CN107236451B - Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating and its preparation method and application - Google Patents
Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating and its preparation method and application Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims abstract description 89
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 35
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 46
- 235000019441 ethanol Nutrition 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 235000013339 cereals Nutrition 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 239000002109 single walled nanotube Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 241000209094 Oryza Species 0.000 claims 2
- GWKBSZQPLYRAAH-UHFFFAOYSA-N 6-trimethoxysilylhexyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCOC(=O)C(C)=C GWKBSZQPLYRAAH-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001722 carbon compounds Chemical class 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 5
- -1 γ (methacryloxypropyl) propyl Chemical group 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 230000002596 correlated effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 206010038743 Restlessness Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/10—Cleaning arrangements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to nano functional coating field, a kind of hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating and its preparation method and application are disclosed.Hydrophilic self-cleaning coating composition disclosed by the invention, wherein the coating composition contains modified complex sol, nano-titanium dioxide powder and alcohol；The modified complex sol is the compound as obtained from being reacted the aqueous dispersions of alcohol, ethyl orthosilicate, modifying agent, deionized water and carbon nanotube in acid condition, wherein, the modifying agent is one or more in γ glycidyl ether oxygen propyl trimethoxy silicanes, γ aminopropyl triethoxysilanes and γ (methacryloxypropyl) propyl trimethoxy silicane.The hydrophilic self-cleaning coating feature of environmental protection provided by the invention is good, and uses it in photovoltaic power generation plate, and good weatherability, light transmittance are high, room temperature film-forming is good, and can effectively reduce dirty attachment, eliminate electrostatic influence.
Description
Technical field
The present invention relates to nano functional coating technical fields, and in particular, to a kind of hydrophilic self-cleaning coating composition and
Hydrophilic self-cleaning coating and its preparation method and application.
Background technology
According to national energy industrial policy, the year two thousand twenty is arrived, domestic photovoltaic installed capacity will at least arrive 50GW, solar energy hair
The opportunity of exhibition has come to.But meanwhile solar panel surface dust accumulation and other pollutant effect light transmittances, and generate quiet
Electric disturbance unrest generation current influences 6.8% or more generating efficiency average out to especially in the north.Dust is difficult to or needs frequent clean,
Cost increase, work difficulty is caused to increase, the practical problems such as design performance is difficult to give full play to, decrease in power generation efficiency.
Self-cleaning coating can generally be divided into hydrophobic self-cleaning coating and hydrophilic self-cleaning coating currently on the market.
Wherein, hydrophobic self-cleaning coating can will appear hydrophobic effect in glass or ceramic surface, show as water in object table
Face is in droplet shape, and is slided to lower, and droplet can wrap up in away the tiny sundries such as dust, to reach clean effect；But by
It is usually the high-molecular organic material of oleophylic in hydrophobic product, due to electrostatic adsorption ash easy to stick, is difficult to after accumulation of pollutants
It is rinsed with water totally, is especially unsuitable for using in the less area of northern rainwater.
Wherein, hydrophilic self-cleaning coating mainly has two kinds of inorganic hydrophilic self-cleaning coating and organic hydrophilic self-cleaning coating.Inorganic parent
Water self-cleaning coating is with nano-TiO2For primary raw material, it is sprayed on glass surface and quickly forms one layer of hydrophilic moisture film, make dirty be difficult to
Attachment, is rinsed, achieve the purpose that self-cleaning under rainwash；But this coating is also easy absorption oiliness pollution
Object, and the durability on glass is bad.Organic hydrophilic self-cleaning coating can make film by adding suitable hydrophilic agent
Hydrophilized surface is formed, coating self-cleaning is assigned；But the coating contact angle formed is larger, and self-cleaning effect is not apparent.
Therefore, a kind of hydrophilic self-cleaning coating that self-cleaning effect is good is researched and developed to be of great significance.
Invention content
The purpose of the invention is to overcome drawbacks described above of the existing technology, a kind of hydrophilic self-cleaning coating group is provided
Close object and hydrophilic self-cleaning coating and its preparation method and application.The hydrophilic self-cleaning coating feature of environmental protection provided by the invention is good, and will
It is used for photovoltaic power generation plate, and good weatherability, light transmittance are high, room temperature film-forming is good, and can effectively reduce dirty attachment, eliminate quiet
Film is rung.
One aspect of the present invention provides a kind of hydrophilic self-cleaning coating composition, wherein the coating composition contains
Modified complex sol, nano-titanium dioxide powder and alcohol；The modified complex sol is by by alcohol, ethyl orthosilicate, modification
Compound obtained from the aqueous dispersions of agent, deionized water and carbon nanotube are reacted in acid condition, wherein described to change
Property agent be γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and γ-(methacryls
Oxygen) it is one or more in propyl trimethoxy silicane.
