CN109321131A - Self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type height and preparation method thereof - Google Patents
Self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type height and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses high self-cleaning super-hydrophobic coatings of a kind of lasting wear-resisting type and preparation method thereof.The coating is solidified at room temperature by fluororesin, low-surface-energy filler, nano-titanium dioxide and isocyanate curing agent, wherein low-surface-energy filler and nano-titanium dioxide are respectively the combination of nano bar-shape and nano particle, or low-surface-energy filler or nano-titanium dioxide are the different nano particle of partial size, the two partial size ratio is greater than 10.The present invention is also able to maintain the ultraphobic water-bound of stable Cassie model in the case where height is dripped, and can degrade the organic pollutant of surface adhesion by itself photocatalysis effect, can persistently keep coating surface super-hydrophobic and high self-cleaning ability.And since the contact area between nanometer rods (line) or large particle size filler and fluororesin matrix is larger, abrasion, which falls off, needs to overcome biggish resistance, thus coating wearability itself is preferable, can guarantee the persistence of super-hydrophobic effect.
Description
Technical field
The invention belongs to organo-mineral complexing technical field of coatings, and in particular to a kind of high self-cleaning super-hydrophobic of lasting wear-resisting type
Coating and preparation method thereof.
Background technique
Automatically cleaning is usually the dust for measuring coating surface or pollutant outside gravity, wind-force, rain drop erosion and illumination etc.
Portion's effect is lower to realize a kind of ability for falling off or degrade and be able to maintain surface cleaning.It can be incited somebody to action according to the difference of surface wettability
Automatically cleaning mechanism is divided into super-hydrophobic and causes automatically cleaning and super hydrophilic cause automatically cleaning.There is super-hydrophobic coating water contact angle to be greater than 150 °,
The real contact area of water droplet on it and coating surface is dripped very in the surface of special wet face state of the roll angle less than 10 °
Small, the large quantity of air of coated trapped inside is held up, thus droplet shape easy to form rolls on the surface.Droplet tumbles process energy
It enough carries under one's arms the dust for being easy to be spontaneously wet out by water or pollutant is detached from coating surface, to reach self-cleaning effect.And super hydrophilic painting
The water contact angle of layer surface less than 5 °, greasy dirt be not easy it is attached to it, and can be by the moisture film that surface is formed by pollutant
It is rinsed and realizes automatically cleaning.Comprising a kind of special photic super-hydrophilic coating in super-hydrophilic coating, usually contain with light
The nano particle of catalytic activity, such as nano-TiO2It is a kind of typical photochemical catalyst, can effectively degrades under the action of illumination
The organic pollutant of coating surface, and the photic Superhydrophilic the characteristics of under, degradation material is capable of the flowing on coated surface
Moisture film washes out.
The preparation method of super-hydrophobic coating has template method, sol-gel method, chemical vapour deposition technique, self-assembly method, phase point
From method, etching method etc., existing common fault is that preparation process is complicated, at high cost and be unfavorable for large-scale production, prepares coating
Weatherability is usually bad, in addition, micro-rough structure necessary to super-hydrophobic coating be easy by external force destroy, drop roll by
Resistance, to lose super-hydrophobic effect bring automatically cleaning advantage.Be matrix using the low-surface-energy film forming matter having excellent weather resistance,
One step blending method of nano particle construction micro-nano coarse structure facilitates super-hydrophobic coating and realizes scale manufacturing.However it is good ultraphobic
Water effect is usually to reduce the mechanical performance especially wearability of coating itself as cost, thus super-hydrophobic coating has clothes
Use as a servant time short drawback.The techniques such as sol-gel method, self-assembly method, hydro-thermal method in the preparation method of super-hydrophilic coating are cumbersome,
Higher cost, prepares coating binding force are weak etc., limit the application of superhydrophilic self-cleaning coating.Contain in photic super-hydrophilic coating
Nano-titania particle when playing photocatalytic degradation effect, also be easy film forming matter is caused to degrade, the power of weaken coating
Learn performance.Super-hydrophobicity is combined with the characteristics of photocatalytic so that coating integrally keep super-hydrophobic effect while, office
The contact site of portion and water droplet can play the photocatalytic degradation effect to organic pollutant, realize height self-cleaning effect, and
With persistent super-hydrophobic effect, there is great application value.
