CN104449357B - A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof - Google Patents

A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof Download PDF

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CN104449357B
CN104449357B CN201410693047.0A CN201410693047A CN104449357B CN 104449357 B CN104449357 B CN 104449357B CN 201410693047 A CN201410693047 A CN 201410693047A CN 104449357 B CN104449357 B CN 104449357B
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super
hydrophobic
dispersion liquid
solvent
fluorine
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CN104449357A (en
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杜淼
李房
郑强
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of transparent hydrophobic coating material, its raw material includes aerosil nanoparticle dispersion liquid and the water repellent agent being made up of aerosil nanoparticle and solvent.The invention also discloses the preparation method of transparent hydrophobic coating, the erasing substrate preparation of aerosil nanoparticle dispersion liquid there is the coating of micro-nano structure, obtain after carrying out surface-hydrophobicized process by water repellent agent.The super-hydrophobic coating material that the present invention provides can change hydrophobic treatment mode flexibly according to applying the different of substrate, the method preparing super-hydrophobic coat is few to Material Needs, and use cost is extremely low, and method is simple, apply conveniently, the preparation of large area high-efficiency multi-function super-hydrophobic coat can be carried out;Prepare super-hydrophobic coat have super-hydrophobicity, high transparent, anti-droplet impact ability, temperature and the pH stability of excellence, durability, can erasing property repeatedly, and can apply to nearly all surface of solids being currently known.

Description

A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof
Technical field
The present invention relates to the technical field of hydrophobic coating material, be specifically related to one and have optical lens simultaneously concurrently Bright property, durability, anti-droplet impact, temperature and pH stability, renewable, can be applied over The transparent hydrophobic material of various material surfaces and the coating of preparation thereof.
Background technology
Nature many biological surfaces all possess special moistened surface behavior.Researcher finds, by water Drip and the most all can obtain the contact more than 150 ° in Folium Nelumbinis upper surface, rice leaf upper surface, water skipper foot Angle.This surface to water droplet performance excess of export anti-wettability is referred to as super hydrophobic surface.Through further section Learning research to find, these biological surfaces are respectively provided with the coarse structure on micro-scale, these microstructures When making water droplet contact with surface cannot complete wetting surface, air retained in micro-structured inner thus Forming air bag, due to the existence of air bag, water droplet can slip away from surface easily.Owing to it is special Surface resist wet behavior, super hydrophobic surface has the features such as waterproof, automatically cleaning.Inspired by this, grind Study carefully and prepare and there is ultra-hydrophobicity surface cause and pay close attention to widely and pay attention to.It is provided simultaneously with the transparency Super-hydrophobic coat, in the application high to optical demands, such as windshield, building There is huge potential using value in the fields such as glass pane, swimming goggle eyepiece.
From the point of view of existing theory, prepare super hydrophobic surface and typically to meet two key factors: one is table Mask has the structure of micro-scale, and this is that super hydrophobic surface is different from the maximum poor of general hydrophobic surface Different;Two is that material itself has low-surface-energy or the material of surface attachment one layered low-surface energy.Preparation Super hydrophobic surface is typically by template, photoetch method, plasma etching method, layer assembly method etc. Multiple technologies and method.These methods are owing to causing it to be only applicable to laboratory to the demand of equipment is the highest Prepared by the super hydrophobic surface of research or little area.
The super-hydrophobic coat developed based on ripe coating technology can reduce the demand to equipment, simultaneously Simplify construction procedure, the most effectively prepare super hydrophobic surface for large area and bring possibility.
Chinese patent application CN104046152A discloses the preparation method of a kind of super-hydrophobic coat, bag Include, step 1: according to volume parts ratio, take 50~80 parts of mass fractions be 2%~15% hydrophobic Nanoparticulate dispersion, 20~50 parts of mass fractions be 1%~10% polystyrene nanoparticles divide Dissipate liquid, 0~30 part of solvent mixing, and ultrasonic disperse, thus obtain a mixed liquor;Step 2: by institute State mixed liquor to be formed in a substrate surface and base internal micro structure;Step 3: by step 2 Substrate is dried, and then heats to 160~230 DEG C of bakings and makes described polystyrene nanoparticles melt, takes Going out nature to dry, the method construction is excessively complicated.
