CN101525504A - Photocatalytic self-cleaning film coating agent with self-layered isolation effect and preparation method thereof - Google Patents
Photocatalytic self-cleaning film coating agent with self-layered isolation effect and preparation method thereof Download PDFInfo
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Abstract
A photocatalytic self-cleaning film coating agent with a self-layered isolation effect contains an inorganic hydrosol binder, resin emulsion or a water dispersing agent, a titanium oxide photocatalyst and an oxide isolation protective agent. The photocatalytic self-cleaning film coating agent is characterized by comprising the following materials in weight percentage: 10-99% of the inorganic hydrosol binder (solid content is 10-45%), 0.1-18% of the resin emulsion or the water dispersing agent (solid content is more than 30%), 0.1-30% of the titanium oxide photocatalyst (titanium dioxide content is 1-30%), 0.01-7% of the oxide isolation protective agent and a proper amount of water; and a certain amount of bonding reinforcing agent can be added as required. The photocatalytic self-cleaning film coating agent can almost form films on surfaces of any materials and form a complete and practical self-cleaning coating layer.
Description
Technical field
The present invention relates to a kind of photochemical catalysis self-cleaning coating agent and preparation method thereof, particularly relate to and a kind ofly having from layering isolation oxidation resist technology, and the surface forms the self-cleaning coating agent of high efficiency photocatalysis characteristic, it belongs to chemicals and forms the coating film technique.
Back of the body border technology
Outdoor architecture or other articles for use material surface are easy to be subjected to Pollutant effects in the environment and dirty, and the surface of organic materials is easily under the direct irradiation of the sun and take place aging simultaneously.Adopt the organic fluorine of hydrophobic silicone resin, hydrophobic oleophobic or the coating that this resin emulsion is made, can play certain antipollution and delay the paint aging effect.But in a single day the hydrophobic coating surface is attached with organic pollutants, will be accelerated pollution.Especially for the fluorocarbon coating or the organosilicon coating of exterior wall, can produce tangible water stain pollution vestige behind the life-time service.Though organic fluorine has the excellent anti-ability of staining, price is high, behind the life-time service, in case contaminated just being difficult to removed.Thereby the photocatalysis coating technology with automatic cleaning action is rapidly developed in recent years, and along with the continuous progress of correlation technique, use cost is also reducing significantly.
Nanometer anatase titania has very strong photocatalytic activity owing to being found, and can produce significantly super water-wet behavior under UV-irradiation, thereby becomes the preferred material that is applied to self-cleaning coating agent in the research.This semi-conductor type photocatalyst is under the irradiation of UV-light, the electronics that is excited can activate the oxygen G﹠W that is adsorbed on the surface, generate the hydroxyl of high reaction activity and the active group of oxygen, oxidizing potential even be higher than simple substance fluoride is enough to the most organic pollutant molecules of oxygenolysis.This characteristic not only gives photocatalyst secular automatically cleaning ability, and is produced simultaneously by light activated super water-wet behavior, can be when rainy, and easier being washed away of pollutent on feasible surface.
Because titanium dioxide is the very strong inorganic materials of polarity, when being used for the processing of inorganic materials article surface overlay film, can adopt the mode that mineral binder bond adheres to through high temperature sintering of adding, form photochemical catalysis automatically cleaning rete at body surface, as photochemical catalysis automatic cleaning coating at glass, ceramic surface.Yet, when being used for inorganic material surface that organic materials surface treatment and some can't high temperature sintering adhere to and handling, just must adopt low temperature or normal temperature adhering mode.As: the automatically cleaning that is used for sunlight board, color steel surface is handled, and is used for the surface treatment of external wall latex coating.This normal temperature or cryogenic processing mode always be unable to do without the matrix material that normal temperature or low temperature use.Application number is 03159019.5,200410015409.7,200510025431.4 Chinese patent, all adopted the prescription mode of emulsion paint, with the organic resin emulsion is bonding film forming host, will adopt dichloride in anatase type titanium oxide and membrane-forming agent after dispersion agent and the water treatment to be mixed and made into again.
But, select this self-cleaning and film-coated that direct mode of adding nanometer anatase titania photocatalyst powder obtains in the film forming polymer emulsion of normal temperature for use, at first face the secular stability problem of filming.Anatase titanium dioxide is found the efflorescence deterioration effect that has coating very early as the filler of emulsion paint, this is because the photocatalytic oxidation of anatase titanium dioxide, hydrocarbon organic compound to direct contact has the decomposition destruction, can make organic film-forming material become loose.Simultaneously, the automatically cleaning mechanism of photocatalyst is that illumination must be arranged, and can directly contact with empty G﹠W.Be blended directly in the performance that obviously can limit the basic role of photocatalyst in the emulsion paint greatly.