Preferably, on the basis of the total weight of the coating composition, the content of the modified complex sol is 15-38
The content of weight %, the nano-titanium dioxide powder are 0.5-5 weight % and the content of the alcohol is 15-62 weight %.
Preferably, the grain size of the modified complex sol is 15-100nm；The grain size of the nano-titanium dioxide powder is
5-25nm, crystal form are anatase.
Preferably, the coating composition also contains coalescents and/or wetting agent, and with the coating composition
On the basis of total weight, the content of the coalescents is 1-8 weight %, and the content of the wetting agent is 1-5 weight %.
Preferably, the carbon nanotube is single-walled carbon nanotube；And the quality of the aqueous dispersions of the carbon nanotube is dense
Degree is 0.1-1 weight %.
Preferably, the alcohol is absolute ethyl alcohol and/or isopropanol.
Another aspect of the present invention additionally provides a kind of preparation method of hydrophilic self-cleaning coating composition, wherein this method
Include the following steps：
(1) in acid condition, the aqueous dispersions of deionized water and carbon nanotube are added drop-wise to containing alcohol, ethyl orthosilicate
With modified complex sol is obtained in the mixture of modifying agent；
(2) in acid condition, deionized water is added drop-wise in the mixture containing butyl titanate, acetylacetone,2,4-pentanedione and alcohol and is obtained
To nano-titanium dioxide powder；
(3) nano-titanium dioxide powder, the modified complex sol and alcohol are mixed.
Preferably, in step (1), on the basis of the total weight of the modified complex sol, the dosage of the alcohol is 30-
The dosage of 50 weight %, the ethyl orthosilicate are 16-28 weight %, and the dosage of the modifying agent is 19-30 weight %, described
The dosage of deionized water is 14-28 weight %, and the dosage of the aqueous dispersions of the carbon nanotube is 0.5-9 weight %.
Preferably, in step (2), on the basis of the total weight of the nano-titanium dioxide powder, the butyl titanate
Dosage be 9-16 weight %, the dosage of the acetylacetone,2,4-pentanedione is 10-17 weight %, and the dosage of the alcohol is 25-45 weight %,
The dosage of the deionized water is 19-32 weight %.
Preferably, it is 2-3 that the acid condition, which is pH value,.
Preferably, the deionized water is added dropwise with the drop rate of 0.01-0.5mL/s, the carbon nanotube it is water-dispersed
Liquid is added dropwise with the drop rate of 0.05-0.5mL/s.
Preferably, in step (2), this method further includes being added drop-wise to containing butyl titanate, levulinic by deionized water
After in the mixture of ketone and alcohol, it is also necessary to which by colloidal sol obtained by the reaction, processing 0.5-2 is small under conditions of temperature is 300-500 DEG C
When.
Another aspect of the present invention additionally provides a kind of hydrophilic self-cleaning coating composition and by above-mentioned preparation method system
Application of the standby obtained hydrophilic self-cleaning coating in the automatically cleaning of photovoltaic cell plate face.
Description of the drawings
Fig. 1 is the contact angle of the hydrophilic self-cleaning coating that is prepared by embodiment 1 on surface of photovoltaic cell panel；
Fig. 2 is coating and is not coated with the photovoltaic battery panel for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 in pair in the rain
The design sketch of ratio；
Fig. 3 is coating and is not coated with the photovoltaic battery panel for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 after one month
The design sketch of comparison afterwards；
Fig. 4 is the visible light transmittance and wave of the quartz glass plate coated with the hydrophilic self-cleaning coating prepared by embodiment 1
The curve graph of long relationship.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
On the one hand, the present invention provides a kind of hydrophilic self-cleaning coating compositions, wherein the coating composition contains
Modified complex sol, nano-titanium dioxide powder and alcohol；The modified complex sol is by by alcohol, ethyl orthosilicate, modification
Compound obtained from the aqueous dispersions of agent, deionized water and carbon nanotube are reacted in acid condition, wherein described to change
Property agent can be γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and γ-(metering systems
Acyl-oxygen) it is one or more in propyl trimethoxy silicane.
The present inventor has found in the course of the study, by that will be modified complex sol, nano-titanium dioxide powder
It is used in combination with alcohol, obtained coating has the characteristics that the feature of environmental protection is good, and uses it in photovoltaic power generation plate, weatherability
Good, light transmittance height, room temperature film-forming are good, and can effectively reduce dirty attachment, eliminate electrostatic influence.
