reflection coating is to be assembled by the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar and the spherical nanoparticle of solid silicon-dioxide.

The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is the SiO that is approximately 28～97nm by the particle diameter as nuclear ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is approximately 1～13nm ₂Spherical small-particle is composited.

The particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is approximately 30～110nm.

The particle diameter of the spherical nanoparticle of described solid silicon-dioxide is approximately 20nm.

Described particle diameter is approximately the solid SiO of 20nm ₂Nano spherical particle and particle diameter are approximately the SiO in the titania-silica composite nanoparticle of 30～110nm ₂Spherical macroparticle can according to

(

W, Fink A, Bohn E.Journal of Colloid ﹠amp; Interface Science, 1968,26:62～69) method is prepared.

Titania-silica composite nanoparticle when described nucleocapsid structure, evenly being adsorbed on substrate (as sheet glass) go up to form after the coating through calcining, the titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle that has with natural raspberry fruit similar, and this titania-silica composite nanoparticle is the SiO that is approximately 28～97nm by the particle diameter as nuclear ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is approximately 1～13nm ₂Spherical small-particle is composited.

Coating described in the present invention is by solid SiO ₂The polyelectrolyte that deposits on the negative charge of nano spherical particle surface band and the substrate or the titania-silica composite nanoparticle of nucleocapsid structure with positive charge the electrostatic attraction self-assembly and form, each step finishes all and thoroughly washs with distilled water, dries up with nitrogen.

Described polyelectrolyte is diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate.

The preparation method of the anti-reflection coating that super hydrophilic automatically cleaning of the present invention is antifog may further comprise the steps:

(1) with tetraethoxy hydrolysis under ammonia-catalyzed, prepares and contain single SiO that disperses particle diameter to be approximately 28～97nm ₂The suspension of nano spherical particle, suspension stirring at room (the general time of stirring is 2～6 hours), dropping and tetraethoxy mol ratio are 1: 1～4: 1 titanium tetraisopropylate under agitation condition, stirring reaction (time of general stirring reaction is 2～6 hours), centrifugation, supersound washing obtains the titania-silica composite nanoparticle of nucleocapsid structure; The titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed the suspension (be preferably and contain the suspension that massfraction is the titania-silica composite nanoparticle of 0.4% nucleocapsid structure) of the titania-silica composite nanoparticle that contains nucleocapsid structure in water;

(2) with tetraethoxy hydrolysis under ammonia-catalyzed, prepare and contain single solid SiO that disperses particle diameter to be approximately 20nm ₂The suspension of nano spherical particle;

(3) sheet glass that obtains after will cleaning up and drying up with nitrogen is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL and takes out after 2～10 minutes, in surface of plate glass deposition one deck diallyl dimethyl ammoniumchloride coating,, dry up with nitrogen to remove the diallyl dimethyl ammoniumchloride of physical adsorption with distilled water wash; And then be immersed in the sodium polystyrene sulfonate aqueous solution that concentration is 1～3mg/mL 2～10 minutes, take out, use distilled water wash, dry up with nitrogen, on the diallyl dimethyl ammoniumchloride coating, deposit one deck sodium polystyrene sulfonate coating again; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until being deposited 5～20 layers of bilayer that is made of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating altogether, obtaining at last one deck that sheet glass deposits is the sheet glass of sodium polystyrene sulfonate coating;

(4) sheet glass that step (3) is prepared is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL to take out in 2～10 minutes and uses distilled water wash, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is approximately 20nm that contains that step (2) prepares ₂Take out after 2～10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer ₂The nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption ₂Nano spherical particle dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition ₂The processing step of nano spherical particle coating is on the sheet glass of sodium polystyrene sulfonate layer until the last one deck that obtains in step (3), is deposited 1～3 layer of solid SiO that is approximately 20nm by diallyl dimethyl ammoniumchloride coating and particle diameter altogether ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer; Or

Last one deck that step (3) is prepared is that the sheet glass of sodium polystyrene sulfonate coating was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes, take out and use distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is approximately 20nm that contains that step (2) prepares ₂Take out the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure in the suspension of nano spherical particle after 2～10 minutes ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer, be on the sheet glass of sodium polystyrene sulfonate coating until the last one deck that obtains in step (3), deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether and be approximately the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

