CN107641345A - A kind of self-cleaning nona coating, inorganic transparent coating and automatically cleaning product - Google Patents
A kind of self-cleaning nona coating, inorganic transparent coating and automatically cleaning product Download PDFInfo
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- CN107641345A CN107641345A CN201711069743.4A CN201711069743A CN107641345A CN 107641345 A CN107641345 A CN 107641345A CN 201711069743 A CN201711069743 A CN 201711069743A CN 107641345 A CN107641345 A CN 107641345A
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Abstract
Present invention is disclosed a kind of self-cleaning nona coating, inorganic transparent coating and automatically cleaning product.Prepare in proportion and contain nanometer conductive material, inorganic hard coat agent, the self-cleaning nona coating of inorganic bond and hydrophilic solvent, coated in body surface and it is formed by curing hydrophilic inorganic clear coat, because of the distinctive static conductive of coating and electrostatic dissipation function, body surface and electrostatic caused by moving air friction can be eliminated immediately, body surface is set from microcosmic to lose the attraction to dirts such as dust granules in surrounding enviroment, it is difficult to be attached to body surface to cause dirt, so as to realize that body surface keeps clean instant automatically cleaning effect at any time, this, which is clearly distinguishable from, needs rain, what could be started working after the external conditions such as illumination is super-hydrophobic, traditional automatically cleaning product such as photocatalyst.
Description
Technical field
The present invention relates to a kind of self-cleaning nona coating, inorganic transparent coating and automatically cleaning product, belongs to nano paint neck
Domain.
Background technology
In order to clean the dirts such as the dust of all kinds of body surfaces such as vehicle, wall, glass, panel, oil stain, current people adopt
Four kinds of modes of self-cleaning surface are cleaned and prepared in scouring, hydroblasting, robot by hand.Automatically cleaning technology is because that can substantially reduce
Operations number and maintenance cost and by attention.Self-cleaning coating is the main mode for preparing object self-cleaning surface, at present
Have developed into the classifications such as super-hydrophobic self-cleaning paint, self-cleaned by photocatalyst coating and silica superhydrophilic self-cleaning coating.
The patent of super-hydrophobic self-cleaning paint such as CN201210326808, CN201410590746,
CN201510539531 and CN201610678746 etc..When raining, water can form the globule of high contact angle in its coating surface, should
The globule can take away the dirts such as the dust of coating surface accumulation when being slid by gravity, therefore have automatically cleaning effect.But super-hydrophobic painting
Material manufactured coating needs this external condition of water, could open self-cleaning function.In addition, because of the made painting of super-hydrophobic self-cleaning paint
Layer usually contains fluorine or resinae organic compound, causes the disadvantages such as poor, the outdoor short life of its weatherability.
The patent of self-cleaned by photocatalyst coating such as CN201210020937, CN201310108270,
CN201410251198, CN201510064039, CN201610484403 and CN201710192117 etc..Self-cleaned by photocatalyst applies
Material must could start organic dirt of degrading after possessing the external conditions such as illumination, steam, and also will be by because by gravity
The moisture film of downslide can just take away the remains after dirt decomposes.The inorganic matters such as sand and dust fine earth in addition, photo-catalytic coating can not degrade, because
And cleaning speed is slow, effect is limited.
Patent such as CN201210411603, CN201310349597 of silica superhydrophilic self-cleaning coating,
CN201410087145 and CN201610221442 etc..The functional component of such coating manufactured coating is silica.When raining,
Water can form the tiling moisture film of low contact angle on its surface, and the moisture film is by the dust that coating surface accumulation can be taken away during Gravitational sliding
Deng dirt, therefore also there is automatically cleaning effect.But this coating manufactured coating is also required to water this external condition, could open from
Cleaning function.
In a word, above-mentioned super hydrophobic coating manufactured coating, photo-catalytic coating manufactured coating, silica coating manufactured coating,
The external conditions such as rainwater are required for, respective self-cleaning function could be opened.Not all rained daily in life, artificial water application is not
Automatically cleaning meaning is only lost, but also spending can be increased, especially positioned at remote or desert area photovoltaic plant.So use
The product of super-hydrophobic, photocatalyst or the super hydrophilic coating of silica, the actual automatically cleaning effect on its surface are simultaneously unsatisfactory.It
The shortcomings that to be all " tolerance " dirt could open after product surface has a period of time, it is necessary to there is the external conditions such as water or light
Self-cleaning function, its work response have serious time-lag effect.There are some researches show photovoltaic cell surface as averagely fallen one layer 4
The dust of grammes per square metre, will make its decrease in power generation efficiency about 40%, and the hysteresis quality of surface cleaning can undoubtedly cause photovoltaic plant huge
Generated energy loses, so there is an urgent need to its surface can be made to keep clean instant self-cleaning coating in time for photovoltaic panel etc..