In the case of preferred, on the basis of the total weight of the coating composition, the content of the modified complex sol
Can be 15-38 weight %, the content of the nano-titanium dioxide powder can be containing for 0.5-5 weight % and the alcohol
Amount can be 15-62 weight %；It is highly preferred that on the basis of the total weight of the coating composition, the modification is compound molten
The content of glue is 35-38 weight %, and the content of the nano-titanium dioxide powder is 0.5-2 weight % and the alcohol contains
Amount is 55-58 weight %；In the present invention, it is used for the ease of proportioning, each component in the coating composition is according to one
Fixed ratio storage.
According to the present invention, the grain size of the modified complex sol can be 15-100nm.
According to the present invention, the light transmission of the coating prepared in order to further increase by the hydrophilic self-cleaning coating composition
The grain size of rate, the nano-titanium dioxide powder can be 5-25nm, preferably 5-15nm, more preferably 5-10nm；And institute
The crystal form for stating nano-titanium dioxide powder is anatase.
According to the present invention, the coating composition can also contain coalescents and/or wetting agent, and be used with the coating
On the basis of the total weight of composition, the content of the coalescents can be 1-8 weight %, and the content of the wetting agent can be
1-5 weight %；In the present invention, the coalescents can be the various coalescents of this field routine, it is preferable that described
Coalescents are aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethylaminopropyl triethoxysilane and ammonia
It is one or more in hydroxypropyl methyl diethoxy silane；The wetting agent can be the various wetting agents of this field routine, excellent
Selection of land, the wetting agent are one or more in BYK-380N, BYK-381, EFKA3030, EFKA3034 and EFKA3500.
According to the present invention, the light transmission of the coating prepared in order to further increase by the hydrophilic self-cleaning coating composition
Rate, the carbon nanotube are preferably single-walled carbon nanotube, can be commercially available, and can also prepare and obtain according to known methods
, details are not described herein.In the present invention, the mass concentration of the aqueous dispersions of the carbon nanotube can be 0.1-1 weight %,
Preferably 0.5-1 weight %.
According to the present invention, the environmental protection of the coating prepared in order to further increase by the hydrophilic self-cleaning coating composition
Property, the alcohol is preferably absolute ethyl alcohol and/or isopropanol.
On the other hand, the present invention also provides a kind of preparation methods of hydrophilic self-cleaning coating composition, wherein this method
Include the following steps：
(1) in acid condition, the aqueous dispersions of deionized water and carbon nanotube are added drop-wise to containing alcohol, ethyl orthosilicate
With modified complex sol is obtained in the mixture of modifying agent；
(2) in acid condition, deionized water is added drop-wise in the mixture containing butyl titanate, acetylacetone,2,4-pentanedione and alcohol and is obtained
To nano-titanium dioxide powder；
(3) nano-titanium dioxide powder, the modified complex sol and alcohol are mixed.
Wherein, the pH value of the mixture containing alcohol, ethyl orthosilicate and modifying agent in step (1) is adjusted to 2-3；It adjusts
The selection of the acid of pH value is not particularly limited, for example, can be hydrochloric acid or nitric acid, preferably hydrochloric acid, wherein HCl contains in hydrochloric acid
Amount is 36.5wt%；
Wherein, in step (1), preferably in the condition of stirring during alcohol, ethyl orthosilicate and modifying agent are mixed
Lower progress, and the condition of stirring and equipment are not particularly limited, and can be the conventional selection of this field；
Wherein, in step (1), effect is prepared in order to further increase, it can be by the deionized water and carbon nanotube
Aqueous dispersions be slowly added into the mixture containing alcohol, ethyl orthosilicate and modifying agent, it is preferable that the deionized water with
The drop rate of 0.01-0.5mL/s is added dropwise, and the aqueous dispersions of the carbon nanotube are dripped with the drop rate of 0.05-0.5mL/s
Add；And still preferably carried out under stirring conditions in step (1), and the condition of stirring and equipment do not limit specifically
It is fixed, can be the conventional selection of this field；
Wherein, in step (1), on the basis of the total weight of the modified complex sol, the dosage of the alcohol can be
The dosage of 30-50 weight %, the ethyl orthosilicate can be 16-28 weight %, and the dosage of the modifying agent can be 19-30
The dosage of weight %, the deionized water can be 14-28 weight %, and the dosage of the aqueous dispersions of the carbon nanotube can be
0.5-9 weight %；Preferably, on the basis of the total weight of the modified complex sol, the dosage of the alcohol is 32-40 weights
Measure %, the dosage of the ethyl orthosilicate is 18-23 weight %, and the dosage of the modifying agent is 23-26 weight %, it is described go from
The dosage of sub- water is 14-18 weight %, and the dosage of the aqueous dispersions of the carbon nanotube is 0.8-5 weight %；
Wherein, in step (1), the modifying agent can be γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-
It is one or more in aminopropyl triethoxysilane and γ-(methacryloxypropyl) propyl trimethoxy silicane.