In addition, because the content of nano titanium dioxide photocatalyst in polymer emulsion must be greater than 5% o'clock of total solid content, tangible photocatalysis characteristic can appear, and the titanium dioxide that is wrapped in paint vehicle inside almost can't be brought into play photocatalysis, therefore, the coating photocatalyst of this mode not only utilization ratio is not high, and can increase making and use cost.
In addition, though the film forming host that application number is 03117023.4 Chinese patent to be selected for use is scale resistance organosilicon or organic fluorine emulsion preferably, but practice is found, because the photocatalytic oxidation in later stage, it is dim that lacquer painting after the film forming will become in short period, and Here it is because present silicone resin or the still very high catalyzed oxidation decomposing phenomenon that causes of the hydrocarbon content in the organic fluorine.
Therefore, development in recent years the self-cleaning and film-coated technology of photochemical catalysis of surface silicon insulation blocking type.
Provided a kind of photocatalysis coating technology that adopts the silicon protection among No. 6337129, the U.S. Pat Patent; but; this coating process is the silicone material that adopts silicone resin or contain inorganic silicon; at first treated material is carried out the bottom pre-treatment, and then the titanium dioxide optical catalyst colloidal sol of coating inorganic or contain the inorganic silicon colloidal sol of photocatalyst.
There is following problem in this technology mode: at first, because the use of the silicone resin layer of basic unit, the technology use cost of causing is still very high; Secondly, this technology generally also needs certain processing of heating, and has therefore limited applying of it.Though used the film forming silicone resin emulsion of normal temperature among No. 6048910, the U.S. Pat Patent, but behind the emulsion drying and forming-film, the optically catalytic TiO 2 colloidal sol of aqueous phase or nano particle and silicone resin remain and are spaced in film coated surface, therefore cause final film forming water contact angle higher (less than 60 °), thereby influenced the effect of automatic cleaning action.
Application number is that to disclose a kind of be the preparation and the method for the photochemical catalysis self-cleaning coating of protective underlayer layer with the inorganic sol for 200710065676.9 Chinese patent; its method is the water-sol for preparing earlier titanium dioxide optical catalyst by the hydrolysis of organic titanium, and doped precious metal, transition metal, rare earth metal, nonmetal or oxide compound further improve the absorption of photocatalyst to visible light then.When concrete the use; form isolated protective layer at the coated one deck inorganics of organic materials bottom colloidal sol earlier; and then the coated above-mentioned photocatalyst water-sol, forming insulation blocking effect to the bottom organic materials, the while can be given full play to the activity of top layer photocatalyst again and be reduced cost.Though this method has solved the problem in work-ing life of photocatalysis membrana, when reality is implemented, must be coated at twice, cost of labor and construction period increase greatly.
Summary of the invention
The object of the invention: aim to provide a kind of low cost, long lifetime, need not adopt bottoming protective layer, disposable composition of smearing the photochemical catalysis self-cleaning coating agent that just can implement and preparation method thereof.
This photochemical catalysis self-cleaning coating agent that has from the layering buffer action that the present invention relates to; contain inorganic water-sol binding agent, resin emulsion or water dispersant; titania photocatalyst and oxidation insulation blocking agent is characterized in that: its component material is in weight percent content once:
Comprise following component material (in weight percent content):
Inorganic water-sol binding agent (solid content 10-45%) 10-99%
Resin emulsion or dispersion liquid (solid content 15-55%) 0.1-18%
Titania photocatalyst (content of titanium dioxide 1-30%) 0.1-30%
Oxidation insulation blocking agent 0.01-7%
Water surplus
Described inorganic water-sol binding agent is one or more the composition in silicon dioxide gel, titanium oxide sol, titanium phosphate colloidal sol, zinc oxide colloidal sol, alumina sol, the tin oxide sol.
In order to increase the sticking power after the mineral binder bond film forming, also add the bonding reinforcing agent of the type siloxane of 0-5% in the component material.
Described resin emulsion or dispersion liquid can be pure-acrylic emulsion, benzene emulsion, organosilicon crylic acid latex, epoxy emulsion or aqueous polyurethane dispersing liquid, or even comparatively costliness but normal temperature filming emulsions such as the better organic silicon emulsion of weathering resistance, organic fluorine emulsion.
Described titania photocatalyst is the titania photocatalyst water-sol or anatase titanium dioxide nano powder aqueous dispersions.