The content of the invention
Problems to be solved by the invention
Hydrophobic class self-cleaning coating manufactured coating by the globule of whereabouts, it is necessary to could start working, but also because using organic
Thing, causes that its durability of coating is poor, outdoor short life；Photocatalyst class self-cleaning coating manufactured coating, can only slowly degrade object
The organic dirt on surface, and need that by the moisture film of whereabouts its self-cleaning function could be completed, photocatalyst is for sand and dust in addition
The inorganic dirt such as fine earth does not have degradation；The super hydrophilic coating manufactured coating of silica, it is also desirable to by the moisture film of whereabouts
Competence exertion function.This three classes self-cleaning coating manufactured coating, all " tolerate " that all kinds of dirts have a period of time in body surface,
Until could start working after having the external conditions such as water or light, its automatically cleaning effect has obvious time-lag effect, all can not and
When remove body surface all kinds of dirts, can not especially meet the clean automatically cleaning need of the instant holding surface of the objects such as photovoltaic panel
Will.
The solution used to solve the problem
The applicant has found after long-term study intensively：Can be with the object phase mutual friction such as glass and continuously generating during air flow
The accumulation of the body surface such as electrostatic, usual glass is positive charge electrostatic, the bulky grain dust accumulation in air and positive charge
Electrostatic, fine particle accumulation in air is negative electrostatic charge, because attraction be present in xenogenesis electric charge, tiny in air
Grain will successively be attracted and be attached to the body surfaces such as glass, form dirt.The organic such as oil smoke dirt can be adhered to glass
Deng body surface, main cause is also the attraction that xenogenesis electric charge be present with body surface.Therefore, the present inventor passes through hydrophilic coating
Electrostatic dissipation or static conductive coating are prepared for body surface, can be eliminated immediately quiet caused by the friction of body surface and moving air
Electricity, body surface is just set from microcosmic to lose the attraction to all kinds of dirts, it is difficult to be attached to body surface to cause dirt, so as to
Realize that body surface can keep clean instant automatically cleaning effect at any time, just can round-the-clock hair without external conditions such as water, illumination
Wave self-cleaning function.
The present invention is realized by following concrete technical schemes：A kind of self-cleaning nona coating is prepared, when it is coated to
Body surface and when solidifying, the hydrophilic inorganic clear coat provided for product, enables product to eliminate electrostatic immediately and realizes
The instant automatically cleaning in surface.The composition of this coating is：
The parts by weight of nanometer conductive material 0.01~20；
The inorganic parts by weight of hard coat agent 0.01~20；
The parts by weight of inorganic bond 0.01~20；
The parts by weight of hydrophilic solvent 40~99.97.
As nanometer conductive material, its microscopic appearance includes nano particle, nanometer rods, nanotube, nano wire, nanometer sheet
Deng, and surface resistivity ρ s are less than 1 × 10 after these nano materials are pressed into solid thin slice with universal testing machine7Ω/
□.Nanometer conductive material includes but is not limited to：Tin-doped indium oxide (SnO2-In2O3That is ITO), tin oxide (SnO2), mix antimony oxygen
Change tin (Sb2O3-SnO2That is ATO), mix bismuth tin oxide (Bi2O3-SnO2That is BTO), p-doped tin oxide (P2O5-SnO2That is PTO), mix
Fluorine tin oxide (F-SnO2That is FTO), the fluorin-doped tin oxide (P-F-SnO of phosphorus2That is PFTO), mix antimony zinc oxide (Sb2O3- ZnO is
AZO bismuth zinc oxide (Bi), is mixed2O3- ZnO is BZO), CNT (CNT), graphene (C), tin alkene (Sn), Nano Silver (Ag), nitrogen
Change dicalcium (Ca2N), stannic acid beryllium (BeSnO3), magnesium stannate (MgSnO3), calcium stannate (CaSnO3), stronitum stannate (SrSnO3), barium stannate
(BaSnO3), zinc stannate (ZnSnO3), wolframic acid caesium (CsxWO3, x ＜ 1), vanadic acid beryllium, vanadic acid magnesium, calcium vanadate, strontium vanadate and vanadic acid
One or more in barium.Its powder can be dispersed in hydrophilic solvent and form dispersion liquid or colloidal sol by nanometer conductive material in advance
Use.Making the method for this dispersion liquid by oneself includes：Disperse nanometer conductive material in hydrophilic solvent using plant equipment, can example
The plant equipment enumerated has mixer, grinder, ball mill, sand mill, homogenizer etc.；Also synthesized using the methods of hydro-thermal
During nanometer conductive material, nanometer conductive material self-dispersing liquid or colloidal sol are just formed in hydrophilic solvent.In addition, this kind of nanometer
The hydrophilic dispersion liquid or colloidal sol of conductive material, directly it can also be bought in addition to self-control to professional supplier.