Chinese patent application CN103469184A discloses the preparation method of a kind of super-hydrophobic bismuth coating. By electroless plating techniques, zinc metal sheet plates layer of metal bismuth.Bismuth metal layer has penniform Micro-nano compound structure, shows super-hydrophobicity after long-chain fatty alcohol hydrophobically modified.But the method is only It is applicable to metal surface, and galvanoplastic are polluted big, various sizes of surface is needed the chi that design is corresponding Very little tankage.
Chinese patent application CN103964701A discloses a kind of SiO2/ politef hydridization is super thin The preparation method of water coating, by silane coupler at suitable temperature and pH value condition at alcohol water Mixed solvent hydrolyze and reacts with Ludox, making silica particle surface grafting organic group;? The PTFE emulsion and the auxiliary agent that add certain volume in modified Ludox make homogeneous mixture system also Ageing certain time waits coating problems;Preparation coating, both can effectively improve politef with The bonding force of base material, improves hardness and wearability, again can with the roughness on structure coating surface, thus Improve the contact angle on surface.
Chinese patent application CN103788802A discloses the preparation method of a kind of super-hydrophobic coat, bag Include following steps: prepare fluorine richness polyacrylate;Prepare silane coupler modified nano silicon; Described fluorine richness polyacrylate is dissolved in organic solvent formation mixed liquor, then to described mixed liquor The described silane coupler modified nano silicon of middle addition, mix homogeneously obtains complex sol;At base Complex sol described in application on material, solidification is dried.Have good after the super-hydrophobic coat solidification of preparation Hydrophobic performance and mechanical property, have preferable heat resistance simultaneously.
Chinese patent application CN103753908A discloses a kind of super-hydrophobic coat, described super-hydrophobic painting Layer is by being alternately coated in suprabasil inorganic layer and organic layer forms, and described inorganic layer is inorganic nano-particle Sublayer, organic layer is organic silicon modified polyurethane layer, and the bottom and top are organic layer.
U.S. Patent application US2014/0106127A1 discloses one and has the transparency and super-hydrophobicity Polymer surfaces and preparation method thereof.Hydrophobic nanoparticle fraction is embedded into surface by this patent The lamella transparent polymer surface of patterning, after molding, polymer surfaces had both remained the transparent of itself Property, possess again super-hydrophobicity.This technology can be applied to large area and prepare super hydrophobic surface, but because of For the special equipment of needs, it is more suitable for rule flat surface.
Chinese patent CN 102051120 A discloses that a kind of mechanical strength is higher, durability preferably, Prepare simple super-hydrophobic coat preparation method.By spraying technology, by composite nano inoganic particle, Polysiloxane compound, water spray to base with a kind of mixed dispersion liquid in emulsifying agent or organic solvent Basal surface, high-temperature heat treatment prepares super hydrophobic surface.But the method remains a need for particular device-spray Rifle could use, and coating is opaque.
Summary of the invention
Technical barrier to be solved by this invention is to overcome the existing super-hydrophobic coat preparation method cannot be with Time obtain the transparency, durability, erasability and repeatedly coating, temperature and pH stability, resist The performance such as droplet impact, versatility, it is provided that a kind of transparent hydrophobic coating material and both can be Factory lines produce can also in daily life according to different surfaces carry out operating transparent super thin The preparation method of water coating.
The transparent hydrophobic coating material of the present invention, its raw material includes: aerosil nanoparticle Dispersion liquid and water repellent agent.
Described aerosil nanoparticle dispersion liquid by aerosil nanoparticle with molten Agent forms, and wherein the percentage by weight of aerosil nanoparticle is 0.01%~50%.
Described solvent is water, alcohols, fat hydrocarbon, arene.Described alcohols solvent be with Under one or more: ethanol, methanol, isopropanol, glycerol etc.;Described fat hydrocarbon solvent is Following one or more: normal hexane, hexamethylene;Described aromatic hydrocarbon solvent is toluene, diformazan Benzene.For the consideration to health, it is typically chosen nontoxic or low toxic and environment-friendly type solvent.