Described oxidation insulation blocking agent is silicon coupling agent, Silicon surfactant or fluorine surfactant; As add the bonding reinforcing agent of the type siloxane of 0-5%.
The making method of this photochemical catalysis self-cleaning coating agent is: at first in adding by final finished gross weight 0.01-7% oxidation insulation blocking agent in the resin emulsion of final finished gross weight 0.1-10% ratio or the aqueous dispersions, and high-speed stirring is mixed stand-by; Then with mass concentration be that the phosphoric acid of 2%-35% will be selected for use, transfer between 6-7.5 by the pH of the inorganic water-sol binding agent of final finished gross weight 10-99%, and add bonding toughener about 0-5%, high-speed stirring was disperseed aging 1-5 hour again; The titania photocatalyst that then under high-speed stirring dispersion situation, adds gross weight 0.1-10% again; Add proper amount of deionized water at last to predetermined surplus ratio, and the resin emulsion that adds oxidation insulation blocking agent that will prepare in advance or dispersion liquid adds and high-speed stirring can make final liniment.
This self-cleaning coating agent according to above technical scheme proposition, adopted normal temperature film forming macromolecule resin emulsion commonly used as one of filmogen of automatically cleaning rete, simultaneously as automatically cleaning film and bottom oleophylic machine thing material, the particularly bonding material of organism material.The method of the film forming macromolecule organic resin of these normal temperature being carried out the silicon protection is to have surface-active silicon coupling agent or Silicon surfactant or fluorine surfactant at the water of emulsion and the interface of oil phase by abundant interpolation; make the organic phase drop of emulsion be in the interface insulation blocking state of silicon coupling agent, make the nano-photo catalytic agent dispersion after water dispersive TiO 2 sol or the final film forming can't directly contact organic resin.Simultaneously; can take place separating of oleophilic layer and hydrophilic layer at film process in this silicon protected mode automatically; the oleophylic section of tensio-active agent or silicon coupling agent is preferentially selected attached to the organic resin surface; almost completely with organic phase and inorganic isolated; thereby final the acquisition in the protection while to underfill resin layer; influence to inferior limit the super water-wet behavior on photochemical catalysis top layer, make the top layer form excellent super hydrophilic automatically cleaning rete.Compare with existing silicon resist technology, silicon guard method of the present invention can make that the use cost of system is lower, and implementation condition is more convenient, and Application Areas is broad more.This self-cleaning coating agent almost can form the automatic cleaning coating of complete practicality in any material surface film forming.Promptly be used in inorganic material surface when coated; also can pass through the consumption of the silica reagent of controlling polymers emulsion and insulation blocking; make that less polymer emulsion is effectively isolated by the silicon protective material in the last film forming; the elasticity hybridized film of segmentation between formation, the hydro-thermal that has overcome single mineral membrane changes the unstable that causes.
Embodiment
Provide case study on implementation of the present invention below, but be not limited to the present invention.
Embodiment 1 (by weight percentage)
Inorganic water-sol caking agent (solid content 10-45%) 75%
Bonding toughener 3.75%
Resin emulsion or dispersion liquid (solid content is greater than 30%) 3%
Titania photocatalyst (content of titanium dioxide 1-30%) 5%
Oxidation insulation blocking agent 3%
Water surplus
The starting material of selecting for use in the present embodiment are marketable material, and wherein, the aqueous polyurethane dispersing liquid (solid content 30%) that the resin aqueous dispersions has selected for use Bayer A.G to provide also can be selected pure-acrylic emulsion, benzene emulsion, organosilicon crylic acid latex, epoxy emulsion etc. for use.
β-(3 is selected in oxidation insulation blocking agent for use; the 4-epoxycyclohexyl) ethyl trimethoxy silane (purity is more than 97%); the 1030 translucent titania hydrosols that the titania photocatalyst water-sol selects for use Shanghai Jiesen Environmental Technology Co., Ltd. to produce, the water mineral binder bond has been selected silicon dioxide gel (silica content 30%) for use.
In the implementation process, in the aqueous polyurethane dispersing liquid of final finished gross weight 3% ratio, add β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane of 3% earlier, and high-speed stirring is mixed stand-by.Phosphoric acid with mass concentration 10% transfers to the silica hydrosol pH value that solid content accounts for gross weight 23.4% between 7-7.5 then, the tetramethoxy-silicane that adds about water-sol weight about 5% strengthens caking agent, can be after the siloxanes hydrolysis with inorganic water-sol generation condensation reaction, form netted spatial connecting key, can obviously strengthen the intensity after the photochemical catalysis liniment film forming.But, also can not add this bonding toughener for some occasion not high to requirement of strength.