Patent CN101962514B reports a kind of super-hydrophobic automatic cleaning coating of long wearing, patent CN103409028B
Also a kind of photocatalytic type self-repairing super-hydrophobic coating is disclosed, Research Thinking is to tie super-hydrophobic and photocatalysis effect
It closes, preparation process simple possible, however the simple matched combined for relying solely on nano-photo catalytic particle or nano particle uses,
The wear-resisting persistence of super-hydrophobic effect is not ensured that.And selfreparing effect is to rely on photocatalytic particle to the drop of film forming matrix
Solution realizes the reconstruct of coarse structure, does not ensure that the mechanical performance of coating.
Summary of the invention
In order to overcome the deficiencies of the prior art, the present invention provides a kind of high self-cleaning super-hydrophobic coating of lasting wear-resisting type and its preparation
Method.The self-cleaning super-hydrophobic coating of the height is existed by fluororesin, low-surface-energy filler, nano-titanium dioxide and isocyanate curing agent
Solidify at room temperature, the prepared self-cleaning super-hydrophobic coating of height is also able to maintain stable in the case where height is dripped
The ultraphobic water-bound of Cassie model, and can degrade the organic pollutant of surface adhesion by itself photocatalysis effect, energy
Enough super-hydrophobic for persistently keeping coating surface and high self-cleaning ability.
To realize that the above technical purpose, the present invention are achieved through the following technical solutions: a kind of lasting wear-resisting type height is self-cleaning
Super-hydrophobic coating, including fluororesin, low-surface-energy filler, nano-titanium dioxide and isocyanate curing agent, fluororesin by with
Isocyanate curing agent carries out crosslinking and realizes solidification, wherein low-surface-energy filler and nano-titanium dioxide be respectively nano bar-shape with
The combination of nano particle or low-surface-energy filler or nano-titanium dioxide are the different nano particle of partial size, low-surface-energy filler
It is greater than 10 with the partial size ratio of nano-titanium oxide.Compound painting is prepared using nano bar-shape low-surface-energy filler and nano titania particle
Layer, micro-nano coarse structure needed for capable of steadily constructing both ultrahydrophobic, coating surface are not easy to be infected with floating ash, and water droplet tumbled
Journey can take pollutant out of surface；Furthermore the titanium dioxide granule being distributed between nano bar-shape filler can be imitated by photocatalysis
Should degrade the organic matter on surface.By the combination of above-mentioned super-hydrophobic and photocatalysis effect, the height for being able to maintain coating surface is self-cleaning
Characteristic.Using the composite filling of nanometer rods and nano particle, or the composite filling of big partial size ratio, prepares coating surface microstructure
It is easier to maintain stable Cassie model, water droplet remains to tumble in coating surface under impact.And due to nanometer rods (line)
Or the contact area between large particle size filler and fluororesin matrix is larger, abrasion, which falls off, needs to overcome biggish resistance, thus applies
Wearability of layer itself is preferable, can guarantee the persistence of super-hydrophobic effect.
The fluororesin is three fluorine-type FEVE resin of room temperature curing, four fluorine-type FEVE resins, fluorine richness silicone resin, fluorine richness
One or more of mixtures of acrylic resin etc..Use fluororesin for film-forming resin, the low, excellent in weather of surface energy, and
And nano-TiO can be kept out2Photocatalytic Degradation, prevent coating dusting, mechanical performance is lasting.
The low-surface-energy filler is silicon fluoride modified Nano filling, and the nanofiller is attapulgite, carbon fiber, carbon
Nanotube, the SiO that partial size is 500-1000nm2、Al2O3、CaCO3Deng one or more of mixtures.The silicon fluoride is complete
The mixture of one or both of fluorine octyltri-ethoxysilane, perfluoro decyl triethoxysilane.
The nano-titanium dioxide is the nano-titanium dioxide or two that the partial size that Detitanium-ore-type is main crystal form is 5-100nm
Titanium oxide nano wire.
The preparation step of the silicon fluoride modified Nano filling are as follows: nanofiller is added in ethyl alcohol and passes through shearing-ultrasound-
The endless form of shearing is dispersed, and is exported by shearing dispersion and the energy of large power supersonic, is realized the high degree of dispersion of nanofiller,
The hydrolyzate of silicon fluoride is added afterwards, wherein silicon fluoride and the mass ratio of nanofiller are 0.2-0.5:1.Then at 100 DEG C -120
DEG C back flow reaction 22 hours or more, silicon fluoride modified Nano filling can be obtained in centrifugal drying.The hydrolyzate of the silicon fluoride is
Silicon fluoride, deionized water, dehydrated alcohol are 3 according to the pH value of 5~1 ︰ of mass ratio 1 ︰, 1 ︰, 1.5 ︰ 15 (1 ︰ of preferably 1 ︰, 5~1 ︰, 1 ︰ 10)
~5 mixed liquor.