What (5) step (4) is prepared deposits 1～3 layer of solid SiO that is approximately 20nm by diallyl dimethyl ammoniumchloride coating and particle diameter altogether ₂The sheet glass of the bilayer that the nano spherical particle layer constitutes was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes, took out and used distilled water wash, and nitrogen dries up, at solid SiO ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is approximately 20nm that contains that step (2) prepares ₂Take out the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure in the suspension of nano spherical particle after 2～10 minutes ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (4) ₂On the sheet glass of nano spherical particle layer, deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether and be approximately the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer; Then this sheet glass is put into retort furnace, be to calcine under 400～550 degrees centigrade in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar; Or

2 layers of titania-silica composite nano-granule sublayer and the particle diameter by nucleocapsid structure that deposit altogether that step (4) is prepared are approximately the solid SiO of 20nm ₂The sheet glass of the bilayer that the nano spherical particle layer constitutes is put into retort furnace, be to calcine under 400～550 degrees centigrade in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar;

Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining; The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is the SiO that is approximately 28～97nm by the particle diameter as nuclear ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is approximately 1～13nm ₂Spherical small-particle is composited.

Before sheet glass is put into retort furnace, the sheet glass that the present invention can further will calcine was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at solid SiO ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer, obtaining at last one deck that sheet glass deposits is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure; And then titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that will prepare ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 400～550 degrees centigrade in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into pattern and has titania-silica composite nanoparticle with natural raspberry fruit similar, obtains the antifog anti-reflection coating of super hydrophilic automatically cleaning.

The described suspension that contains the titania-silica composite nanoparticle of nucleocapsid structure, the massfraction of the titania-silica composite nanoparticle of nucleocapsid structure is 0.4% in its suspension.

Described is that the time of calcining under 400～550 degrees centigrade is 1～3 hour in temperature.

Described sheet glass, for example, the glass window of family and commercial building, glass sunroof, glass curtain wall, Household bathroom mirror, windshield, automobile rearview mirror, automobile background glass or eye plate etc.

The present invention with the cheap and sheet glass easily obtained as substrate, again by layer upon layer electrostatic self-assembly deposition charged polyelectrolytes and solid SiO ₂Nano spherical particle.Because the increase of the porosity between the nanoparticle makes the transmittance of the sheet glass that scribbles the antifog anti-reflection coating of super hydrophilic automatically cleaning bring up to 97% from 91%.

The present invention is further illustrated below in conjunction with drawings and Examples, and wherein the ST in the accompanying drawing represents that particle diameter is the titania-silica composite nanoparticle with raspberry fruit similar of having of 75nm, and S represents that particle diameter is the solid SiO of 20nm ₂Nano spherical particle, the following number of plies that is designated as coating that bracket is outer.

Description of drawings

Fig. 1. (a-b) particle diameter of the embodiment of the invention 1 is the transmission electron microscope picture of titania-silica composite nanoparticle of the nucleocapsid structure of 75nm; (c-d) be that particle diameter is titania-silica composite nanoparticle calcining transmission electron microscope pictures after 3 hours under temperature is 550 degrees centigrade of the nucleocapsid structure of 75nm; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.

Fig. 2. the depositing of the embodiment of the invention 1 (ST/S) ₂The scanning electron microscope picture of the sheet glass of coating, the following number of plies that is designated as coating that bracket is outer.

Fig. 3. the embodiment of the invention 2 deposit S ₃(ST/S) ₂The scanning electron microscope picture of the sheet glass of coating, the following number of plies that is designated as coating that bracket is outer.

Fig. 4. the embodiment of the invention 3 deposit S ₃(ST/S) ₂The scanning electron microscope picture of the sheet glass of ST coating, the following number of plies that is designated as coating that bracket is outer.

Fig. 5. the embodiment of the invention 1～3 deposits (ST/S) ₂, S ₃(ST/S) ₂, S ₃(ST/S) ₂ST coating and do not have the transmitted light spectrogram of the sheet glass of coating.