High-speed stirring was disperseed aging 1-5 hour; the titania hydrosol that under high-speed stirring dispersion situation, adds gross weight 5% then; add balance of deionized water again to suitable consistency for, add the aqueous polyurethane dispersing liquid high-speed stirring that adds oxidation insulation blocking agent for preparing in advance at last and can make final liniment.
Above-mentioned photochemical catalysis self-cleaning coating agent is coated on the emulsion paint test sample plate, seasoning and outdoor placement two days, the contact angle that records itself and water is less than 3 °; Behind the dip-coating oleic acid of surface,, record water contact angle greater than 45 °, then at 1mW/cm 70 ℃ of dryings 15 minutes
2Above UVA rayed recorded its water contact angle less than 8 ° after 72 hours.
Embodiment 2 (by weight percentage)
Inorganic water-sol caking agent (dioxide-containing silica 30%) 85%
Bonding toughener 4.25%
Resin emulsion or dispersion liquid (solid content 45%) 6.7%
Titania photocatalyst (titanium oxide content 1%-35%) 3.5%
Oxidation insulation blocking agent 0.15%
Water surplus
The pure-acrylic emulsion that the resin emulsion of selecting for use in the present embodiment provides for U.S. Rhom and Hass (solid content 45%) also can be selected organosilicon crylic acid latex, epoxy emulsion or aqueous polyurethane dispersing liquid etc. for use.
The rare acyl-oxygen Union carbide A-162 of methyl-prop (purity is more than 97%) is selected in oxidation insulation blocking agent for use; the titanium dioxide optical catalyst aqueous dispersions that the titanium dioxide optical catalyst water-sol selects for use Japanese Shi Yuan company to produce, the water mineral binder bond has been selected silicon dioxide gel (silica content 30%) for use.
In the implementation process, in the pure-acrylic emulsion of final finished gross weight 6.7% ratio, add 0.15% the rare acyl-oxygen Union carbide A-162 of methyl-prop earlier, and high-speed stirring is mixed stand-by.The silica hydrosol pH value that will account for gross weight 85% with phosphoric acid transfers between 7-7.5 then; the tetramethoxy-silicane that adds about water-sol weight about 5% strengthens caking agent; high-speed stirring was disperseed aging 1-5 hour; the titanium dioxide water-dispersion liquid that under high-speed stirring dispersion situation, adds gross weight 3.5% then; add proper amount of deionized water again to adding proper amount of deionized water, add the pure-acrylic emulsion high-speed stirring that adds oxidation insulation blocking agent for preparing in advance at last and can make final liniment to suitable consistency for.
Above-mentioned photochemical catalysis self-cleaning coating agent is coated on the emulsion paint test sample plate, seasoning and outdoor placement two days, the contact angle that records itself and water is less than 4 °; Behind the dip-coating oleic acid of surface,, record water contact angle greater than 45 °, then at 1mW/cm 70 ℃ of dryings 15 minutes
2Above UVA rayed recorded its water contact angle less than 9 ° after 72 hours.
Embodiment 3 (by weight percentage)
Inorganic water-sol binding agent (solid content 1%-45%) 85%
Resin emulsion or dispersion liquid (solid content 20%-55%) 4%
Titania photocatalyst (titanium oxide content 1%-35%) 4%
Oxidation insulation blocking agent 3%
Water surplus
The fluorine modification organosilicon crylic acid latex (solid content is greater than 42%) that the resin emulsion of selecting for use in the present embodiment is clear for Japan and polymer company provides also can be selected pure-acrylic emulsion, benzene emulsion, epoxy emulsion or aqueous polyurethane dispersing liquid etc. for use.
The rare acyl-oxygen Union carbide A-162 of methyl-prop (purity is more than 97%) is selected in oxidation insulation blocking agent for use; the titanium dioxide optical catalyst aqueous dispersions that the titanium dioxide optical catalyst water-sol selects for use Japanese Shi Yuan company to produce, the water mineral binder bond has been selected alumina sol (alumina content 20%) for use.
In the implementation process, in the fluorine modification organosilicon crylic acid latex of final finished gross weight 4% ratio, add 3% the rare acyl-oxygen Union carbide A-162 of methyl-prop earlier, and high-speed stirring is mixed stand-by.The alumina hydrosol pH value that will account for gross weight 85% with phosphoric acid transfers between 7-7.5 then; high-speed stirring was disperseed aging 1-5 hour; the titanium dioxide water-dispersion liquid that under high-speed stirring dispersion situation, adds gross weight 4% then; add proper amount of deionized water again to predetermined proportion, add at last the fluorine modification organosilicon crylic acid latex high-speed stirring that adds oxidation insulation blocking agent prepare in advance get final product final liniment.