A kind of high self-cleaning super-hydrophobic coating of lasting wear-resisting type of the present invention, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluororesin 20-40%, low-surface-energy nano-attapulgite 3-40%, nanometer
TiO 2 particles 4-30%, organic solvent 20-60% and isocyanate curing agent 2.5-7.5%.
The fluororesin is fluorinated silicone modified resin (abbreviation fluorine silicon resin)；The low-surface-energy concave convex rod is perfluoro decyl
(or octyl) triethoxysilane modified attapulgite, diameter 3-10nm, length are 0.1-1 μm；The organic solvent is second
The mixed solvent of acid butyl ester and dimethylbenzene, mass ratio are (1-3) ︰ 1；The isocyanate curing agent is HDI trimer, preferably
Bayer Bitterfeld GmbH N3390.
A kind of high self-cleaning super-hydrophobic coating of lasting wear-resisting type of the present invention, is the coating room temperature by another certain component
Solidify, wherein in coating each component mass percent are as follows: fluororesin 20-60%, low-surface-energy concave convex rod 5-20% change
Property nano silica 3-15%, nano-titania particle 1-20%, organic solvent 20-60% and isocyanate curing agent 2-
7%.
The fluororesin is modified fluoro-silicone resin；The low-surface-energy concave convex rod is perfluoro capryl (or decyl) three ethoxy
Base silane modified attapulgite, diameter 3-10nm, length are 0.1-1 μm；The organic solvent is butyl acetate and dimethylbenzene
Mixed solvent, mass ratio are (1-3) ︰ 1；The isocyanate curing agent is HDI trimer, preferably Bayer Bitterfeld GmbH N3390.
The high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type of the present invention, through the following steps that being prepared: by low surface
Can filler and nano-titanium dioxide mixed grinding according to a certain percentage, be added in organic solvent and be dispersed into using large power supersonic
Row dispersion 30min-1h, is added fluororesin into finely dispersed filler suspension, mixes 1h-2h using mechanical stirring first,
30min-1h is ground using blue-type mulling machine afterwards, coating composition A can be obtained.Before coating construction, component A is consolidated with isocyanates
Agent is proportionally uniformly mixed, and can obtain high self-cleaning super-hydrophobic coating coated in substrate surface drying at room temperature.
The large power supersonic dispersion power is 50W-100W.When power is too low, some particle agglomerations can not be opened,
Influence mixing and the dispersion effect of filler；Power is excessively high, and dispersion liquid heating is too fast, and generates the more bubble for being difficult to eliminate, shadow
Post-coatings preparation is rung, and causes the waste of energy.
The mechanical stirring speed is 500rpm-1500rpm.When mixing speed is too low, weaken the mixing of filler and resin
Effect；Mixing speed is excessively high, and the vortex of generation can be involved in large quantity of air, is unfavorable for the defoaming of coating itself.
Persistently high self-cleaning super-hydrophobic coating of wear-resisting type and preparation method thereof has the advantage that (1) to one of present invention
Preparation process is simple, large-scale production application easy to accomplish；(2) low-surface-energy, weatherability are good, can be realized long service；(3) surpass
Hydrophobic effect is good, and coating surface is not easy to be infected with floating ash, and water droplet, which tumbles process, can take pollutant out of on surface to realize surface
Automatically cleaning；(4) titanium dioxide granule can be realized by the organic matter on photocatalytic effect degradation surface to the clear of organic matter
It is clean, there is Dual high-efficiency self-cleaning ability.(5) composite filling of nanometer rods and nano particle, or the combination of big partial size ratio is used to fill out
Material, prepares coating surface microstructure are easier to maintain stable Cassie model, and water droplet remains under certain velocity shock
It tumbles and leaves no trace in coating surface；(6) due to the contact between nanometer rods (line) or large particle size filler and fluororesin matrix
Area is larger, and abrasion, which falls off, needs to overcome biggish resistance, thus coating wearability itself is preferable, can guarantee super-hydrophobic effect
Persistence.(7) as a kind of natural nano bar-shape fibrous material, attapulgite has unique gap structure and interface characteristics
Matter, and have excellent absorption property.Such gap structure provides adequate condition, and itself for the construction of ultraphobic water-bound
Structural property can promote the catalytic effect of photochemical catalyst.