Wherein, the pH value of the mixture containing butyl titanate, acetylacetone,2,4-pentanedione and alcohol in step (2) is adjusted to 2-3；It adjusts
The selection of the acid of pH value is not particularly limited, for example, can be hydrochloric acid or nitric acid, preferably hydrochloric acid, wherein HCl contains in hydrochloric acid
Amount is 36.5wt%；
Wherein, in step (2), by butyl titanate, acetylacetone,2,4-pentanedione and alcohol mix during preferably room temperature (such as temperature
Degree be 15-35 DEG C) under conditions of stir 15-20 minutes, and stir condition and equipment be not particularly limited, can be ability
The conventional selection in domain；
Wherein, in step (2), effect is prepared in order to further increase, and the deionized water is slowly added into step
(1) in mixture, it is preferable that the deionized water is added dropwise with the drop rate of 0.01-0.5mL/s；
Wherein, in step (2), deionized water is being added drop-wise to the drop rate of 0.01-0.5mL/s containing metatitanic acid fourth
In the mixture of ester, acetylacetone,2,4-pentanedione and alcohol, then titanium colloidal sol obtained by the reaction is handled under conditions of temperature is 300-500 DEG C
0.5-2 hours, it is preferable that handled 1.5-2 hours under conditions of temperature is 350-450 DEG C, obtain the nano-titanium dioxide
Powder；
Wherein, in step (2), it is preferable that by titanium colloidal sol carry out high-temperature process before, can also by the titanium colloidal sol into
Row drying and processing, the condition and equipment of the drying are not particularly limited, for example, can be under conditions of temperature is 60-80 DEG C
Drying, the time of drying are not particularly limited, as long as the titanium colloidal sol is dried；
Preferably, in step (2), on the basis of the total weight of the nano-titanium dioxide powder, the butyl titanate
Dosage can be 9-16 weight %, the dosage of the acetylacetone,2,4-pentanedione can be 10-17 weight %, and the dosage of the alcohol can be
The dosage of 25-45 weight %, the deionized water can be 19-32 weight %；Preferably, with the nano-titanium dioxide powder
Total weight on the basis of, the dosage of the butyl titanate is 12-16 weight %, and the dosage of the acetylacetone,2,4-pentanedione is that 14-17 is weighed
% is measured, the dosage of the alcohol is 35-44 weight %, and the dosage of the deionized water is 27-32 weight %.
Wherein, in step (3), the nano-titanium dioxide powder, the modified complex sol and alcohol are mixed, at this
In invention, hydrophilic self-cleaning coating can be configured to according to certain proportioning；Preferably, in the present invention, first by the nano-silica
Change titanium valve body and the modified complex sol is stirred, then will contain the nano-titanium dioxide powder and the modification is answered
The mixture for closing colloidal sol is mixed with alcohol again.
The present invention it should be noted that the present invention hydrophilic self-cleaning coating composition in, each component contained, example
Such as, the components such as modified complex sol, nano-titanium dioxide powder and alcohol are separated presence.According still further to the side of the present invention when to be used
Method carries out being hybridly prepared into hydrophilic self-cleaning coating.
On the other hand, the present invention also provides described in above-mentioned any one hydrophilic self-cleaning coating composition and by upper
Application of the hydrophilic self-cleaning coating that preparation method described in stating is prepared in the automatically cleaning of photovoltaic cell plate face.Fig. 1 to Fig. 4
Be to the present invention hydrophilic self-cleaning applying coating on the surface of photovoltaic battery panel, then its correlated performance is tested；
Wherein, the mode of coating is not particularly limited, for spraying, showering or can be brushed on the surface of the photovoltaic battery panel
On, can drying and forming-film at normal temperatures, form a film after can also being toasted at 60-70 DEG C.
The present invention will be described in detail by way of examples below.
In following embodiment, unless otherwise instructed, each material and reagent can be commercially available.
The measurement of water contact angle is carried out using self-control water contact angle test equipment；
The measurement of visible light transmittance is carried out using the instrument purchased from Pu Xi all purpose instruments Co., Ltd model 722；
Using purchased from big bright scientific and technological testing equipment Co., Ltd, the instrument of model W-XD1 carries out resistance to artificial weathering aging
Measurement；
Using purchased from Suzhou Jingge Electronic Co., Ltd., the instrument of model ST2258C carries out the measurement of sheet resistance；
Single-walled carbon nanotube is purchased from Jin Hu chemical companies.