Fig. 6. the embodiment of the invention 1～3 deposits (ST/S) ₂, S ₃(ST/S) ₂, S ₃(ST/S) ₂ST coating and do not have the reflected light spectrogram of the sheet glass of coating.

Fig. 7. (a) Jie Jing simple glass sheet and deposit S ₃(ST/S) ₂The anti-fog performance photo of the sheet glass of ST coating (embodiment 3).Method is two samples to be put into to take out behind-5 degrees centigrade the refrigerator simultaneously be placed on room temperature environment, and simple glass sheet (descend) produces the little water droplet that atomizes rapidly, and cated sheet glass (on) do not produce atomizing, keep transparent always.(b) be clean simple glass sheet (left side) and deposit S ₃(ST/S) ₂The photo of the reflective situation of the sheet glass of ST coating (right side, embodiment 3).

Fig. 8. (a) deposit S ₃(ST/S) ₂The abosrption spectrogram of the photocatalytic degradation methylene blue of the sheet glass of ST coating (embodiment 3) experiment (b) has shown the time comparison diagram that the glass that do not have coating and cated glass light transmitance are recovered.

Fig. 9. (a-b) particle diameter of the embodiment of the invention 4 is the transmission electron microscope picture of titania-silica composite nanoparticle of the nucleocapsid structure of 30nm; (c-d) be that particle diameter is titania-silica composite nanoparticle calcining transmission electron microscope pictures after 2.5 hours under temperature is 550 degrees centigrade of the nucleocapsid structure of 30nm; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.

Figure 10. (a-b) particle diameter of the embodiment of the invention 5 is the transmission electron microscope picture of titania-silica composite nanoparticle of the nucleocapsid structure of 110nm; (c-d) be that particle diameter is titania-silica composite nanoparticle calcining transmission electron microscope pictures after 3 hours under temperature is 550 degrees centigrade of the nucleocapsid structure of 110nm; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.

Embodiment

Embodiment 1

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: the solid SiO that is respectively 20nm by particle diameter ₂Two bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes assemble, and its preparation method may further comprise the steps:

(1) with 5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirred 1～3 minute down at 60 degrees centigrade, and Dropwise 5 mL tetraethoxy (TEOS) under agitation, 60 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 20nm ₂The translucent suspension of nano spherical particle, and to become massfraction with alcohol dilution be that 0.1%～4% suspension is standby;

With 7.5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirs 1～3 minute down at 40 degrees centigrade, and under agitation drips 3mL tetraethoxy (TEOS), 40 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 70nm ₂The translucent suspension of nano spherical particle, after the suspension stirring at room 2 hours, dropping and tetraethoxy mol ratio are 1: 1 titanium tetraisopropylate under agitation condition, stirring reaction 6 hours, centrifugation, supersound washing, obtaining particle diameter is the titania-silica composite nanoparticle of the nucleocapsid structure of 75nm, the titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed in water contain the suspension that massfraction is the titania-silica composite nanoparticle of 0.4% nucleocapsid structure;

(2) sheet glass that obtains after will cleaning up and drying up with nitrogen is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL and takes out after 2～10 minutes, in glass sheet surface deposition one deck diallyl dimethyl ammoniumchloride coating,, dry up with nitrogen to remove the diallyl dimethyl ammoniumchloride of physical adsorption with distilled water wash; And then be immersed in the sodium polystyrene sulfonate aqueous solution that concentration is 1～3mg/mL 2～10 minutes, take out, use distilled water wash, dry up with nitrogen, on the diallyl dimethyl ammoniumchloride coating, deposit one deck sodium polystyrene sulfonate coating again; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until being deposited 5～20 layers of bilayer that is made of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating altogether, obtaining at last one deck that sheet glass deposits is the sheet glass of sodium polystyrene sulfonate coating;

(3) sheet glass that step (2) is prepared is immersed in that step (1) prepares contains in the suspension of titania-silica composite nanoparticle (particle diameter is 75nm) that massfraction is 0.4% nucleocapsid structure 2～10 minutes, take out and use distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer, be on the sheet glass of sodium polystyrene sulfonate coating until the last one deck that obtains in step (2), being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(4) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (3) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 550 degrees centigrade 3 hours in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar be by as nuclear particle diameter be the solid SiO of 70nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited.Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

Observe the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 75nm (Fig. 1 a-b) and after calcining, change pattern into and the titania-silica composite nanoparticle of natural raspberry fruit similar (Fig. 1 c-d) by transmission electron micrograph.