Specific embodiment
Below with reference to embodiment, the present invention is further described.
Although specific embodiment is described in the present invention, it is not intended to limit the protection scope of the present invention, affiliated
Field technical staff should be understood that based on the technical solutions of the present invention those skilled in the art do not need to pay creation
Property the labour various modifications or changes that can make still within protection scope of the present invention.
Embodiment 1
1) it prepares silicon fluoride modified Nano concave convex rod and mixes 6 parts of deionized waters with 60 parts of dehydrated alcohols, adjusted with acetic acid
The pH value of mixed liquor is 4.6 parts of perfluoro capryl triethoxysilanes are added to it, magnetic agitation 30 minutes, promote silicon fluoride abundant
Hydrolysis.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, high-shearing dispersion emulsifying machine 6000rpm shearing dispersion 20min,
30min is dispersed using large power supersonic 80W afterwards, again using 6000rpm shearing dispersion 20min.
By silicon fluoride hydrolyzate be added concave convex rod dispersion liquid in, 100 DEG C of back flow reactions for 24 hours, centrifugal drying can obtain
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 25%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 15%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm) 5%；Butyl acetate 39%；Diformazan
Benzene 13%；Bayer B3390 3%.The high self-cleaning super-hydrophobic coating of lasting wear-resisting type in the present embodiment, through the following steps that system
It is standby to form: perfluoro capryl triethoxysilane modified Nano concave convex rod and nano-titanium dioxide proportionally mixed grinding add
Enter into organic solvent and dispersion 30min is carried out using large power supersonic dispersion 80W, is added into finely dispersed filler suspension
Fluorine silicon resin uses mechanical stirring 800rpm mixing 2h first, grinds 30min using blue-type mulling machine afterwards, can obtain coating
Component A.Before coating construction, component A is proportionally uniformly mixed with Bayer N3390, is coated in substrate surface drying at room temperature just
It can get high self-cleaning super-hydrophobic coating.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 155.7 °, roll angle is 2 °.With substrate of glass
Binding force wears 40 circulations on 400# sand paper and (carries out vertical and horizontal intersection 10cm respectively under the weight of 100g counterweight up to 1 grade
Abrasion be 1 circulation) contact angle is 155.2 °, roll angle is 4 ° afterwards.Diameter is the water droplet of 5mm apart from coating 80cm-
The height of 120cm is dripped, and remains to walk in coating surface rolling easily.Coating is immersed in the methylene blue solution of 10mg/L simultaneously
In 1W/m2Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to illumination
Solution after penetrating is demarcated, concentration 0.7mg/L.
Embodiment 2
1) silicon fluoride modified Nano concave convex rod is prepared
6 parts of deionized waters are mixed with 30 parts of dehydrated alcohols, the pH value with acetic acid adjustment mixed liquor is 4.6 parts are added to it
Perfluoro capryl triethoxysilane magnetic agitation 30 minutes, promotes silicon fluoride to be fully hydrolyzed.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, and 6000rpm shearing dispersion 20min uses large power supersonic afterwards
Disperse 30min, again using 6000rpm shearing dispersion 20min.
Silicon fluoride hydrolyzate is added in the dispersion liquid of concave convex rod, in 120 DEG C of back flow reaction 22h, centrifugal drying can be obtained
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 23%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 23%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm) 4.5%；Butyl acetate 32%；Two
Toluene 14%；Bayer B3390 3.5%.The high self-cleaning super-hydrophobic coating production of lasting wear-resisting type and implementation in the present embodiment
Example 1 is identical.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 156 °, roll angle is 2.5 °.With substrate of glass
Binding force wears 40 circulations on 400# sand paper and (carries out vertical and horizontal intersection 10cm respectively under the weight of 100g counterweight up to 1 grade
Abrasion be 1 circulation) contact angle is 155.9 °, roll angle is 3 ° afterwards.Diameter is the water droplet of 5mm apart from coating 100cm's
Height is dripped, and remains to walk in coating surface rolling easily.Coating is immersed in the methylene blue solution of 10mg/L and in 1W/m2
Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to light irradiation after
Solution is demarcated, concentration 1mg/L.