As inorganic hard coat agent, it is the hardness for improving the made film layer of coating that it, which is acted on, or suppresses substrate surface and ooze out chemistry
Material injures to caused by film layer.Inorganic hard coat agent includes but is not limited to：Tungsten oxide, titanium oxide, cerium oxide, aluminum oxide, platinum,
One or more nano materials in tungsten carbide.Its powder can be dispersed in be formed in hydrophilic solvent by inorganic hard coat agent in advance to be divided
Dispersion liquid or colloidal sol use.When also synthesizing inorganic hard coat agent using the methods of hydro-thermal, nothing is just formed in hydrophilic solvent
The self-dispersing liquid or colloidal sol of machine hard coat agent.In addition, the hydrophilic dispersion liquid or colloidal sol of this kind of inorganic hard coat agent, may be used also in addition to self-control
Directly to be bought to professional supplier.
As inorganic bond, it is to be bonded to nanometer conductive material, nano inorganic hard coat agent by its viscosity that it, which is acted on,
Substrate surface.Inorganic bond includes but is not limited to：One kind or more in silica, Ludox, sodium metasilicate, potassium silicate
Kind.Its powder also can be dispersed or dissolved in hydrophilic solvent in advance and form dispersion liquid, solution or colloidal sol use by inorganic bond.
When also using inorganic bond is synthesized the methods of hydro-thermal, the self-dispersing of inorganic bond is just formed in hydrophilic solvent
Liquid, solution or colloidal sol.In addition, the hydrophilic dispersion liquid of this kind of inorganic bond, solution or colloidal sol, also can also be straight in addition to self-control
Connect to professional supplier and buy.
As hydrophilic solvent, its effect is provided for above-mentioned nanometer conductive material, inorganic hard coat agent and inorganic bond
Carrier.Hydrophilic solvent, preferably water, can also and with water and hydrophilic organic solvent., can example as hydrophilic organic solvent
Enumerate methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-pentyl alcohol,
1- ethyl -1- propyl alcohol, 2-methyl-1-butene alcohol, n-hexyl alcohol and cyclohexanol etc..
As a kind of self-cleaning nona coating, mix in proportion before coating above-mentioned nanometer conductive material, inorganic hard coat agent,
Inorganic bond and hydrophilic solvent, and used after stirring in a reservoir.Coating method is spraying, showering, roller coat, rotation
Apply, one or more combinations in blade coating.
As coated base material, to prevent some base material chemistry insides from causing to hinder to inorganic transparent coating after oozing out
Evil, separation layer is optionally coated in substrate surface in advance.The material that can form fine and close hard film layer, bag can be selected in separation layer
Include and be not limited to silica, tungsten oxide etc., preparation method such as magnetron sputtering method, vapour deposition process, liquid phase rubbing method,
The existing many open source literatures of these specific methods, also known to related personnel and use, be that those skilled in the art " need not be again
Pay creative work " the just method that can implement.In addition, coated substrate surface should be anticipated as clean and dry shape
State.
As inorganic transparent coating, can be carried out solidifying under low temperature, room temperature and high temperature, specifically solidification temperature
For -50 DEG C~4000 DEG C, preferably 10 DEG C~800 DEG C, more preferably 25 DEG C~700 DEG C.Manufactured coating composition is inorganic nano
Material and coating layer thickness are usually below 1000nm, so the coating is also big with the transparency, the visible light transmissivity of coating
In 51%, preferably greater than 70%, further preferably greater than 80%.The surface resistivity ρ s of manufactured coating are less than 1 × 1012Ω/
, preferably less than 109Ω/, further preferably less than 108Ω/□.Therefore this inorganic transparent coating have static conductive,
Static electricity discharge or electrostatic dissipation function, make coating surface will not because accumulating electrostatic with windage, it is microcosmic on make in air
Dust particle and oil smoke lose the adhesion mutually adsorbed with coating and to form dirt, so as to realize without external worlds such as rainwater or illumination
Condition is with regard to workable round-the-clock self-cleaning function.In addition, manufactured coating also has hydrophily, its water drop contact angle is hydrophilic
Angle is less than 40 °, and preferably less than 10 °, further preferably less than 5 °, applicant have also found that hydrophilic angle is smaller, this is inorganic
The self-cleaning function of bright coating is better.