By the surface topography of this anti-reflection coating of scanning electron microscopic observation as can be known, the surface of this anti-reflection coating has and the similar coarse structure of the lotus leaf surface of occurring in nature, and it is to be the solid SiO of 2nm by particle diameter ₂Nano spherical particle and particle diameter are that the titania-silica composite nano-granule sublayer of the pattern of 75nm and natural raspberry fruit similar assembles (is the solid SiO of 70nm by the particle diameter as nuclear ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited), and the surface is that particle diameter is the solid SiO of 20nm ₂The structure of nano spherical particle layer (Fig. 2).

The transmittance of this anti-reflection coating as shown in Figure 5, maximum transmission is 96.3%, reflectivity as shown in Figure 6.

Embodiment 2

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle and particle diameter are respectively the solid SiO of 20nm ₂2 bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes assemble, and its preparation method may further comprise the steps:

(3) sheet glass that step (2) is prepared is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL to take out in 2～10 minutes and uses distilled water wash, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer ₂The nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption ₂Nano spherical particle dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition ₂The processing step of nano spherical particle coating is on the sheet glass of sodium polystyrene sulfonate coating until the last one deck that obtains in step (2), is deposited altogether that to have three layers by diallyl dimethyl ammoniumchloride coating and particle diameter be the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(4) sheet glass that step (3) is prepared is immersed in that step (1) prepares contains in the suspension of titania-silica composite nanoparticle (particle diameter is 75nm) that massfraction is 0.4% nucleocapsid structure 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of skin ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (3) ₂On the sheet glass of nano spherical particle layer, being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (4) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 400～550 degrees centigrade 1 hour in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar be by as nuclear particle diameter be the solid SiO of 70nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited.Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

By the surface topography of this anti-reflection coating of scanning electron microscopic observation as can be known, the coarse structure that this anti-reflection coating has is to be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle and particle diameter are respectively the solid SiO of 20nm ₂Two bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes assemble, and the surface is that particle diameter is the solid SiO of 20nm ₂The structure of nano spherical particle layer (Fig. 3).

The transmittance of this anti-reflection coating as shown in Figure 5, maximum transmission is 97.1%, reflectivity as shown in Figure 6.

Embodiment 3

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle, particle diameter are respectively the solid SiO of 20nm ₂2 bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes, with one deck particle diameter be that the pattern of 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble, its preparation method may further comprise the steps:

(4) sheet glass that step (3) is prepared is immersed in that step (1) prepares contains in the suspension of titania-silica composite nanoparticle (particle diameter is 75nm) that massfraction is 0.4% nucleocapsid structure 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of one deck ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (3) ₂On the sheet glass of nano spherical particle layer, being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) sheet glass that step (4) prepared immerses that step (1) prepares, and to contain massfraction be that 0.4% particle diameter is in the suspension of titania-silica composite nanoparticle of nucleocapsid structure of 75nm 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of skin ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; Obtain at last one deck that sheet glass deposits is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;

(6) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (5) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 400～550 degrees centigrade 2 hours in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar be by as nuclear particle diameter be the solid SiO of 70nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited.Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

By the surface topography of this anti-reflection coating of scanning electron microscopic observation as can be known, the coarse structure that this anti-reflection coating has is to be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle, particle diameter are respectively the solid SiO of 20nm ₂Two bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes, with one deck particle diameter be that the pattern of 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble, and the surface is that particle diameter is the titania-silica composite nano-granule sublayer (Fig. 4) of the natural raspberry fruit of 75nm similar.

The transmittance of this anti-reflection coating as shown in Figure 5, maximum transmission is 97.3%, reflectivity as shown in Figure 6.

Antifog contrast picture as shown in Figure 7.It is freezing that simple glass sheet and the sheet glass that scribbles this coating are put into refrigerator earlier, takes out observation then rapidly, compares with simple glass, and the sheet glass that scribbles this coating has significantly anti-fog effect.