Embodiment 3
1) silicon fluoride modified Nano concave convex rod is prepared
10 parts of deionized waters are mixed with 100 parts of dehydrated alcohols, the pH value with acetic acid adjustment mixed liquor is 4.It is added to it
10 parts of perfluoro capryl triethoxysilanes magnetic agitation 30 minutes, promote silicon fluoride to be fully hydrolyzed.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, and 6000rpm shearing dispersion 20min uses large power supersonic afterwards
Disperse 30min, again using 6000rpm shearing dispersion 20min.
Silicon fluoride hydrolyzate is added in the dispersion liquid of concave convex rod, in 100 DEG C of back flow reaction 30h, centrifugal drying can be obtained
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 33%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 4%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm) 26%；Butyl acetate 22%；Diformazan
Benzene 11%；Bayer B3390 4%.The high self-cleaning super-hydrophobic coating production of lasting wear-resisting type and embodiment 1 in the present embodiment
It is identical.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 155 °, roll angle is 3.5 °.With substrate of glass
Binding force wears 40 circulations on 400# sand paper and (carries out vertical and horizontal intersection 10cm respectively under the weight of 100g counterweight up to 1 grade
Abrasion be 1 circulation) contact angle is 154 °, roll angle is 4.5 ° afterwards.Diameter is the water droplet of 5mm in the height apart from coating 90cm
Degree drippage remains to walk in coating surface rolling easily.Coating is immersed in the methylene blue solution of 10mg/L and in 1W/m2's
Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to molten after light irradiation
Liquid is demarcated, concentration 0.5mg/L.
Embodiment 4
1) silicon fluoride modified Nano concave convex rod is prepared
6 parts of deionized waters are mixed with 60 parts of dehydrated alcohols, the pH value with acetic acid adjustment mixed liquor is 4.6 parts are added to it
Perfluoro capryl triethoxysilane magnetic agitation 30 minutes, promotes silicon fluoride to be fully hydrolyzed.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, and 6000rpm shearing dispersion 20min uses large power supersonic afterwards
Disperse 30min, again using 6000rpm shearing dispersion 20min.
Silicon fluoride hydrolyzate is added in the dispersion liquid of concave convex rod, in 110 DEG C of back flow reaction 22h, centrifugal drying can be obtained
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 30%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 30%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm) 6%；Butyl acetate 20%；Diformazan
Benzene 10%；Bayer B3390 4%.The high self-cleaning super-hydrophobic coating production of lasting wear-resisting type and embodiment 1 in the present embodiment
It is identical.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 157.5 °, roll angle is 2.5 °.With glass base
Bear building-up resultant force is worn 40 circulations on 400# sand paper and (is intersected anyhow respectively under the weight of 100g counterweight up to 1 grade
The abrasion of 10cm is 1 circulation) contact angle is 157 °, roll angle is 2.5 ° afterwards.Diameter is the water droplet of 5mm apart from coating 90cm
Height drippage, remain to easily coating surface rolling walk.Coating is immersed in the methylene blue solution of 10mg/L and in 1W/
m2Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to light irradiation after
Solution demarcated, concentration 0.8mg/L.
Embodiment 5
1) silicon fluoride modified Nano concave convex rod is prepared
6 parts of deionized waters are mixed with 60 parts of dehydrated alcohols, the pH value with acetic acid adjustment mixed liquor is 4.6 parts are added to it
Perfluoro capryl triethoxysilane, magnetic agitation 30 minutes, so that silicon fluoride is fully hydrolyzed.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, and 6000rpm shearing dispersion 20min uses large power supersonic afterwards
Disperse 30min, again using 6000rpm shearing dispersion 20min.
Silicon fluoride hydrolyzate is added in the dispersion liquid of concave convex rod, in 110 DEG C of back flow reaction 22h, centrifugal drying can be obtained
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) modified manometer silicon dioxide is prepared
Perfluoro decyl triethoxysilane is used to be modified processing to granularity for the nano silica of 20nm, other works
Skill is identical as concave convex rod modified technique, obtains modified manometer silicon dioxide.
3) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 38%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 8%；Modified manometer silicon dioxide 8%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm)
4%；Butyl acetate 28%；Dimethylbenzene 10%；Bayer B3390 4%.The high self-cleaning super-hydrophobic of lasting wear-resisting type in the present embodiment
Coating, through the following steps that being prepared: modified Nano concave convex rod, modified manometer silicon dioxide and nano-titanium dioxide are mixed
Grinding is closed, is added in organic solvent and dispersion 30min is carried out using large power supersonic dispersion 100W, it is outstanding to finely dispersed filler
Fluorine silicon resin is added in turbid, uses mechanical stirring 1000rpm mixing 2h first, grinds 30min using blue-type mulling machine afterwards, just
It can get coating composition A.Before coating construction, component A is proportionally uniformly mixed with Bayer N3390, is coated in substrate surface
Drying at room temperature can obtain high self-cleaning super-hydrophobic coating.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 157.5 °, roll angle is 2 °.With substrate of glass
Binding force wears 40 circulations on 400# sand paper and (carries out vertical and horizontal intersection 10cm respectively under the weight of 100g counterweight up to 1 grade
Abrasion be 1 circulation) contact angle is 157.1 °, roll angle is 2.5 ° afterwards.Diameter is the water droplet of 5mm apart from coating 120cm
Height drippage, remain to easily coating surface rolling walk.Coating is immersed in the methylene blue solution of 10mg/L and in 1W/
m2Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to light irradiation after
Solution demarcated, concentration 1.2mg/L.
Embodiment 6
1) silicon fluoride modified Nano concave convex rod is prepared
10 parts of deionized waters are mixed with 100 parts of dehydrated alcohols, the pH value with acetic acid adjustment mixed liquor is 4.It is added to it
10 parts of perfluoro capryl triethoxysilanes, magnetic agitation 30 minutes, so that silicon fluoride is fully hydrolyzed.
20 parts of concave convex rods are added in 400 parts of dehydrated alcohols, and 6000rpm shearing dispersion 20min uses large power supersonic afterwards
Disperse 30min, again using 6000rpm shearing dispersion 20min.
By silicon fluoride hydrolyzate be added concave convex rod dispersion liquid in, 100 DEG C of back flow reactions for 24 hours, centrifugal drying can obtain
To silicon fluoride modified Nano concave convex rod, diameter 3-10nm, length is 0.1-1 μm.
2) modified manometer silicon dioxide is prepared
Perfluoro decyl triethoxysilane is used to be modified processing to granularity for the nano silica of 20nm, other works
Skill is identical as concave convex rod modified technique, obtains modified manometer silicon dioxide.
3) the high self-cleaning super-hydrophobic coating of lasting wear-resisting type is prepared
The high self-cleaning super-hydrophobic coating of the lasting wear-resisting type of the present embodiment, is the coating room temperature curing by certain component
At, wherein in coating each component mass percent are as follows: fluorine silicon resin 27%；Perfluoro capryl triethoxysilane modified Nano is recessed
Convex stick 22%；Modified manometer silicon dioxide 4%；Nano-titania particle (Detitanium-ore-type is main crystal form, partial size 20nm)
3%；Butyl acetate 30%；Dimethylbenzene 10%；Bayer B3390 4%.The high self-cleaning super-hydrophobic of lasting wear-resisting type in the present embodiment
Coating, through the following steps that being prepared: modified Nano concave convex rod, modified manometer silicon dioxide and nano-titanium dioxide are mixed
Grinding is closed, is added in organic solvent and dispersion 30min is carried out using large power supersonic dispersion 100W, it is outstanding to finely dispersed filler
Fluorine silicon resin is added in turbid, uses mechanical stirring 1000rpm mixing 2h first, grinds 30min using blue-type mulling machine afterwards, just
It can get coating composition A.Before coating construction, component A is proportionally uniformly mixed with Bayer N3390, is coated in substrate surface
Drying at room temperature can obtain high self-cleaning super-hydrophobic coating.
The self-cleaning super-hydrophobic coating of height prepared by the formula, contact angle is 156.8 °, roll angle is 3 °.With substrate of glass
Binding force wears 40 circulations on 400# sand paper and (carries out vertical and horizontal intersection 10cm respectively under the weight of 100g counterweight up to 1 grade
Abrasion be 1 circulation) contact angle is 156.5 °, roll angle is 2.8 ° afterwards.Diameter is the water droplet of 5mm apart from coating 100cm
Height drippage, remain to easily coating surface rolling walk.Coating is immersed in the methylene blue solution of 10mg/L and in 1W/
m2Ultraviolet light 168h, it is possible to find methylene blue solution color is obviously thin out, using ultraviolet spectrometry degree meter to light irradiation after
Solution demarcated, concentration 1mg/L.