As automatically cleaning product, it is characterized in that surface is provided with the article of above-mentioned inorganic transparent coating, these articles include
And the car bodies such as high ferro, motor-car, automobile are not limited to, and the aircraft such as aerodone, unmanned plane, the electricity such as Mobile phone screen, TV screen, computer screen
Subclass display, billboard, sculpture, portrait, building, furniture, clothing shoes and hats, ceramics, ceramic tile, plastics, glass, photovoltaic face
Plate, glasses, floor etc..
The effect of invention
The present invention is applied by preparing a kind of self-cleaning nona containing nanometer conductive material, inorganic hard coat agent and inorganic bond
Material, the inorganic transparent coating that can make its self-cleaning surface is provided for object, make product surface be not easy accumulation electrostatic, it is microcosmic on
The fine earth dust in air and oil smoke is set to lose the strength mutually adsorbed with product surface and to form dirt.Particularly, it is this inorganic
Clear coat can just start automatically cleaning work at any time without external conditions such as rainwater or illumination, product surface is kept clean at any time
State.Therefore, this self-cleaning function, be also understood that or for timely automatically cleaning, instant automatically cleaning, moment automatically cleaning, with
When automatically cleaning, the automatically cleaning without external conditions such as rainwater or illumination, round-the-clock automatically cleaning etc..
It is this without external conditions such as rainwater or illumination moreover, according to known to the applicant, just can self-cleaning nanometer immediately
Coating is not to be disclosed what is reported so far in academia and industrial circle.
Brief description of the drawings
Fig. 1 is the schematic diagram of automatically cleaning product；
Fig. 2 is the previously prepared schematic diagram of the automatically cleaning product of separation layer；
Fig. 3 is that inorganic transparent coating and automatically cleaning product properties detect table；
Wherein, 11 be base material, and 12 be inorganic transparent coating, and 13 be separation layer.
Embodiment
Embodiment 1
(1) conductive nano SnO is prepared2.By 25 parts by weight butter of tin hydrate (SnCl4·5H2O 100 parts by weight) are dissolved into
In deionized water, the 25wt% concentrated ammonia liquors of 30 parts by weight are added dropwise, tin ion is fully converted to Sn (OH)4Precipitation, is washed with water 5
Secondary to remove removing chloride etc., redisperse is 10.5 into 100 parts by weight of deionized water and with ammoniacal liquor regulation pH, under agitation quickly
Add the sodium peroxide Na of 1.2 parts by weight2O2, it is transferred completely into hydrothermal reaction kettle, hydro-thermal reaction cools after 5 hours until room
Temperature, it is washed with deionized 5 times by NF membrane and removes and receive the residual impurities such as ion, will filtering net surface canescence material transfer
Into container and a small amount of water is supplemented, just obtains SnO2The aqueous liquid dispersion of conductive nano-particles, solid content are 9.8 g/ml, and
And SnO2Particle diameter is about 2 nanometers.
(2) tungsten oxide hard coat agent is prepared.The tungsten hexachloride of 1 parts by weight is dissolved into the ethanol of 10 parts by weight, then adds 90
The deionized water of parts by weight, 180 DEG C are then warming up in hydrothermal reaction kettle and is incubated 3 hours, naturally cools to room temperature, by
NF membrane is washed with deionized 5 times and removes the residual impurities such as removing chloride, will filter the faint yellow material of net surface and is transferred to container
In and supplement appropriate deionization, it is 10g/ml to make its solid content, just obtains the WO of water-based system3Hard coat agent.
(3) silica binder is prepared.420 milliliters of tetraethyl orthosilicates (TEOS) are added to 435 milliliters of anhydrous second
In alcohol, then be added dropwise 82.5 milliliters deionized water and 18.75 milliliters of 1M aqueous hydrochloric acid solutions, stirring 60 minutes after at room temperature
Ageing 24 hours, is then heated to after being stirred 40 minutes at 80 DEG C and naturally cools to room temperature, just obtain silica aqueous sol
Adhesive, solid content are 11.35 g/ml.