Embodiment 1
The present embodiment is used to illustrate hydrophilic self-cleaning coating composition of the invention and hydrophilic self-cleaning coating and its preparation side
Method and application
(1) by γ-(methacryloxypropyl) propyl trimethoxy of 46g absolute ethyl alcohols, 26g ethyl orthosilicates and 29.5g
Silane mixture stirs evenly, and is 2 with salt acid for adjusting pH；Again under agitation, by 18g deionized waters with the dropwise addition of 0.1mL/s
Rate is added dropwise, and by the aqueous dispersions for the single-walled carbon nanotube that 1g mass fractions are 0.5wt% with the dropwise addition speed of 0.05mL/s
Rate is added dropwise, and is stirred to react 5 hours under conditions of temperature is 60 DEG C, obtains the modified complex sol that grain size is 80nm；
(2) 10.6g butyl titanates and 10.5g acetylacetone,2,4-pentanediones are mixed evenly, under agitation with the anhydrous second of 30g
Alcohol is mixed evenly, and is 3 with salt acid for adjusting pH；Again under agitation, by 20g deionized waters with the dropwise addition speed of 0.1mL/s
Rate is added dropwise, and continues stirring 30min and obtains titanium colloidal sol；After drying the titanium colloidal sol under the conditions of temperature is 60 DEG C, then in temperature it is
High heat treatment 2h is carried out under conditions of 350 DEG C, it is the nano-titanium dioxide powder that 20nm crystal forms are anatase to obtain grain size；
(3) that the nano-titanium dioxide powder that 0.5g steps (2) obtain is distributed to the modification that 30g steps (1) obtain is compound
In colloidal sol, stirring obtains water white transparency silicon titanium colloidal sol after 1 hour, then is diluted with 48g absolute ethyl alcohols, adds 5g aminopropyls
The BYK-380N of triethoxysilane and 2g, you can obtain hydrophilic self-cleaning coating.
Hydrophilic self-cleaning applying coating to being prepared by embodiment 1 carries out phase on the surface of photovoltaic battery panel to it
Performance test is closed, main performance data are as shown in table 1：
Table 1
| Water contact angle (°) | 8 |
| Visible light transmittance (400mm, blank glass are reference) | 103% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 10% |
| Sheet resistance (Ω) | 1.1×109 |
As known from Table 1, water contact angle is 8 °, and water contact angle refers to solution-air circle made by gas, liquid, solid three-phase point of intersection
Angle theta of the tangent line in face across liquid and solid-liquid boundary line, is the measurement of wetness degree, if θ<90 °, then the surface of solids
It is hydrophilic, i.e., liquid is easier to wetting solid, and angle is smaller, indicates that wetability is better；Using blank glass as reference,
Visible light transmittance at 400nm is 101%, and light transmittance is good；Resistance to artificial weathering test, after 600h, contact angle increases
Rate is 10%, it is seen that weatherability is relatively good；When the value of body surface resistance is between 105-1011Between when, the object can be defined
For antistatic body, the sheet resistance measured in table 1 is 1.1 × 109Ω, it is seen then that anti-static effect is good.
And Fig. 1 shows contact angle of the hydrophilic self-cleaning coating prepared by embodiment 1 on surface of photovoltaic cell panel.This
Known in field technology personnel：As 90 ° of contact angle θ ﹤, show partially wetted.Obviously, hydrophilic self-cleaning coating of the invention is in photovoltaic
Wetting effect in battery plate surface is good；
Wherein, Fig. 2 shows apply and be not coated with the photovoltaic battery panel for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 in rain
In comparison design sketch, be to be not coated with the photovoltaic electric for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 in the left half of the Fig. 2
Pond plate is in the rain the case where, it is seen then that has apparent dirty attachment, is to apply in the right half (part inside black wire) of the Fig. 2
The photovoltaic battery panel of the hydrophilic self-cleaning coating prepared by embodiment 1 is covered in the rain the case where, it is seen then that without apparent dirty attached
It, film formation surface is smooth, shows：Electrostatic influence is eliminated, cleaning effect is good and room temperature film-forming is good；
Wherein, Fig. 3 is coating and is not coated with the photovoltaic battery panel for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 after one
The design sketch of comparison after a month is to be not coated with the light for being covered with the hydrophilic self-cleaning coating prepared by embodiment 1 in the left half of the Fig. 3
Solar panel is lied prostrate after the situation after one month, it is seen then that have apparent dirty attachment, in right half (the black wire the inside of the Fig. 3
Part) it is to be coated with the photovoltaic battery panel of the hydrophilic self-cleaning coating prepared by embodiment 1 after the situation after one month, it is seen then that
Without apparent dirty attachment, film formation surface is smooth, shows：Electrostatic influence is eliminated, cleaning effect is good, and room temperature film-forming is good, with
And weatherability is good；
Wherein, Fig. 4 is the visible light transmittance of the quartz glass plate coated with the hydrophilic self-cleaning coating prepared by embodiment 1
With the curve graph of the relationship of wavelength, it is seen then that in 350nm between 850nm, with the increase of wavelength, light transmittance with wavelength change
Change amplitude is little, therefore, can be used in the light transmittance of the entire visible light section of light transmittance approximate representation at 400nm, and its light transmission
Rate is all higher than 100%, it is seen then that light transmittance is preferable.