Claims (10)
1. a kind of high self-cleaning super-hydrophobic coating of lasting wear-resisting type, including fluororesin, low-surface-energy filler, nano-titanium dioxide and different
Cyanate curing agent solidifies at room temperature, and wherein low-surface-energy filler and nano-titanium dioxide are respectively nano bar-shape and receive
The combination of rice grain or low-surface-energy filler and the nano-titanium dioxide nano particle that be partial size different, low-surface-energy filler with
The partial size ratio of nano-titanium oxide is greater than 10.
2. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as described in claim 1, characterized in that
The nano-titanium dioxide is the nano-titanium dioxide or titanium dioxide that the partial size that Detitanium-ore-type is main crystal form is 5-100nm
Titanium nano wire；
The fluororesin is three fluorine-type FEVE resin of room temperature curing, four fluorine-type FEVE resins, fluorine richness silicone resin, fluorine richness propylene
The mixture of one or more of acid resin.
3. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as described in claim 1, characterized in that
The low-surface-energy filler is the modified nanofiller of silicon fluoride, and the nanofiller is concave convex rod, carbon fiber, carbon nanometer
Pipe, partial size are the SiO of 500-1000nm2、Al2O3Or CaCO3, the mixture of one or more of above-mentioned raw materials；
The silicon fluoride is the mixing of one or both of perfluoro capryl triethoxysilane, perfluoro decyl triethoxysilane
Object.
4. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as described in any one of claim 1-3, characterized in that institute
Stating the modified nanofiller of silicon fluoride is to be prepared by the following method: nanofiller is added in ethyl alcohol through shearing-ultrasound-
The endless form of shearing is dispersed, and the hydrolyzate of silicon fluoride is then added, and wherein silicon fluoride and the mass ratio of nanofiller are 0.2-
0.5:1.Then 100 DEG C -120 DEG C of back flow reactions 22 hours or more, centrifugal drying obtains silicon fluoride modified Nano filling.
5. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as claimed in claim 4, characterized in that the water of the silicon fluoride
Solution liquid is that the hydrolyzate hydrolyzed in the mixed liquor that the pH value of deionized water and dehydrated alcohol is 3~5 is added in silicon fluoride.
6. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as claimed in claim 4, characterized in that be by following components
Coating room temperature curing forms, wherein in coating each component mass percent are as follows: fluororesin 20-40%, low-surface-energy nanometer are recessed
Convex stick 3-40%, nano-titania particle 4-30%, organic solvent 20-60% and isocyanate curing agent 2.5-7.5%.
7. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as claimed in claim 4, characterized in that be by following components
Coating room temperature curing forms, wherein in coating each component mass percent are as follows: fluororesin 20-60%, low-surface-energy concave convex rod
5-20%, modified manometer silicon dioxide 3-15%, nano-titania particle 1-20%, organic solvent 20-60% and isocyanic acid
Ester curing agent 2-7%.
8. the high self-cleaning super-hydrophobic coating of a kind of lasting wear-resisting type as claimed in claims 6 or 7, characterized in that
The fluororesin is modified fluoro-silicone resin；The low-surface-energy concave convex rod is perfluoro capryl triethoxysilane or perfluor
Ruthenium triethoxysilane modified attapulgite, diameter 3-10nm, length are 0.1-1 μm；The organic solvent is butyl acetate
With the mixed solvent of dimethylbenzene, mass ratio is (1-3) ︰ 1；The isocyanate curing agent is HDI trimer.
9. a kind of preparation method of the high self-cleaning super-hydrophobic coating of lasting wear-resisting type as claimed in claims 6 or 7, characterized in that
By low-surface-energy filler and nano-titanium dioxide mixed grinding, it is added in organic solvent and is divided using large power supersonic
30min-1h is dissipated, fluororesin is added into finely dispersed filler suspension, 1h-2h, rear benefit are mixed using mechanical stirring first
30min-1h is ground with blue-type mulling machine, obtains coating composition A；Before coating construction, by component A and isocyanate curing agent according to
Ratio is uniformly mixed, and can obtain high self-cleaning super-hydrophobic coating coated in substrate surface drying at room temperature.
10. a kind of preparation method of the high self-cleaning super-hydrophobic coating of lasting wear-resisting type as claimed in claim 9, characterized in that institute
The power for stating large power supersonic dispersion is 50W-100W；The churned mechanically speed is 500rpm-1500rpm.
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