(4) self-cleaning nona coating is prepared.The above-mentioned conductive nanometer SnO of 10 milliliters of mixing2Water-based self-dispersing liquid, 5 milli
The tungsten oxide hard coat agent of liter, 4 milliliters of silica binder, 981 ml deionized waters, stir and this nanometer is just made certainly
Coating is cleaned, its composition is the conductive nano tin oxide of 9.8 parts by weight, the tungsten oxide hard coat agent of 5 parts by weight, 4.54 weight
The silica binder of part, ethanol, the water of 80.52 parts by weight of 0.14 parts by weight.
(5) inorganic transparent coating and its product are prepared.It is equal using spin coating tool by 50 milliliters of above-mentioned nano self-cleaning paints
Even be coated to a piece of has been prepared for the photovoltaic that silica antireflective coating and length, width and height size are 1956mm × 992mm × 100mm
On panel, after 25 DEG C of following table solidization, a piece of instant automatically cleaning photovoltaic panel with inorganic transparent coating is just obtained.In addition,
Previously prepared antireflection film layer is also the separation layer between photovoltaic panel and the inorganic transparent coating, prepares this silica and subtracts
The technology of reflectance coating is current to be known and is used by the personnel of many relevant enterprises.
(6) self-cleaning performance, static electricity resistance, contact angle, the transparency, the rub resistance of product photovoltaic panel face coat are detected
Property etc., see the performance detection table of accompanying drawing 3.
Embodiment 2
(1) conductive nano SnO is prepared2, solid content is 9.8g/ml SnO2Aqueous liquid dispersion, SnO2Particle diameter is about 2nm, with reality
It is identical to apply example 1.
(2) hard coat agent a is bought, and solid content is 5wt% WO3Methanol dispersion liquid, WO3Particle diameter is less than 100 nanometers.
Hard coat agent b is bought, solid content is 1wt% Pt microparticles aqueous liquid dispersion, and Pt particle diameters are less than 100 nanometers.
(3) adhesive A is bought, and solid content is 20wt% SiO2Methanol dispersion liquid, SiO2Particle diameter is less than 10 nanometers.
Adhesive B is bought, solid content is 1.5wt% noncrystal SiO2Aqueous liquid dispersion, SiO2Particle diameter is less than 2 nanometers.
(4) self-cleaning nona coating is prepared.Mix proper amount of above-mentioned conductive nano SnO2, it is tungsten oxide hard coat agent, inorganic viscous
Mixture, deionized water and methanol, make the composition of the nano self-cleaning paint for 2.95 parts by weight conductive nano tin oxide,
The tungsten oxide hard coat agent of 0.05 parts by weight, the platinum hard coat agent of 0.01 parts by weight, the SiO of 8.1 parts by weight2Adhesive, 6.9 weight
The noncrystal SiO of part2The water of adhesive, the methanol of 70 parts by weight and 11.99 parts by weight.
(5) inorganic transparent coating and its product are prepared.By 100 milliliters of above-mentioned nano paints, one is uniformly coated to using spray gun
Compact car body and glass surface, after 25 DEG C of following table solidization, just obtaining a surface has the instant of inorganic transparent coating
Automatically cleaning car.
(6) the self-cleaning performance of detection product car coating, static electricity resistance, contact angle, the transparency, rub resistance etc., are shown in
The performance detection table of accompanying drawing 3.
Embodiment 3
(1) conductive nano FTO is made by oneself.By 10 parts by weight butter of tin (SnCl4·5H2O) hydrate dissolution is to 100 parts by weight
In deionized water, the 25wt% concentrated ammonia liquors of 30 parts by weight are added dropwise, tin ion is fully converted to Sn (OH)4Precipitation, is washed with water 5
It is secondary to remove after removing chloride to shift sediment into hydrothermal reaction kettle, add 0.1 parts by weight hydrofluoric acid (HF), 20 parts by weight go from
After sub- water, hydrothermal reaction kettle is warming up to 180 DEG C and constant temperature is cooled to room temperature after 15 hours.By the turbid solution in reactor point
Colorless precipitation is obtained from after, shows that fluorine ion has been adulterated into SnO2(fluorine doped aoxidizes lattice generation conductive nanometer FTO
Tin, F-SnO2), it is washed with deionized 5 times by NF membrane and goes the removal of impurity, filtering net surface sediment is transferred in container
And a small amount of water is supplemented, just obtains conductive nano FTO dispersion liquid.
(2) hard coat agent bought, and solid content is 5wt% cerium oxide alcohol dispersion liquid, CeO2Particle diameter is less than 100 nanometers.
(3) inorganic bond is bought, and solid content is 20wt% sodium silicate aqueous solution.