Embodiment 2
The present embodiment is used to illustrate hydrophilic self-cleaning coating composition of the invention and hydrophilic self-cleaning coating and its preparation side
Method
(1) by the γ of 42g absolute ethyl alcohols, 23g ethyl orthosilicates and 28.5g-glycidyl ether oxygen propyl trimethoxy silicon
Alkane is mixed evenly, and is 3 with salt acid for adjusting pH；Again under agitation, by 20g deionized waters with the dropwise addition speed of 0.5mL/s
Rate is added dropwise, and the aqueous dispersions for the single-walled carbon nanotube that 3g mass fractions are 0.8wt% are dripped with the drop rate of 0.1mL/s
Add, be stirred to react 1 hour under conditions of temperature is 100 DEG C, obtains the modified complex sol that grain size is 15nm；
(2) 9.6g butyl titanates and 11.5g acetylacetone,2,4-pentanediones are mixed evenly, under agitation with the anhydrous second of 28g
Alcohol is mixed evenly, and is 2.5 with salt acid for adjusting pH；Again under agitation, by 21g deionized waters with the dropwise addition of 0.3mL/s
Rate is added dropwise, and continues stirring 30min and obtains titanium colloidal sol；The titanium colloidal sol is dried under the conditions of temperature is 70 DEG C, then is in temperature
High heat treatment 2h is carried out under conditions of 400 DEG C, it is that the nano-titanium dioxide powder that 5nm crystal forms are anatase is received to obtain grain size
Rice titanium dioxide powder；
(3) that the nano-titanium dioxide powder that 0.7g steps (2) obtain is distributed to the modification that 29g steps (1) obtain is compound
In colloidal sol, stirring obtains water white transparency silicon titanium colloidal sol after 1 hour, then is diluted with 50g absolute ethyl alcohols, adds 1.1g ammonia second
The EFKA3030 of base aminopropyl triethoxysilane, 1.2g, you can obtain hydrophilic self-cleaning coating.
Correlated performance test, main performance data such as 2 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by embodiment 2
Show：
Table 2
| Water contact angle (°) | 7 |
| Visible light transmittance (400mm, blank glass are reference) | 103% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 12% |
| Sheet resistance (Ω) | 3.4×109 |
Embodiment 3
The present embodiment is used to illustrate hydrophilic self-cleaning coating composition of the invention and hydrophilic self-cleaning coating and its preparation side
Method
(1) gamma-aminopropyl-triethoxy-silane of 39g absolute ethyl alcohols, 25g ethyl orthosilicates, 28.8g are mixed equal
It is even, it is 2.5 with salt acid for adjusting pH；Again under agitation, 17g deionized waters are added dropwise with the drop rate of 0.3mL/s, and
The aqueous dispersions for the single-walled carbon nanotube that 5g mass fractions are 1wt% are added dropwise with the drop rate of 0.2mL/s, are 80 in temperature
It is stirred to react under conditions of DEG C 3 hours, obtains the modified complex sol that grain size is 100nm；
(2) 11g butyl titanates and 11.3g acetylacetone,2,4-pentanediones are mixed evenly, under agitation with 27g absolute ethyl alcohols
It is mixed evenly, is 3 with salt acid for adjusting pH；Again under agitation, by 23g deionized waters with the drop rate of 0.2mL/s
It is added dropwise, continues stirring 30min and obtain titanium colloidal sol；Temperature be 80 DEG C under the conditions of by the titanium colloidal sol dry, then temperature be 450 DEG C
Under conditions of carry out high heat treatment 2h, it is the nano-titanium dioxide powder that 25nm crystal forms are anatase to obtain grain size；
(3) that the nano-titanium dioxide powder that 1g steps (2) obtain is distributed to the modification that 34g steps (1) obtain is compound molten
In glue, stirring obtains water white transparency silicon titanium colloidal sol after 1 hour, then is diluted with 52g absolute ethyl alcohols, adds 1.7g aminopropyls
The EFKA3030 of methyldiethoxysilane and 1.3g, you can obtain hydrophilic self-cleaning coating.
Correlated performance test, main performance data such as 3 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by embodiment 3
Show：
Table 3
| Water contact angle (°) | 6 |
| Visible light transmittance (400mm, blank glass are reference) | 103% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 11% |
| Sheet resistance (Ω) | 9.2×109 |
Comparative example 1
Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating are prepared according to the method for embodiment 1, institute's difference exists
In：That γ-(methacryloxypropyl) propyl trimethoxy silicane is not added in step (1).