Above-mentioned photochemical catalysis self-cleaning coating agent is coated on the emulsion paint test sample plate, seasoning and outdoor placement two days, the contact angle that records itself and water is less than 4 °; Behind the dip-coating oleic acid of surface,, record water contact angle greater than 48 °, then at 1mW/cm 70 ℃ of dryings 15 minutes
2Above UVA rayed recorded its water contact angle less than 8 ° after 72 hours.
Embodiment 4 (by weight percentage)
Inorganic water-sol binding agent (solid content 1%-45%) 10%
Resin emulsion or dispersion liquid (solid content 20%-55%) 1%
Titania photocatalyst (titanium oxide content 1%-35%) 10%
Oxidation insulation blocking agent 0.5%
Water surplus
The fluorine modification organosilicon crylic acid latex (solid content reaches 45%) that the resin emulsion of selecting for use in the present embodiment is clear for Japan and polymer company provides also can be selected pure-acrylic emulsion, benzene emulsion, epoxy emulsion or aqueous polyurethane dispersing liquid etc. for use.
The rare acyl-oxygen Union carbide A-162 of methyl-prop (purity is more than 97%) is selected in oxidation insulation blocking agent for use; the titanium dioxide optical catalyst aqueous dispersions that the titanium dioxide optical catalyst water-sol selects for use Japanese Shi Yuan company to produce, the water mineral binder bond has been selected alumina sol (alumina content 20%) for use.
In the implementation process, in the fluorine modification organosilicon crylic acid latex of final finished gross weight 1% ratio, add 0.5% the rare acyl-oxygen Union carbide A-162 of methyl-prop earlier, and high-speed stirring is mixed stand-by.The alumina hydrosol pH value that will account for gross weight 10% with phosphoric acid transfers between 7-7.5 then; high-speed stirring was disperseed aging 5 hours; the titanium dioxide water-dispersion liquid that under high-speed stirring dispersion situation, adds gross weight 10% then; add proper amount of deionized water again to predetermined proportion; add at last the fluorine modification organosilicon crylic acid latex high-speed stirring that adds oxidation insulation blocking agent prepare in advance get final product final liniment, the rete that is coated with that this scheme forms is the coating that a kind of coating approached, was bordering on vitreous state.
Below in conjunction with the foregoing description, the photochemical catalysis self-cleaning coating agent of introduction of the present invention is further set forth:
Normal temperature film-forming resin emulsion or dispersion liquid can be pure-acrylic emulsion, benzene emulsion, organosilicon crylic acid latex, epoxy emulsion or aqueous polyurethane dispersing liquid in the technical program, or even comparatively costliness but normal temperature filming emulsions (wherein part emulsion film forming when heating is faster) such as the better organic silicon emulsion of weathering resistance, organic fluorine emulsion, the weight ratio of its consumption in final finished photochemical catalysis liniment is at 0.1%-10% the ratio of finished product gross weight (solid content of the surfactant that extracting and separating is come out after by breakdown of emulsion with).
The consumption of insulation blocking agent in finished product of photocatalytic oxidation accounts for the ratio of gross weight at 0.01%-7%; element atom mass rate in main antioxygenation; as the content of silicon in Silicon surfactant, the silicon coupling agent, or the content of fluorine in the fluorine surfactant.
The silicon coupling agent that adopts in the insulation blocking agent of photocatalytic oxidation is following basic structure:
Y-R-Si-X3
Wherein, R: alkyl or aryl; X: hydrolysable group such as methoxyl group, oxyethyl group or chlorine; Y: organic reaction group (vinyl, amino, epoxy group(ing), sulfydryl etc.)
The hydrolization group of X representative can combine with active group (as: the silicon hydroxyl of silicon oxide, titanium oxide, the titanium hydroxyl) reaction of inorganic materials, and the represented reactive group of Y can combine with active group (as the vinyl in the resin emulsion, amino, epoxy group(ing), sulfydryl, the hydroxyl etc.) chemical reaction of organic materials.Thereby silicon coupling agent plays chemically combined function served as bridge between organic materials and the inorganic materials.Simultaneously, in the present invention, also play organic film-forming resin and the inorganic titanium oxide water-sol or the insulation blocking effect between the water-dispersion mutually.