The specific surface area of described aerosil nanoparticle is preferably 10m2/ g~1000m2/ g, It is preferably greater than 250m2/g.The percentage by weight of described aerosil nanoparticle is 0.01% ~50%, preferably 0.1%~30%.
Described water repellent agent refers to the hydrophobic material with low-surface-energy, and this hydrophobic material can be composed Precoat low-surface-energy, reduces or eliminates the polar bond of microstructural surfaces, at microstructural surfaces Form protective layer, the simultaneously fixing porous microstructure formed by Nano particles of silicon dioxide, for coating And adhesion is provided between substrate.The described hydrophobic material with low-surface-energy can be according to applying area And use the time to select and the control of consumption coating.
The described hydrophobic material with low-surface-energy generally comprises following one or more: alkyl silicon Alkane coupling agent, containing fluoro alkyl-silane coupling agent, fluorine-containing methacrylate base polymer, fluorine-containing propene Esters of gallic acid polymer, organo-silicon compound, fluorine-containing organic silicon compound etc..Specific as follows:
(1) the alkyl silane coupling agent described in from chosen below one or more: Formulas I (a), Formulas I (b), Formulas I (c).
Wherein, W represents hydrolyzable groups, can be methoxyl group (-OCH3), ethyoxyl (-OC2H5) Or chlorine (-Cl) etc., it is contemplated that the factors such as reactivity, prioritizing selection methoxyl group (-OCH3) or second Epoxide (-OC2H5);R1、R2、R3Independently represent the straight or branched alkane that carbon number is 1 to 30 Base, it is contemplated that cost, the synthesis straight chain that factor, preferably carbon number are 1 to 18 such as difficulty or Alkyl group.
(2) described in containing fluoro alkyl-silane coupling agent from chosen below one or more: Formula II (a), Formula II (b), Formula II (c).
Wherein, W represents hydrolyzable groups, can be methoxyl group (-OCH3), ethyoxyl (-OC2H5) Or chlorine (-Cl) etc., it is contemplated that the factors such as reactivity, prioritizing selection methoxyl group (-OCH3) or second Epoxide (-OC2H5);Rf1、Rf2、Rf3Independently represent fluorine-containing straight chain that carbon number is 1 to 20 or Branched alkyl, correspondingly, hydrogen moiety on alkyl or be all replaced by fluorine atoms, corresponding fluorine is former Subnumber is 1 to 40, it is contemplated that the factors, preferably carbon number such as cost, synthesis difficulty are 1 to 12 Fluorine-containing straight chain or straight chained alkyl, corresponding number of fluorine atoms is 1 to 36.
(3) the fluorine-containing methacrylate base polymer described in must comprise following fluorine-containing methyl-prop Olefin(e) acid esters monomer:
Wherein, Yf be carbon number be the fluorine-containing straight or branched alkyl of 1 to 20, correspondingly, alkane Hydrogen moiety on base or be all replaced by fluorine atoms, corresponding number of fluorine atoms is 1 to 40, it is contemplated that The factors such as cost, synthesis difficulty, Yf prioritizing selection carbon number is the fluorine-containing straight chain of 1 to 12 or props up Alkyl group, corresponding number of fluorine atoms is 1 to 36.
The described homopolymer that fluorine-containing methacrylate base polymer is monomer shown in formula III (a) or Person's copolymer, can add shown in other methacrylate-based monomer and the formula III (a) of different proportion Monomer carries out copolymerization.In the present invention, the formula of other methacrylate-based monomer is:
Wherein, Y be carbon number be the straight or branched alkyl of 1 to 20, double bond containing straight chain or Side chain unsaturated alkyl, unsaturated alkyl etc. containing phenyl ring.Y prioritizing selection carbon number is 1 to 8 Straight or branched alkyl;Carbon number is the double bond containing straight or branched unsaturated alkyl of 1 to 8; Carbon number is the unsaturated alkyl containing phenyl ring of 1 to 8.