(4) self-cleaning nona coating is prepared.Mix proper amount of above-mentioned conductive nano FTO, cerium oxide hard coat agent, sodium metasilicate
Adhesive, deionized water and ethanol, the composition for making the nano paint is the conductive nano FTO of 5 parts by weight, 0.05 parts by weight
Cerium oxide hard coat agent, the sodium silicate binder of 13 parts by weight, the ethanol of the water of 80 parts by weight and 1.95 parts by weight.
(5) inorganic transparent coating and its product are prepared.By 100 milliliters of above-mentioned nano paints, uniformly coated using roller coat instrument
Onto a piece of ultra-white photovoltaic cover-plate glass for being prepared for silica antireflective coating, automatically cleaning is obtained after surface drying at subzero 20 DEG C
Photovoltaic cover-plate glass.
(6) the self-cleaning performance of detection product photovoltaic cover-plate glass, static electricity resistance, contact angle, the transparency, rub resistance etc.,
See the performance detection table of accompanying drawing 3.
Embodiment 4
Buy conductive nano strontium vanadate, solid content be 20wt% strontium vanadate alcohol dispersion liquid, SrVO3Particle diameter is received less than 100
Rice.
(2) hard coat agent bought, and solid content is 5wt% titanium oxide alcohol dispersion liquid, TiO2Particle diameter is less than 100 nanometers.
(3) inorganic bond is bought, and solid content is 20wt% potassium silicate aqueous solution.
(4) self-cleaning nona coating is prepared.Mix proper amount of above-mentioned conductive nano SrVO3、TiO2Hard coat agent, potassium silicate glue
Mixture, deionized water and ethanol, the composition for making the nano paint are the conductive nano SrVO of 5 parts by weight3, 0.1 parts by weight
Titanium oxide hard coat agent, the potassium silicate binder of 10 parts by weight, the ethanol of the water of 80 parts by weight and 4.9 parts by weight.
(5) inorganic transparent coating and its product are prepared.By 50 milliliters of above-mentioned nano paints, uniformly coated using showering instrument
To a piece of 5 square metres and sputtered on the building glass of tungsten oxide separation layer, at room temperature after surface drying again through 300 DEG C of high temperature at
Reason obtains automatically cleaning building glass after 30 minutes.
(6) self-cleaning performance, static electricity resistance, contact angle, the transparency, the rub resistance of product automatically cleaning building glass are detected
Deng seeing the performance detection table of accompanying drawing 3.
Embodiment 5
(1) conductive nano ITO is bought, and solid content is 10wt% ITO aqueous liquid dispersions, and ITO particle diameters are less than 100 nanometers.
(2) hard coat agent bought, and solid content is the alcohol dispersion liquid of 5wt% aluminum oxide, Al2O3Particle diameter is less than 100 nanometers.
(3) inorganic bond is bought, and solid content is 20wt% water silica sol.
(4) self-cleaning nona coating is prepared.Mix proper amount of above-mentioned conductive nano ITO, Al2O3Hard coat agent, Ludox glue
Mixture, deionized water and ethanol, the composition for making the nano paint is the conductive nano ITO of 5 parts by weight, 0.1 parts by weight
Al2O3Hard coat agent, the silica sol binder of 10 parts by weight, the ethanol of the water of 80 parts by weight and 4.9 parts by weight.
(5) inorganic transparent coating and its product are prepared.By 30 milliliters of above-mentioned nano paints, uniformly coated using instrument is scratched
Onto a piece of 1.5 square metres of shield glass, automatically cleaning vehicle glass is obtained after surface drying at room temperature.
(6) self-cleaning performance, static electricity resistance, contact angle, the transparency, the rub resistance of product automatically cleaning vehicle glass are detected
Deng seeing the performance detection table of accompanying drawing 3.
Embodiment supplemental content
(1) current industrial circle prepares three kinds of methods of the functional membranes such as silica or separation layer.
1. magnetron sputtering method.The titanium dioxide silicon target for the use of purity being 99.9% is target, and the argon gas that purity is 99.9% is to splash
Emanate body, vacuumizing makes chamber vacuum degree be less than 1 × 10-3Magnetron sputtering is come into effect after Pa, this is current coated glass enterprise
Common practice, be also applied in the previously prepared silica separation layer of the insulator surfaces such as ceramic tile, TV screen, electronic display.
In addition, using high-purity mangesium oxide tungsten target material, or substrate surface magnetron sputtering prepares tungsten oxide separation layer.