Silicon surfactant is meant that hydrophobic group is the tensio-active agent based on polysiloxane, as hexamethyl siloxanes, low polymethyl hydrogen siloxane etc.
The molecular structure of common hydrocarbon-surfactant is made up of two portions: promptly hydrocarbon alkyl (hydrophobic group) and polar group (hydrophilic group).Fluorine surfactant has similar molecular structure, is that hydrocarbon alkyl is replaced by fluorine carbon alkyl, and polar group is then roughly the same.As: Perfluorocaprylic Acid and salt thereof, perfluoro octyl sulfonic acid and salt, full-fluorine octyl sulfuryl fluoride etc.
It has been comparatively sophisticated technology of preparing that aqueous phase uses the titania photocatalyst water-sol, has multiple commercially available finished product to sell.Adopted Shanghai Jiesen Environmental Technology Co., Ltd. with the metatitanic acid colloidal sol of titanyl sulfate, again through the acidifying and the aging transparent or semitransparent photocatalyst water-sol that makes of complexing in the present invention through the alkali precipitation preparation; The anatase titanium dioxide nano powder aqueous dispersions that uses has adopted the oyster white aqueous dispersions of the dichloride in anatase type titanium oxide powder that Japanese Shi Yuan company produces.In the above photocatalyst water-sol or the dispersion liquid, the titanium dioxide particle diameter requires less than 100 nanometers, and best size is less than 30 nanometers, to guarantee the catalytic activity of final photochemical catalysis automatically cleaning film.Also can adopt commercially availablely, re-use 0.01%-2% polymerization of carboxylic acid sodium type dispersion agent and carry out dispersion treatment, make the dispersion liquid of photocatalyst less than 30 nanometer anatase titanium dioxide powders.
The selected inorganic sol of water film-forming binder is one or more the composition in silicon dioxide gel or titanium oxide sol (titanic sour water colloidal sol) or titanium phosphate colloidal sol or zinc oxide colloidal sol or alumina sol or the tin oxide sol.In order to increase the sticking power after the mineral binder bond film forming, can also add the siloxanes that 0-5% strengthens inorganic water-sol binding agent adhesiveproperties, its typical chemical formula is as follows:
Si (OR)
4, RSi (OR)
3Or R
3Si (OR)
The alkyl that wherein has 1-6 carbon atom on the R, or their oligopolymer.
When the photochemical catalysis liniment prepares, the mode of optimizing is to join the photocatalyst water-sol (or aqueous dispersions) in the inorganic water-sol in proportion and stir, and oxidation insulation blocking agent is added the resin emulsion high speed mix, and then the emulsion high-speed mixing of the water-sol that will add photocatalyst and adding oxidation insulation blocking agent gets final product; Also photocatalyst sol (or aqueous dispersions) can be joined in proportion the inorganic sol high speed and disperse, add oxidation insulation blocking agent then and carry out even dispersed with stirring, add polymer emulsion at last and stir and get final product.
The use-pattern of photochemical catalysis liniment can adopt spraying or brushing mode, also can adopt the mode of dip-coating.Got final product surface drying in 1-2 hour under the general normal temperature, did solid work in 5-6 hour, the basic hardness of film and photocatalysis characteristic reached best formation situation after 2-3 days.The surface hydrophilic contact angle can reach below 4 °, and the decomposition decolorization that 2% methylene blue is detected liquid can obviously manifest in tens minutes under the sunlight direct projection situation outdoor need not.
Above-mentioned photochemical catalysis self-cleaning coating agent is coated on the emulsion paint test sample plate, seasoning and outdoor placement two days, the contact angle that records itself and water is less than 4 °; Behind the dip-coating oleic acid of surface,, record water contact angle greater than 48 °, then at 1mW/cm 70 ℃ of dryings 15 minutes
2Above UVA rayed recorded its water contact angle less than 8 ° after 72 hours.