(4) the acrylate containing fluorine polymer described in must comprise following acrylate containing fluorine list Body:
Wherein, Xf be carbon number be the fluorine-containing straight or branched alkyl of 1 to 20, correspondingly, alkane Hydrogen moiety on base or be all replaced by fluorine atoms, corresponding number of fluorine atoms is 1 to 40, it is contemplated that The factors such as cost, synthesis difficulty, the preferred carbon number of Xf is the fluorine-containing straight or branched alkane of 1 to 12 Base, corresponding number of fluorine atoms is 1 to 36.
The described homopolymer that fluorine-containing methacrylate base polymer is monomer shown in formula IV (a) or Person's copolymer, it is contemplated that the factors such as cost, in a solvent dispersibility, can add other of different proportion Monomer shown in methacrylate-based monomer and formula IV (a) carries out copolymerization.In the present invention, other first The formula of base acrylic ester monomer is:
Wherein, X be carbon number be the straight or branched alkyl of 1 to 20, double bond containing straight chain or Side chain unsaturated alkyl, unsaturated alkyl etc. containing phenyl ring.The preferred carbon number of X be 1 to 8 straight Chain or branched alkyl;Carbon number is the double bond containing straight or branched unsaturated alkyl of 1 to 8;Carbon Atomic number is the unsaturated alkyl containing phenyl ring of 1 to 8.
(5) under organo-silicon compound described in and the formula of fluorine-containing organic silicon compound are:
Wherein, R51~R62Stand alone as alkyl that carbon number is 1~20, carbon number is 1~20 Fluorine-containing alkyl, carbon number are the groups such as the alkoxyl of 1~10, and preferentially choosing carbon number is 1~10 Alkyl, carbon number be 1~10 fluorine-containing alkyl.If R51~R62In be non-fluoro-containing group, then Formula V representation compound is organo-silicon compound;If R51~R62In have one and above fluoro-containing group, Then Formula V representation compound is fluorine-containing organic silicon compound.R51~R62It is asynchronously hydroxyl, R53、R54、 R55、R58、R59、R60It is asynchronously hydroxyl, R51、R52、R57It is asynchronously hydroxyl, R56、 R60、R61It it is asynchronously hydroxyl;N, m, p stand alone as the integer of 0~1000, and can not be 0 simultaneously; Compound shown in Formula V at least contains two hydroxyls or alkoxyl or hydroxyl and alkoxyl sum is not less than 2.Above-mentioned alkyl is preferably alkyl.
Present invention also offers the transparent hydrophobic prepared by above-mentioned transparent hydrophobic coating material Coating.
Present invention also offers the preparation method of transparent hydrophobic coating, including:
(1) disperseed in a solvent to prepare by aerosil nanoparticle and obtain stable gas phase two Silicon oxide nanoparticle dispersion liquid;
(2) aerosil nanoparticle dispersion liquid is added drop-wise to lines (non-pure flat) On cloth, make cloth by aerosil nanoparticle dispersion liquid moistening;
(3) cloth after being wet rubs in substrate surface;
(4), after treating that solvent volatilizees completely, use water repellent agent that coating is carried out hydrophobization process.
Cloth described in step (2) be have certain surface pattern or surface hole defect structure weaving cloth, Non-woven fabrics, described cloth can be by solvent quickly and completely moistening.
Substrate described in step (3) includes glass, metal, plastics, rubber, concrete, paper Deng.
Hydrophobization described in step (4) processes and can be divided into following a few class according to the difference of its processing method:
(1) chemical gaseous phase sedimentation (chemical vapor deposition, CVD), by hydrophobic place Manage the alkyl silane coupling agent in agent or containing fluoro alkyl-silane coupling agent with through rubbing to put to surface In hermetic container, after utilizing coupling agent gasification reaction be deposited to rub the microstructural surfaces that obtains from And microstructural surfaces is carried out hydrophobization process.More preferably, evacuation can be carried out at hermetic container Process or heat to container, increasing coupling agent vapour density, strengthening hydrophobic treatment effect.