2. Ludox method.The silica antireflective anti-reflection film prepared using Ludox on ultra-white photovoltaic glass surface, it is
Separation layer.The regulation of commodity Ludox solid content is first arrived about 3%, then using equipment such as roller coat, sprayings, in ultra-white photovoltaic glass
Surface coating, at room temperature after surface drying, then be heating and curing at 100~700 DEG C, be just prepared on ultra-clear glasses surface silica every
Absciss layer, this is the common practice of current photovoltaic glass manufacturing enterprise, is also applied in energy ultrawhite figured glass, glass, ceramic tile, ceramics
Deng the previously prepared silica separation layer in high-temperature insulation body surface face.In addition, using the colloidal sol containing tungsten oxide, or base material table
Face prepares tungsten oxide separation layer.
3. silica rubbing method.Using the nano oxidized silicon coating of commodity, directly object is implemented to coat with equipment such as sprayings
And be solidified into silica separation layer at room temperature, this method has had many success use cases in China, this method be applied to intolerant to
The previously prepared silica separation layer of substrate surface of high temperature.In addition, utilize commodity nanometer tungsten oxide coating, or base material table
Face prepares tungsten oxide separation layer.
(2) article coatings performance evaluation
1. static electricity resistance.The automatically cleaning product of inorganic transparent coating is coated with, detects its surface resistivity less than 1 × 1011(Ω/
Static electricity resistance is represented to be qualified with zero when), less than 1 × 109(Ω/) uses to be good ● represents, less than 1 × 108(Ω/□)
Represented to be outstanding with ★.Detection method is that sheet resistance tester directly is placed on into product surface and Pen-down detection key, root
Its surface resistivity is determined according to the indicator lamp on instrument, with reference to current standard《GA/T 1410-2006 solid insulating material volumes
Resistivity and surface resistivity test method》.
2. the transparency.The automatically cleaning product of inorganic transparent coating, the wherein transparent substance such as glass, glasses are coated with, can be straight
Connect and measure its visible light transmittance rate using light transmittance detector, and for the nontransparent object such as car body, display screen and billboard, can
Its identical coating is prepared using glass etc., its visible light transmittance rate is measured using light transmittance detector, measures the antistatic indirectly
The light transmittance of inorganic nano coating.If coating visible light transmittance rate TVis＞ 51% judges qualified zero table of the coating transparent
Show, TVis＞ 70% uses to be good ● represents, TVis＞ 80% is represented to be outstanding with ★.Alternatively, it is also possible to ready visual contrast, the product applies
Layer region and the aberration of neighboring area, such as indifference, then show that coating does not cover in original color of object, also can determine that painting
The layer transparency is qualified.
3. contact angle（contact angle）Refer to the tangent line of liquid-vapor interface made at gas, liquid, solid three-phase intersection point,
This tangent line is measuring for wetness degree in the angle theta between solid-liquid boundary line of the side of liquid one.Inorganic transparent in the present invention
The contact angle of coating is measured using profile image analysis method.Specific method is to drip water droplet in the coating sample surface, is passed through
Microlens and camera obtain the outline drawing picture of water droplet, then with Digital Image Processing and Young-Laplace equations by image
In the contact angle meter of water droplet calculate.If the contact angle of inorganic transparent coating and water droplet is less than 40 °, that is, judge the painting thickness
Spend it is qualified represented with zero, used less than 10 ° to be good ● represent, represented less than 5 ° to be outstanding with ★.
4. coating layer thickness.The automatically cleaning product of inorganic transparent coating is prepared for, is detected using equipment such as THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILSs
Its specific thickness.If thickness is 0.1~1000 nanometer or cannot recognize that surface relief injustice with human eye, that is, judge the coating
Thickness is qualified to be represented with zero, and it is good use that average thickness, which is less than 700 nanometers, ● is represented, it is outstanding that average thickness, which is less than 100 nanometers,
Represented with ★.
5. self-cleaning property.Under the same conditions, to the product surface and the phase without the coating for being prepared for automatic cleaning coating
Same article surface, brushed simultaneously with fan from some outdoor photovoltaic cell surface collections to sand and dust fine earth, stop after 30 minutes
Brush, if the laying dust amount of product surface is less than the 50% of uncoated article surface laying dust amount, you can judge the instant of the product
Self-cleaning performance is qualified to be represented with zero, is used less than 30% to be good ● is represented, is represented less than 10% to be outstanding with ★.The self checking method
It with reference to current standard《GA/T 31815-2015 outer surface of building self-cleaning coatings》,《JC/T 2210-2014 architectural potteries
Self-cleaning performance method of testing》With《GA/T 23764-2009 photocatalytic self-cleaning material performance test methods》Deng.