The photochemical catalysis self-cleaning performance as shown in Figure 8.This anti-reflection coating was put into the 10mg/L methylene blue solution 5 minutes, the transmitance of coating decline to some extent because of the methylene blue of absorption after the standing and drying after 100mm/min lifts.Under the irradiation of 250W ultraviolet mercury lamp, degraded the gradually methylene blue of surface adsorption of coating, therefore the transmitance of coating is recovered gradually.After irradiation 30 minutes, the coating transmitance has returned to the not preceding transmitance of absorption fully.Fig. 8 b has shown the time comparison diagram that the glass that do not have coating and cated glass transmitance are recovered, this process explanation this anti-reflection coating have good self-cleaning performance.

Embodiment 4

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle, particle diameter are respectively the solid SiO of 20nm ₂2 bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 30nm and natural raspberry fruit similar constitutes, with one deck particle diameter be that the pattern of 30nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble, its preparation method may further comprise the steps:

(1) with 5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirred 1～3 minute down at 60 degrees centigrade, and Dropwise 5 mL tetraethoxy (TEOS) under agitation, 60 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 20nm ₂The translucent suspension of nano spherical particle;

With 7.5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirs 1～3 minute down at 40 degrees centigrade, and under agitation drips 3mL tetraethoxy (TEOS), 40 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 28nm ₂The translucent suspension of nano spherical particle, after the suspension stirring at room 2 hours, dropping and tetraethoxy mol ratio are 1: 1 titanium tetraisopropylate under agitation condition, stirring reaction 6 hours, centrifugation, supersound washing, obtaining particle diameter is the titania-silica composite nanoparticle of the nucleocapsid structure of 30nm, the titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed in water contain the suspension that massfraction is the titania-silica composite nanoparticle of 0.4% nucleocapsid structure;

(3) sheet glass that step (2) is prepared is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL to take out in 2～10 minutes and uses distilled water wash, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂Take out after 2～10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer ₂The nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption ₂Nano spherical particle dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition ₂The processing step of nano spherical particle coating is on the sheet glass of sodium polystyrene sulfonate coating until the last one deck that obtains in step (2), is deposited altogether that to have three layers by diallyl dimethyl ammoniumchloride coating and particle diameter be the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(4) sheet glass that step (3) is prepared is immersed in that step (1) prepares contains in the suspension of titania-silica composite nanoparticle (particle diameter is 30nm) that massfraction is 0.4% nucleocapsid structure 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of one deck ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂Take out the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure in the suspension of nano spherical particle after 2～10 minutes ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (3) ₂On the sheet glass of nano spherical particle layer, being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) sheet glass that step (4) prepared immerses that step (1) prepares, and to contain massfraction be that 0.4% particle diameter is in the suspension of titania-silica composite nanoparticle of nucleocapsid structure of 30nm 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of skin ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; Obtain at last one deck that sheet glass deposits is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;

(6) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (5) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 550 degrees centigrade 2.5 hours in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar be by as nuclear particle diameter be the solid SiO of 28nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited.Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

Embodiment 5

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: be the solid SiO of 20nm by 3 layers of particle diameter ₂Nano spherical particle, particle diameter are respectively the solid SiO of 20nm ₂2 bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 110nm and natural raspberry fruit similar constitutes, with one deck particle diameter be that the pattern of 110nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble, its preparation method may further comprise the steps:

With 7.5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirred 1～3 minute down at 40 degrees centigrade, and under agitation drip 3mL tetraethoxy (TEOS), 40 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 100nm ₂The translucent suspension of nano spherical particle, after the suspension stirring at room 2 hours, dropping and tetraethoxy mol ratio are 1: 1 titanium tetraisopropylate under agitation condition, stirring reaction 6 hours, centrifugation, supersound washing, obtaining particle diameter is the titania-silica composite nanoparticle of the nucleocapsid structure of 110nm, the titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed in water contain the suspension that massfraction is the titania-silica composite nanoparticle of 0.4% nucleocapsid structure;