(2) spraying, dissolves water repellent agent or is stably dispersed in solvent, then by spray Automatic doubler surface glouer sprays to rub the coating surface obtained and carries out hydrophobization process.In the present invention, used It is molten that alkyl silane coupling agent and the coupling agent Han fluoro alkyl-silane are dissolvable in water ethanol, isopropanol, toluene etc. In agent;Organo-silicon compound, fluorine-containing organic silicon compound are dissolvable in water ethanol, isopropanol, toluene etc. In solvent or be dispersed in water.Fluorine-containing methacrylate class, acrylate containing fluorine are according to wherein containing The difference of fluorine monomer content, can dissolve (fluorochemical monomer content is less) or dispersion (fluorochemical monomer respectively Content is more) in solvent, usually, toluene, dimethylbenzene etc. to fluorine-containing methacrylate class, Acrylate containing fluorine has preferable solvability.Solution dense for the water repellent agent of spraying Degree preferably 0.01%~30%, more preferably 0.05%~20%.Described percentage ratio is mass percent.
The method have technical effect that:
1, the super-hydrophobic coating material of the present invention and the preparation method of coating are the most simple and convenient, adopt Method with magnetic agitation or ultrasonic disperse i.e. can get the dispersion of aerosil nanoparticle Liquid, can be coated on substrate surface by swabbing process by aerosil nanoparticle, and solvent is quick Volatilization i.e. can get the microstructure of porous surface, it is not necessary to the extreme conditions such as High Temperature High Pressure process, not only It is prone to commercial introduction, and possesses the application prospect of daily life.When need not super hydrophobic functional or After coating is destroyed by accidentalia, can quickly be wiped by methods such as scourings and not damage original substrate Surface nature.When needs super hydrophobic functional, can quickly rub again, there is updatability.
2, the super-hydrophobic coat of the present invention possesses the outstanding transparency, the most permissible by controlling Prepare the super-hydrophobic coat with certain antireflective effect.
3, the super-hydrophobic coat of the present invention can use in the range of-30 DEG C~400 DEG C of temperature ranges.
4, the aqueous solution in the range of the super-hydrophobic coat of the present invention to pH is 1~14 all shows stable Super-hydrophobicity, for complicated aqueous dispersion, all show such as coffee, milk etc. and stablize anti-profit Moist, it is also equipped with certain superoleophobic property simultaneously, and the drop for different volumes all shows stable Super-hydrophobicity.
5, the super-hydrophobic coat of the present invention possesses self-cleaning function, it is possible to the most ideally imitate Folium Nelumbinis Automatically cleaning ability.
6, the super-hydrophobic coat of the present invention has stronger anti-droplet impact, it is possible to soak for a long time Super-hydrophobicity is kept under water.
7, the super-hydrophobic coat of the present invention is applicable to be currently known the almost all of surface of solids.
Accompanying drawing explanation
Fig. 1 is the particle structure schematic diagram of Nano particles of silicon dioxide of the present invention;
Fig. 2 is the scanning electron microscopic picture of the super-hydrophobic coat that the embodiment of the present invention 1 prepares;
Fig. 3 is the contact angle test figure of the prepared super-hydrophobic coat of the embodiment of the present invention 1 and water droplet;
Fig. 4 is to drip at coating surface after the super-hydrophobic coat that the embodiment of the present invention 1 prepares is positioned on paper Add the photo of the water droplet dyeed by blue ink;
Fig. 5 is the super-hydrophobic coat self-cleaning function demonstration graph that the embodiment of the present invention 1 prepares;
Fig. 6 is to record after the super-hydrophobic coat that the embodiment of the present invention 1 prepares soaks different time under water Contact angle data;
After Fig. 7 is the water droplet impingement that the super-hydrophobic coat that the embodiment of the present invention 1 prepares stands different quality The contact angle data recorded;
Fig. 8 is the contact to the drop of different pH value of the embodiment of the present invention 1 prepared super-hydrophobic coat Angle and roll angle data;
Fig. 9 is that described in the embodiment of the present invention 1, same glass is carried out instead by super-hydrophobic coat preparation method The contact angle data of overcoating layer-cleaning.