6. rub resistance.With rotation friction rubber wheel method measure automatically cleaning product coating abrasion performance, i.e., temperature (23 ±
2) DEG C, relative humidity (100 ± 5) %, rotating are the experimental condition that 60 ± 2r/min and arm carry 500g counterweights
Under, use external diameter to wear away coating surface for (51.6 ± 0.1) mm vulcanie friction wheel（Such as CS-10F abrasive wheels）, coating is resistance to
Mill property is lost the laboratory mean values three times of (weight-loss method) to grind coating quality after 50 revolutions and evaluated, and is accurate to 0.1mg, such as
Mass loss can determine that rub resistance is qualified less than 0.05g and be represented with zero, be used less than 0.03g to be good ● represent, less than 0.01g
Represented to be outstanding with ★.In addition, the adhesive force of coating rub resistance and coating, weatherability, hardness etc. are substantially coincident, i.e., it is resistance to
When frictional property is qualified, the adhesive force of the coating, weatherability, hardness etc. are also qualified.The detection method is with reference to existing international mark
It is accurate《ISO 7784-2-1997, Paints and varnishes, Determination of resistance to
Abrasion, Part 2: Rotating abrasive rubber wheel method》With《GA/T 1768-2006 colored paints
With the measure rotation rubber emery wheel method of varnish wearability》.
The foregoing is merely illustrative of the preferred embodiments of the present invention, and not to limit the present invention, it is all the present invention's
All any modification, equivalent and improvement made within spirit and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of self-cleaning nona coating, it is characterised in that its composition is in parts by weight：Nanometer conductive material 0.01~20
Part, 0.01~20 part of inorganic hard coat agent, 0.01~20 part of inorganic bond, 40~99.97 parts of hydrophilic solvent.
2. self-cleaning nona coating according to claim 1, it is characterised in that the nanometer conductive material is that particle diameter is
0.1~100 nanometer of conductive material, specially tin-doped indium oxide, tin oxide, antimony doped tin oxide, mix bismuth tin oxide, p-doped oxygen
Change tin, fluorine doped tin oxide, the fluorin-doped tin oxide of phosphorus, mix antimony zinc oxide, mix bismuth zinc oxide, CNT, graphene, tin alkene,
Nano Silver, nitridation dicalcium, stannic acid beryllium, magnesium stannate, calcium stannate, stronitum stannate, barium stannate, zinc stannate, wolframic acid caesium, vanadic acid beryllium, vanadic acid
One or more in magnesium, calcium vanadate, strontium vanadate, vanadic acid barium.
3. self-cleaning nona coating according to claim 1, it is characterised in that the inorganic hard coat agent is that particle diameter is 0.1
One or more in~100 nanometers of tungsten oxide, titanium oxide, cerium oxide, aluminum oxide, platinum, tungsten carbide.
4. self-cleaning nona coating according to claim 1, it is characterised in that the inorganic bond be silica,
One or more in Ludox, sodium metasilicate, potassium silicate.
5. self-cleaning nona coating according to claim 1, it is characterised in that the hydrophilic solvent is water, methanol, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-pentyl alcohol, 1- ethyls -1- third
One or more in alcohol, 2-methyl-1-butene alcohol, n-hexyl alcohol and cyclohexanol.
6. a kind of inorganic transparent coating, it is characterised in that be coated in any described self-cleaning nona coating of claim 1-5
Body surface and the coating being formed by curing, the painting method of prepares coating are one kind in spraying, showering, roller coat, spin coating, blade coating
Or multiple combinations, the solidification temperature of prepares coating are -50 DEG C~4000 DEG C, preferably 10 DEG C~800 DEG C, more preferably 25 DEG C~
700℃。
7. inorganic transparent coating according to claim 6, it is characterised in that coating has hydrophily, the contact with water droplet
Angle is less than 40 °, preferably less than 10 °, further preferably less than 5 °.
8. inorganic transparent coating according to claim 6, it is characterised in that the visible light transmissivity of coating is excellent more than 51%
Elect as more than 70%, further preferably greater than 80%.
9. inorganic transparent coating according to claim 6, it is characterised in that the surface resistivity ρ s of coating are less than 1 × 1012
Ω/, preferably less than 109Ω/, further preferably less than 108Ω/□。
10. a kind of automatically cleaning product, it is characterised in that the surface of the automatically cleaning product is provided with any institutes of claim 1-9
The inorganic transparent coating stated.
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| CN103627227A (en) * | 2013-11-27 | 2014-03-12 | 天津市职业大学 | Solar glass self-cleaning antireflection paint and production method thereof |
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