The photochemical catalysis self-cleaning coating agent that above case study on implementation makes, after existing exterior wall is with pure acrylate dope, the coated film forming in fluorine modification silicon-acrylic coatings surface, carry out the anti-property testing of staining through Shanghai building research institute, contamination resistance all is significantly improved, and correlation data is as follows:
Table one: contamination resistance contrast behind pure acrylate dope sample and the same coated photochemical catalysis self-cleaning coating agent of the present invention of sample surfaces
| Test item | The standard value requirement | Assay | The result judges |
| Pure acrylate dope model | ≤ 15 (white or light color) | 10 | Qualified |
| Model behind the coating photocatalysis membrana | ≤ 15 (white or light color) | 3 | Qualified |
Table two: contamination resistance contrast behind fluorine modification silicon-acrylic coatings sample and the same coated photochemical catalysis self-cleaning coating agent of the present invention of sample surfaces
| Test item | The standard value requirement | Assay | The result judges |
| Pure acrylate dope model | ≤ 15 (white or light color) | 8 | Qualified |
| Model behind the coating photocatalysis membrana | ≤ 15 (white or light color) | 2 | Qualified |
Claims (9)
1, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action; contain inorganic water-sol binding agent, resin emulsion or water dispersant; titania photocatalyst and oxidation insulation blocking agent is characterized in that: its component material is in weight percent content once:
Inorganic water-sol caking agent (solid content 10-45%) 10-99%
Resin emulsion or dispersion liquid (solid content is greater than 30%) 0.1-18%
Titania photocatalyst (content of titanium dioxide 1-30%) 0.1-30%
Oxidation insulation blocking agent 0.01-7%
Water surplus.
2, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1 is characterized in that: the described inorganic water-sol is one or more assembly adhesives in silicon dioxide gel or titanium oxide sol, titanium phosphate colloidal sol, zinc oxide colloidal sol, alumina sol, the tin oxide sol.
3, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1 is characterized in that: the described photocatalyst water-sol or water dispersant are titania hydrosol or the nanometer anatase titania nano powder aqueous dispersions with photocatalytic activity.
4, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1, it is characterized in that: described oxidation insulation blocking agent is silicon coupling agent, Silicon surfactant or fluorine surfactant.
5, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1 is characterized in that: the solid content 1%-45% of the described inorganic water-sol; Described resin emulsion or dispersion liquid solid content are at 15%-55%; The titanium oxide content of described titania photocatalyst is at 1-30%.
6, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1, it is characterized in that: described photochemical catalysis self-cleaning coating agent also contains bonding reinforcing agent, and its add-on is the 0-5% of material gross weight.
7, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 3, it is characterized in that: the described nanometer anatase titania nano powder aqueous solution, adopt commercially availablely, re-use 0.01%-2% polymerization of carboxylic acid sodium type dispersion agent and carry out dispersion treatment and make dispersion liquid less than 30 nanometer anatase titanium dioxide powders.
8, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 6, it is characterized in that: the particle diameter of described nanometer anatase titania nano powder should be less than 100 nanometers.
9, a kind of photochemical catalysis self-cleaning coating agent that has from the layering buffer action as claimed in claim 1, its making method is: at first add the oxidation insulation blocking agent of 0.01-7% in the resin emulsion of selecting for use of final finished gross weight 0.1-18% ratio or dispersion liquid, and high-speed stirring is mixed stand-by; The pH that will account for the water-sol of selecting for use of gross weight 10-99% with mass concentration 2%-35% phosphoric acid transfers between 6-7.5 then, adds the bonding toughener of 0-5%, and high-speed stirring was disperseed aging 1-5 hour again; The titania photocatalyst that then under high-speed stirring dispersion situation, adds gross weight 0.1-30% again; Add proper amount of deionized water at last to predetermined proportion, and the resin emulsion that adds oxidation insulation blocking agent that will prepare in advance or dispersion liquid add and high-speed stirring can make final liniment.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101967327A (en) * | 2010-09-30 | 2011-02-09 | 江苏大象东亚制漆有限公司 | Long-acting formaldehyde-resistant water-based crylic acid wood lacquer composite |