Detailed description of the invention
If no special instructions, the various raw materials in the present invention are commercially available prod;Or can be according to this The method that is typically prepared in field obtains.Unless otherwise indicated or explanation, used herein specialty art Language is identical with this area routine term.
Embodiment 1
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid obtaining stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1.With This weaving cloth rubs at glass surface.
3, after treating that ethanol is evaporated completely completely, by the glass after erasing with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, heats.? 3h it is incubated at 180 DEG C.Then glass is taken out from exsiccator and i.e. obtain super-hydrophobic coat.
Use SEM to observe and can find that coating has porous microstructure (Fig. 2).Employing contact angle is surveyed It is 165.7 ° (Fig. 3) that examination instrument measures this super-hydrophobic coat to the contact angle of drop, and roll angle is 1 °.Figure 4 show that this super-hydrophobic coat possesses the outstanding transparency.Fig. 5 shows that this super-hydrophobic coat has from clear Clean ability.
Embodiment 2
1, (specific surface area is 100m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g water, is scattered in water by magnetic agitation and ultrasonic disperse instrument by aerosil nanoparticle In prepare the dispersion liquid of stable homogeneous.
2, intercept the non-woven fabrics of certain size, infiltrate this non-woven fabrics with the dispersion liquid in step 1, so After rub at glass surface.
3, after treating that water is evaporated completely completely, by the glass after coating with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, adds it Temperature, is incubated 3h at 100 DEG C.Then glass is taken out from exsiccator and i.e. prepare super-hydrophobic coat.
This super-hydrophobic coat contact angle is 162.1 °, and roll angle is 2 °.Other performances are as transparent, certainly Cleaning capacities etc. are same as in Example 1.
Embodiment 3
1, (specific surface area is 600m to weigh 0.1g aerosil nanoparticle respectively2/ g) and 50g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1, so Afterwards glass surface is rubbed.
3, after treating that ethanol is evaporated completely completely, by the glass after coating with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, adds it Temperature, is incubated 3h at 160 DEG C.Then glass is taken out from exsiccator and i.e. prepare super-hydrophobic coat.
This super-hydrophobic coat contact angle is 168.5 °, and roll angle is 2 °.The transparency is more excellent compared with embodiment 1.
Embodiment 4
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1, right Glass surface rubs.
3, after treating that ethanol is evaporated completely completely, by the glass after coating with equipped with the methyl three of 200 μ L Methoxy silane is put in airtight exsiccator together, heats it, is incubated 4h at 60 DEG C.So After by glass from exsiccator take out i.e. prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 164.2 °, and roll angle is 3 °, the transparency, automatically cleaning ability Deng excellent.
Embodiment 5
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 10g dehydrated alcohol, by magnetic agitation and ultrasonic disperse instrument by hydrophobic fumed silica nanoparticle Son is scattered in ethanol the dispersion liquid preparing stable homogeneous.
2, intercepting the weaving cloth (1cm × 5cm) of certain size, infiltrating with the dispersion liquid in step 1 should Weaving cloth, then rubs glass surface.
3, after treating that ethanol is evaporated completely completely, by the glass after coating with equipped with the methyl three of 200 μ L Methoxy silane is put in airtight exsiccator together, heats it, is incubated 4h at 60 DEG C.So After by glass from exsiccator take out i.e. prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 164.2 °, and roll angle is 3 °, and the transparency is than embodiment 1 slightly Difference.
Embodiment 6
1, (specific surface area is 800m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercepting the weaving cloth (1cm × 5cm) of certain size, infiltrating with the dispersion liquid in step 1 should Weaving cloth.Then aluminum flake surface is rubbed.
3, after treating that ethanol is evaporated completely completely, by the aluminium flake after coating with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, adds it Temperature, is incubated 4h at 200 DEG C.Then aluminium flake is taken out from exsiccator and i.e. prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 167.3 °, and roll angle is 1 °.