Correlated performance test, main performance data such as 4 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by comparative example 1
Show：
Table 4
| Water contact angle (°) | 7 |
| Visible light transmittance (400mm, blank glass are reference) | 102% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 9% |
| Sheet resistance (Ω) | 0.7×109 |
Comparative example 2
Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating are prepared according to the method for embodiment 1, institute's difference exists
In：In step (2), after drying the titanium colloidal sol under the conditions of temperature is 60 DEG C, then carried out under conditions of temperature is 500 DEG C
Height heat treatment 2h, it is the nano-titanium dioxide powder that 11nm crystal forms are rutile titania to obtain grain size；
Correlated performance test, main performance data such as 5 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by comparative example 2
Show：
Table 5
| Water contact angle (°) | 4 |
| Visible light transmittance (400mm, blank glass are reference) | 102% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 7% |
| Sheet resistance (Ω) | 1.0×109 |
Comparative example 3
Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating are prepared according to the method for embodiment 3, institute's difference exists
In：In step (3), the nano-titanium dioxide powder that 0.3g steps (2) obtain is distributed to the modification that 36g steps (1) obtain
In complex sol.
Correlated performance test, main performance data such as 6 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by comparative example 3
Show：
Table 6
| Water contact angle (°) | 5 |
| Visible light transmittance (400mm, blank glass are reference) | 102% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 8% |
| Sheet resistance (Ω) | 0.9×109 |
Comparative example 4
Hydrophilic self-cleaning coating composition and hydrophilic self-cleaning coating are prepared according to the method for embodiment 1, institute's difference exists
In：In step (1), 18g deionized waters are added dropwise with the drop rate of 0.02mL/s.
Correlated performance test, main performance data such as 7 institute of table are carried out to the hydrophilic self-cleaning coating being prepared by comparative example 4
Show：
Table 7
| Water contact angle (°) | 3 |
| Visible light transmittance (400mm, blank glass are reference) | 102% |
| Resistance to artificial weathering aging (600h, contact angle Magnification) | 5% |
| Sheet resistance (Ω) | 0.6×109 |
According to the experimental result of embodiment 1-3 and comparative example 1-4：The hydrophilic self-cleaning coating feature of environmental protection provided by the invention
It is good, and use it in photovoltaic power generation plate, good weatherability, light transmittance are high, room temperature film-forming is good, and can effectively reduce dirty attached
It, eliminates electrostatic influence.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (6)
1. a kind of hydrophilic self-cleaning coating composition, which is characterized in that the coating composition contains modified complex sol, receives
Rice titanium dioxide powder and alcohol；The modified complex sol is by by alcohol, ethyl orthosilicate, modifying agent, deionized water and carbon
Compound obtained from the aqueous dispersions of nanotube are reacted in acid condition, wherein the modifying agent is that γ-shrink is sweet
Oily ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and γ-(methacryloxypropyl) propyl trimethoxy silicon
It is one or more in alkane；
Wherein, it is 2-3 that the acid condition, which is pH value,；
Wherein, on the basis of the total weight of the coating composition, the content of the modified complex sol is 15-38 weight %,
The content of the nano-titanium dioxide powder is 0.5-5 weight % and the content of the alcohol is 15-62 weight %；
Wherein, the grain size of the modified complex sol is 15-100nm；The grain size of the nano-titanium dioxide powder be 5-25nm,
Crystal form is anatase；
Wherein, the carbon nanotube is single-walled carbon nanotube；And the mass concentration of the aqueous dispersions of the carbon nanotube is
0.1-1 weight %；
Wherein, the alcohol is absolute ethyl alcohol and/or isopropanol.
2. coating composition according to claim 1, wherein the coating composition also contain coalescents and/
Or wetting agent, and on the basis of the total weight of the coating composition, the content of the coalescents is 1-8 weight %, described
The content of wetting agent is 1-5 weight %.
3. the preparation method of hydrophilic self-cleaning coating composition as claimed in claim 1 or 2, which is characterized in that this method includes
Following steps：
（1）In acid condition, the aqueous dispersions of deionized water and carbon nanotube are added drop-wise to containing alcohol, ethyl orthosilicate and are changed
Property agent mixture in obtain modified complex sol；
（2）In acid condition, deionized water is added drop-wise in the mixture containing butyl titanate, acetylacetone,2,4-pentanedione and alcohol and is received
Rice titanium dioxide powder；
（3）The nano-titanium dioxide powder, the modified complex sol and alcohol are mixed；
Wherein, in step（2）In, this method further includes being added drop-wise to containing butyl titanate, acetylacetone,2,4-pentanedione and alcohol by deionized water
Mixture in after, it is also necessary to by colloidal sol obtained by the reaction temperature be 300-500 DEG C under conditions of handle 0.5-2 hours.