| CN102796407A (en) * | 2011-05-23 | 2012-11-28 | 河源海川科技有限公司 | Organic-inorganic hybrid photocatalytic coating and preparation method thereof |
| CN103525141A (en) * | 2013-09-16 | 2014-01-22 | 安徽欧尚建材有限公司 | Waterborne high temperature-resistant inorganic coating |
| CN103555008A (en) * | 2013-09-29 | 2014-02-05 | 中国海洋石油总公司 | Water-based photocatalyst transparent coating |
| CN104017398A (en) * | 2014-06-09 | 2014-09-03 | 复旦大学 | Preparation method of TiO2-based aqueous self-cleaning coatings |
| CN105400248A (en) * | 2015-11-30 | 2016-03-16 | 洛阳绿仁环保设备有限公司 | Weather-resistant coating and preparation method thereof |
| CN105789448A (en) * | 2016-04-18 | 2016-07-20 | 北京大学 | Thin film preparation method utilizing nanoparticle to improve surface wettability |
| CN106947345A (en) * | 2017-03-28 | 2017-07-14 | 江苏晨光涂料有限公司 | Reflective heat-insulation paint with self-cleaning function |
| CN107151496A (en) * | 2017-05-24 | 2017-09-12 | 佛山实瑞先导材料研究院（普通合伙） | A kind of nano-TiO2Modified water-soluble composite coating and preparation method thereof |
| CN107266990A (en) * | 2017-07-21 | 2017-10-20 | 张娟 | A kind of wall environmental protection coating material and preparation method thereof |
| CN108625182A (en) * | 2018-06-08 | 2018-10-09 | 厦门安踏体育用品有限公司 | The preparation method of titania hydrosol, top finish liquid, fabric and fabric |
| CN112143306A (en) * | 2020-09-17 | 2020-12-29 | 鹤山市顺鑫实业有限公司 | Covering base film and preparation method thereof |
| CN112852239A (en) * | 2020-12-29 | 2021-05-28 | 重庆中防德邦防水技术有限公司 | Organic/inorganic composite coating capable of independently forming gradient distribution layer |
| CN113881259A (en) * | 2021-11-12 | 2022-01-04 | 亚士创能科技(上海)股份有限公司 | Inorganic coating and preparation method and application thereof |
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| CN101967327A (en) * | 2010-09-30 | 2011-02-09 | 江苏大象东亚制漆有限公司 | Long-acting formaldehyde-resistant water-based crylic acid wood lacquer composite |
| CN102796407A (en) * | 2011-05-23 | 2012-11-28 | 河源海川科技有限公司 | Organic-inorganic hybrid photocatalytic coating and preparation method thereof |
| CN103525141A (en) * | 2013-09-16 | 2014-01-22 | 安徽欧尚建材有限公司 | Waterborne high temperature-resistant inorganic coating |
| CN103525141B (en) * | 2013-09-16 | 2016-05-04 | 安徽欧尚建材有限公司 | A kind of aqueous high-temperature-resistant inorganic coating |
| CN103555008A (en) * | 2013-09-29 | 2014-02-05 | 中国海洋石油总公司 | Water-based photocatalyst transparent coating |
| CN103555008B (en) * | 2013-09-29 | 2015-12-23 | 中国海洋石油总公司 | A kind of water-based photocatalyst Clear paint |
| CN104017398A (en) * | 2014-06-09 | 2014-09-03 | 复旦大学 | Preparation method of TiO2-based aqueous self-cleaning coatings |
| CN105400248A (en) * | 2015-11-30 | 2016-03-16 | 洛阳绿仁环保设备有限公司 | Weather-resistant coating and preparation method thereof |
| CN105789448A (en) * | 2016-04-18 | 2016-07-20 | 北京大学 | Thin film preparation method utilizing nanoparticle to improve surface wettability |
| CN106947345A (en) * | 2017-03-28 | 2017-07-14 | 江苏晨光涂料有限公司 | Reflective heat-insulation paint with self-cleaning function |
| CN107151496A (en) * | 2017-05-24 | 2017-09-12 | 佛山实瑞先导材料研究院（普通合伙） | A kind of nano-TiO2Modified water-soluble composite coating and preparation method thereof |
| CN107266990A (en) * | 2017-07-21 | 2017-10-20 | 张娟 | A kind of wall environmental protection coating material and preparation method thereof |
| CN108625182A (en) * | 2018-06-08 | 2018-10-09 | 厦门安踏体育用品有限公司 | The preparation method of titania hydrosol, top finish liquid, fabric and fabric |
| CN112143306A (en) * | 2020-09-17 | 2020-12-29 | 鹤山市顺鑫实业有限公司 | Covering base film and preparation method thereof |
| CN112852239A (en) * | 2020-12-29 | 2021-05-28 | 重庆中防德邦防水技术有限公司 | Organic/inorganic composite coating capable of independently forming gradient distribution layer |
| CN113881259A (en) * | 2021-11-12 | 2022-01-04 | 亚士创能科技(上海)股份有限公司 | Inorganic coating and preparation method and application thereof |
| CN114456635A (en) * | 2022-03-25 | 2022-05-10 | 西安前沿材料研究院有限公司 | Self-cleaning self-stratifying inner wall coating and preparation method and application thereof |
| CN115678376A (en) * | 2022-09-08 | 2023-02-03 | 宁波甬安光科新材料科技有限公司 | Photovoltaic antireflection coating liquid capable of being cured at normal temperature and super-hydrophilic photovoltaic antireflection glass |
| CN116925634A (en) * | 2023-08-28 | 2023-10-24 | 西安交通大学 | Titanium dioxide photocatalysis self-cleaning paint, coating and preparation method thereof |
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