Embodiment 7
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g isopropanol, is disperseed aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument The dispersion liquid of stable homogeneous is prepared in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1.So Afterwards polymethyl methacrylate is molded disk surfaces to rub.
3, after treating that isopropanol is evaporated completely completely, by the glass after coating with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, at 60 DEG C Lower insulation 1h.Then disk is taken out from exsiccator and i.e. prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 163.9 °, and roll angle is 1 °, and still have high transparent, Automatically cleaning ability etc..
Embodiment 8
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g normal hexane, is disperseed aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument The dispersion liquid of stable homogeneous is prepared in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1.So Afterwards A4 paper surface is rubbed.
3, after treating that normal hexane is evaporated completely completely, by the A4 paper after coating with equipped with 200 μ L's 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane is put in airtight exsiccator together, adds it Temperature, is incubated 3h at 40 DEG C.Then take out from exsiccator and i.e. prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 162.5 °, and roll angle is 2 °.
Embodiment 9
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1.So Afterwards glass surface is rubbed.
3, after treating that ethanol is evaporated completely completely, the fluorine-containing methacrylate resin that concentration is 5% is divided Scattered liquid sprays to glass surface, treats solvent to be evaporated completely afterwards and can prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 159.8 °, and roll angle is 4 °, and the transparency is excellent.
Embodiment 10
1, (specific surface area is 400m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1.So Afterwards glass surface is rubbed.
3, after treating that ethanol is evaporated completely completely, by 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilane Mass concentration be 1% ethanol solution spray to, on the glass after coating, glass be stood 30 minutes i.e. Prepare super-hydrophobic coat.
The contact angle of this super-hydrophobic coat is 161.3o, roll angle is 3o.Other performances such as transparency, Automatically cleaning abilities etc. are close with embodiment 1.
Embodiment 11
1, (specific surface area is 300m to weigh 0.2g aerosil nanoparticle respectively2/ g) and 20g dehydrated alcohol, is divided aerosil nanoparticle by magnetic agitation and ultrasonic disperse instrument Dissipate the dispersion liquid preparing stable homogeneous in ethanol.
2, intercept the weaving cloth of certain size, infiltrate this weaving cloth with the dispersion liquid in step 1, so Afterwards glass surface is rubbed.
3, after treating that ethanol is evaporated completely completely, by the ethanol solution (concentration is 3%) of organo-silicon compound Spray on the glass after coating, i.e. prepare super-hydrophobic coat by static for glass.
The contact angle of this super-hydrophobic coat is 158.9 °, and roll angle is 5 °.Other performances such as transparency, Automatically cleaning abilities etc. are same as in Example 1.
Performance test
One, durability test
The super-hydrophobic coat of preparation in embodiment 1 is soaked in water, surveys after taking out at set intervals Amount contact angle and roll angle, be shown in Fig. 6.Visible, in the range of the testing time, super-hydrophobic coat is equal Showing stable contact angle and roll angle, and contact angle is all more than 160 °, roll angle is respectively less than 2°。
After the super-hydrophobic coat of preparation is fixing in embodiment 1, at regular intervals, use certain mass Water go to impact super-hydrophobic coat surface, then measure contact angle and roll angle, be shown in Fig. 7.It is visible, This super-hydrophobic coat remains to keep stable super-hydrophobicity under 10kg water constant impingement, and this is described Bright super-hydrophobic coat possesses the water droplet impact capacity of excellence.
Two, corrosion resistance liquid testing
By pH value from 1 to 14 drop be added drop-wise on the super-hydrophobic coat embodiment 1, then survey Amount contact angle and roll angle, be shown in Fig. 8.Visible, this super-hydrophobic coat is for whole pH value range Interior drop all shows super-hydrophobicity.Illustrate that the super-hydrophobic coat of the present invention possesses certain corrosion resistant The ability of erosion property liquid.
Three, to organic solvent and complicated aqueous dispersion drop anti-wettability test
Different drops are added drop-wise on the super-hydrophobic coat in embodiment 1, then measure contact angle and rolling Dynamic angle, is shown in Table 1, and from table 1, this super-hydrophobic coat has possessed certain superoleophobic performance, and For complicated aqueous dispersion, also there is stable super anti-wettability.