(4) sheet glass that step (3) is prepared is immersed in that step (1) prepares contains in the suspension of titania-silica composite nanoparticle (particle diameter is 110nm) that massfraction is 0.4% nucleocapsid structure 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of one deck ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (3) ₂On the sheet glass of nano spherical particle layer, being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) sheet glass that step (4) prepared immerses that step (1) prepares, and to contain massfraction be that 0.4% particle diameter is in the suspension of titania-silica composite nanoparticle of nucleocapsid structure of 110nm 2～10 minutes, take out and use distilled water wash, nitrogen dries up, at the solid SiO of skin ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; Obtain at last one deck that sheet glass deposits is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;

(6) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (5) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 550 degrees centigrade 3 hours in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 100nm by the particle diameter as nuclear ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 5nm ₂Spherical small-particle is composited.Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

Observe the titanium dioxide of core-shell structure that particle diameter is 110nm-silicon-dioxide composite nanoparticle (Figure 10 a-b) changes pattern and natural raspberry fruit similar into after calcining titania-silica composite nanoparticle (Figure 10 c-d) by transmission electron micrograph.

Embodiment 6

The anti-reflection coating that super hydrophilic automatically cleaning is antifog: be the solid SiO of 20nm by particle diameter ₂The nano spherical particle layer, be respectively the solid SiO of 20nm with particle diameter ₂Two bilayers that the titania-silica composite nano-granule sublayer of the pattern of nano spherical particle and 75nm and natural raspberry fruit similar constitutes assemble, and its preparation method may further comprise the steps:

With 7.5mL ammoniacal liquor, 50～150mL dehydrated alcohol joins in the Erlenmeyer flask and stirred under the room temperature 8～12 minutes, stirs 1～3 minute down at 40 degrees centigrade, and under agitation drips 3mL tetraethoxy (TEOS), 40 degrees centigrade of vigorous stirring 10～14 hours, obtain containing the solid SiO that particle diameter is 70nm ₂The translucent suspension of nano spherical particle, suspension stirring at room are after 2 hours, and dropping and tetraethoxy mol ratio are 1: 1 titanium tetraisopropylate under agitation condition, stirring reaction 6 hours, centrifugation, supersound washing, obtaining by the particle diameter as nuclear is the solid SiO of 70nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂The particle diameter that spherical small-particle is composited is the titania-silica composite nanoparticle of the nucleocapsid structure of 75nm, the titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed in water contain the suspension that massfraction is the titania-silica composite nanoparticle of 0.4% nucleocapsid structure;

(3) sheet glass that step (2) is prepared is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL to take out in 2～10 minutes and uses distilled water wash, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (1) prepares ₂The massfraction of nano spherical particle is to take out after 2～10 minutes in 0.1%～4% the suspension, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer ₂The nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption ₂Nano spherical particle dries up with nitrogen; Obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) titania-silica composite nanoparticle and the solid SiO with nucleocapsid structure that step (4) is prepared ₂The sheet glass of nano spherical particle coating is put into retort furnace, be to calcine under 400～550 degrees centigrade 1 hour in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar be by as nuclear particle diameter be the solid SiO of 70nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1nm ₂Spherical small-particle is composited.Finally obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining.

Claims

1. anti-reflection coating that super hydrophilic automatically cleaning is antifog, it is characterized in that: the surface of described anti-reflection coating has the structure similar to the lotus leaf surface of occurring in nature, and this anti-reflection coating is to be assembled by the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar and the spherical nanoparticle of solid silicon-dioxide;

The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar be by as nuclear particle diameter be the SiO of 28～97nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1～13nm ₂Spherical small-particle is composited;

Described solid SiO ₂The particle diameter of nano spherical particle is 20nm.

2. the antifog anti-reflection coating of super hydrophilic automatically cleaning according to claim 1, it is characterized in that: the particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is 30～110nm.