4. preparation method according to claim 3, wherein in step（1）In, with the total weight of the modified complex sol
On the basis of, the dosage of the alcohol is 30-50 weight %, and the dosage of the ethyl orthosilicate is 16-28 weight %, the modifying agent
Dosage is 19-30 weight %, and the dosage of the deionized water is 14-28 weight %, the dosage of the aqueous dispersions of the carbon nanotube
For 0.5-9 weight %.
5. preparation method according to claim 3, wherein the deionized water is dripped with the drop rate of 0.01-0.5mL/s
Add, the aqueous dispersions of the carbon nanotube are added dropwise with the drop rate of 0.05-0.5mL/s.
6. the system described in any one of hydrophilic self-cleaning coating composition as claimed in claim 1 or 2 and claim 3-5
Application of the hydrophilic self-cleaning coating that Preparation Method is prepared in the automatically cleaning of photovoltaic cell plate face.
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| CN110093050A (en) * | 2018-01-29 | 2019-08-06 | 新材料与产业技术北京研究院 | Superhydrophilic self-cleaning coating composition, superhydrophilic self-cleaning glass and preparation method thereof |
| CN110317476B (en) * | 2018-03-28 | 2021-08-06 | 新材料与产业技术北京研究院 | Nano functional coating and preparation method and application thereof |
| CN110131202A (en) * | 2018-08-22 | 2019-08-16 | 广东美的制冷设备有限公司 | Wind wheel and air conditioner |
| CN110173766B (en) * | 2018-08-22 | 2023-07-21 | 广东美的制冷设备有限公司 | Heat exchanger and air conditioner |
| CN110872464B (en) * | 2018-09-04 | 2021-09-14 | 上海沪正实业有限公司 | Hydrophilic self-cleaning nano aluminum hydroxide, preparation method thereof and acrylic acid composition |
| CN110218488A (en) * | 2019-06-14 | 2019-09-10 | 湖南城市学院 | A kind of wind-driven generator shell with self-cleaning function |
| CN111548655A (en) * | 2020-04-28 | 2020-08-18 | 嘉兴海欣生态科技有限公司 | Super-hydrophilic transparent anti-static self-cleaning coating composition and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
| CN102382490A (en) * | 2011-08-30 | 2012-03-21 | 西北永新集团有限公司 | Preparation method and use of hydrophilic automatically-cleaning coating with photocatalytic activity |
| CN102718410A (en) * | 2012-06-11 | 2012-10-10 | 常州大学 | Method for preparing self-cleaning antifogging coating film |
| CN103086613A (en) * | 2013-03-05 | 2013-05-08 | 福建圣元电子科技有限公司 | Preparation method of anti-reflection self-cleaning coated glass |
| CN103275615A (en) * | 2004-05-28 | 2013-09-04 | Ppg工业俄亥俄公司 | Hydrophilic compositions, methods for their production, and substrates coated with such compositions |
| CN104629617A (en) * | 2015-02-03 | 2015-05-20 | 南京米福新材料科技有限公司 | Inorganic-organic hybrid super-hydrophilic self-cleaning coating and production method thereof |
| CN104710919A (en) * | 2015-04-02 | 2015-06-17 | 济南大学 | Self-cleaning and environmental-friendly interior and exterior wall coating of buildings and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792633B (en) * | 2010-03-09 | 2013-04-24 | 浙江大学 | Preparation method for antistatic super hydrophobic composite coating |
-
2017
- 2017-06-19 CN CN201710462897.3A patent/CN107236451B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275615A (en) * | 2004-05-28 | 2013-09-04 | Ppg工业俄亥俄公司 | Hydrophilic compositions, methods for their production, and substrates coated with such compositions |
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
| CN102382490A (en) * | 2011-08-30 | 2012-03-21 | 西北永新集团有限公司 | Preparation method and use of hydrophilic automatically-cleaning coating with photocatalytic activity |
| CN102718410A (en) * | 2012-06-11 | 2012-10-10 | 常州大学 | Method for preparing self-cleaning antifogging coating film |
| CN103086613A (en) * | 2013-03-05 | 2013-05-08 | 福建圣元电子科技有限公司 | Preparation method of anti-reflection self-cleaning coated glass |
| CN104629617A (en) * | 2015-02-03 | 2015-05-20 | 南京米福新材料科技有限公司 | Inorganic-organic hybrid super-hydrophilic self-cleaning coating and production method thereof |
| CN104710919A (en) * | 2015-04-02 | 2015-06-17 | 济南大学 | Self-cleaning and environmental-friendly interior and exterior wall coating of buildings and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 溶胶－凝胶法制备玻璃基增透自清洁薄膜;方建辉;《玻璃与搪瓷》;20130630;第41卷(第3期);第13-16页 * |
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| CN107236451A (en) | 2017-10-10 |
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