Table 1 Surface Tension of Liquid Drops and the contact angle on super-hydrophobic coat and roll angle
Four, reperformance test
First prepare super-hydrophobic coat according to the method in embodiment 1, measure contact angle and roll angle, Then with the glass after commercially available glass cleaner coating cleaning, contact angle is measured, by above-mentioned steps weight Carry out again, investigate the repeatability of the used method of the present invention, be shown in Fig. 9.Visible, the side of the present invention Method is a kind of method of gentleness, substrate will not be caused damage, and the method for the present invention can be used base Basal surface carries out coating repeatedly, and can coating be removed easily when not needed.

Claims (7)

1. a transparent hydrophobic coating, it is characterised in that use super-hydrophobic coating material to be prepared into Arriving, the raw material of described transparent hydrophobic coating material includes: aerosil nanoparticle dispersion liquid And water repellent agent;Described aerosil nanoparticle dispersion liquid is by aerosil nanometer Particle forms with solvent;
The preparation method of described super-hydrophobic coat, including:
(1) disperseed in a solvent to prepare by aerosil nanoparticle and obtain stable gas phase two Silicon oxide nanoparticle dispersion liquid;
(2) it is added drop-wise to carry on textured cloth by aerosil nanoparticle dispersion liquid, makes cloth By aerosil nanoparticle dispersion liquid moistening;
(3) cloth after being wet rubs in substrate surface;
(4), after treating that solvent volatilizees completely, use water repellent agent that coating surface is carried out hydrophobization Process.
2. transparent hydrophobic coating as claimed in claim 1, it is characterised in that described solvent For water, alcohols, fat hydrocarbon or arene;Described alcohols solvent is following one or many Kind: ethanol, methanol, isopropanol, glycerol;Described fat hydrocarbon solvent be following one or Several: normal hexane, hexamethylene;Described aromatic hydrocarbon solvent is toluene or dimethylbenzene.
3. transparent hydrophobic coating as claimed in claim 1, it is characterised in that described hydrophobic place Reason agent be alkyl silane coupling agent, containing fluoro alkyl-silane coupling agent, fluorine-containing methacrylate Type of Collective Thing, acrylate containing fluorine polymer, organo-silicon compound or fluorine-containing organic silicon compound.
4. transparent hydrophobic coating as claimed in claim 1, it is characterised in that step (1) institute The percent mass of aerosil nanoparticle in the aerosil nanoparticle dispersion liquid stated Ratio is 0.01%~50%.
5. transparent hydrophobic coating as claimed in claim 3, it is characterised in that step (4) institute The hydrophobization stated is processed as the one in following methods: a) by alkyl silane coupling agent or containing fluoroalkyl Silane coupler carries out hydrophobization process by chemical gaseous phase sedimentation to coating surface, and treatment temperature is 30~200 DEG C, the process time is 0.5~10h;B) by alkyl silane coupling agent or containing fluoro alkyl-silane Coupling agent is dissolved or dispersed in easy volatile solvent and is sprayed at coating surface and carries out hydrophobization process;c) Fluorine-containing methacrylate base polymer or acrylate containing fluorine polymer are dissolved in solvent or It is scattered in solvent and is sprayed at coating surface and carries out hydrophobization process;D) by organo-silicon compound or contain Fluorine organo-silicon compound are sprayed on coating surface and solidify and carry out hydrophobization process.
6. transparent hydrophobic coating as claimed in claim 5, it is characterised in that described is hydrophobic Change in processing method b), molten for alkyl silane coupling agent or the coupling agent Han fluoro alkyl-silane of spraying The concentration of liquid or dispersion liquid is 0.01%~30%.
7. transparent hydrophobic coating as claimed in claim 5, it is characterised in that described is hydrophobic Change in processing method c), for fluorine-containing methacrylate base polymer, the fluorine-containing of spraying The dispersion liquid concentration of esters polymer is 0.05%~30%.
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