3. the preparation method of the antifog anti-reflection coating of a super hydrophilic automatically cleaning according to claim 1 and 2 is characterized in that this method may further comprise the steps:

(1) with tetraethoxy hydrolysis under ammonia-catalyzed, prepares and contain the SiO that particle diameter is 28～97nm ₂The suspension of nano spherical particle, stirring at room suspension, dropping and tetraethoxy mol ratio are 1: 1～4: 1 titanium tetraisopropylate under agitation condition, stirring reaction, centrifugation, supersound washing obtains the titania-silica composite nanoparticle of nucleocapsid structure; The titania-silica composite nanoparticle ultra-sonic dispersion of the nucleocapsid structure that obtains is formed the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure in water;

(2) with tetraethoxy hydrolysis under ammonia-catalyzed, prepare and contain the solid SiO that particle diameter is 20nm ₂The suspension of nano spherical particle;

(4) sheet glass that step (3) is prepared is immersed in the aqueous solution of diallyl dimethyl ammoniumchloride that concentration is 1～3mg/mL to take out in 2～10 minutes and uses distilled water wash, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (2) prepares ₂Take out after 2～10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer ₂The nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption ₂Nano spherical particle dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition ₂The processing step of nano spherical particle coating is on the sheet glass of sodium polystyrene sulfonate layer until the last one deck that obtains in step (3), and being deposited 1～3 layer altogether is the solid SiO of 20nm by diallyl dimethyl ammoniumchloride coating and particle diameter ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer; Or

Last one deck that step (3) is prepared is that the sheet glass of sodium polystyrene sulfonate coating was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes, take out and use distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (2) prepares ₂Take out the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure in the suspension of nano spherical particle after 2～10 minutes ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer, be on the sheet glass of sodium polystyrene sulfonate coating until the last one deck that obtains in step (3), being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer;

(5) step (4) is prepared to deposit 1～3 layer altogether be the solid SiO of 20nm by diallyl dimethyl ammoniumchloride coating and particle diameter ₂The sheet glass of the bilayer that the nano spherical particle layer constitutes was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes, took out and used distilled water wash, and nitrogen dries up, at solid SiO ₂The titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO that particle diameter is 20nm that contains that step (2) prepares ₂Take out the solid SiO of surface deposition one deck in the titania-silica composite nano-granule sublayer of nucleocapsid structure in the suspension of nano spherical particle after 2～10 minutes ₂The nano spherical particle layer is used distilled water wash, dries up with nitrogen again; Repeat titania-silica composite nano-granule sublayer and the solid SiO of above-mentioned deposition nucleocapsid structure ₂The processing step of nano spherical particle layer is solid SiO until the last one deck that obtains in step (4) ₂On the sheet glass of nano spherical particle layer, being deposited 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether is the solid SiO of 20nm ₂The bilayer that the nano spherical particle layer constitutes, obtaining at last one deck that sheet glass deposits is solid SiO ₂The sheet glass of nano spherical particle layer; Then this sheet glass is put into retort furnace, be to calcine under 400～550 degrees centigrade in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar; Or

With step (4) prepare to deposit 2 layers of titania-silica composite nano-granule sublayer and particle diameter by nucleocapsid structure altogether be the solid SiO of 20nm ₂The sheet glass of the bilayer that the nano spherical particle layer constitutes is put into retort furnace, be to calcine under 400～550 degrees centigrade in temperature, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar;

Obtain the antifog anti-reflection coating of super hydrophilic automatically cleaning after the calcining; The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar be by as nuclear particle diameter be the SiO of 28～97nm ₂Spherical macroparticle be coated on the TiO that outer field particle diameter is 1～13nm ₂Spherical small-particle is composited.

4. preparation method according to claim 3, it is characterized in that: before sheet glass is put into retort furnace, the sheet glass that will calcine was immersed in the suspension of the titania-silica composite nanoparticle that contains nucleocapsid structure that step (1) prepares 2～10 minutes earlier, take out and use distilled water wash, nitrogen dries up, at solid SiO ₂Putting into retort furnace again behind the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer calcines.

5. according to claim 3 or 4 described preparation methods, it is characterized in that: the described suspension that contains the titania-silica composite nanoparticle of nucleocapsid structure, the massfraction of the titania-silica composite nanoparticle of nucleocapsid structure is 0.4% in its suspension.

6. preparation method according to claim 3, it is characterized in that: the time of the described stirring of step (1) is 2～6 hours.

7. according to claim 3 or 4 described preparation methods, it is characterized in that: the time of described calcining is 1～3 hour.

8. preparation method according to claim 3, it is characterized in that: the particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is 30～110nm.