CN1445312A - Aqueous functional coatings possessing effects of self-cleaning, anti mold, sterilization and purifying air - Google Patents

Aqueous functional coatings possessing effects of self-cleaning, anti mold, sterilization and purifying air Download PDF

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Publication number
CN1445312A
CN1445312A CN 02112793 CN02112793A CN1445312A CN 1445312 A CN1445312 A CN 1445312A CN 02112793 CN02112793 CN 02112793 CN 02112793 A CN02112793 A CN 02112793A CN 1445312 A CN1445312 A CN 1445312A
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coating
water
cleaning
self
sterilization
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CN1216951C (en
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王大志
刘金华
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

A functional water paint with self-cleaning, antimildew, bactericiding and air-cleaning functions for building contains (5-100)-nm anatase-type titanium oxide as photocatalyst (10-46%) and water-soluble resin or polymer emulsion or silicon sol or their composition as water adhesive (26-35%). It features that the various organic substances in the air or water in contact with its surface can be decomposed into CO2 and water. Its advantages are high effect and safety and durable acting.

Description

Have self-cleaning, anti-mildew, the aqueous functional coatings of the effect of sterilizing and purify air
Technical field:
The present invention relates to be used for the coating on the inside and outside surface of buildings.
Background technology:
At present, the coating that is used for the inside and outside surface of buildings all is infected with by various spots (as: oil, cigarette, really, vegetables etc.) easily, and is difficult to remove even produce mildew after polluting, and is neither attractive in appearance, also can cause the breeding of harmful bacterium; Though added antimildew disinfectant in some coating, because antimildew disinfectant often itself has toxicity its consumption is restricted, and antimildew disinfectant often can only kill harmful bacterium but can not remove harmful residual toxin of bacterium.In addition, the atmospheric pollution that current people work in the indoor and outdoor surroundings of life also is on the rise, by the oxynitride (NO of the vehicles and Industrial processes discharging x), carbon monoxide (CO), sulfurous gas (SO 2) wait the outside atmosphere that causes to pollute, the room air pollution that the waste gas of the toxic gas that the furniture and fixtures material discharges (as: formaldehyde), the generation of smoking etc. causes, existing coating is all powerless to this.
Summary of the invention:
The purpose of this invention is to provide a kind of aqueous functional coatings that has self-cleaning, anti-mildew, sterilizes and purify air effect.
Solution of the present invention is as follows:
Contain following component in the coating: 1. photocatalyst: be of a size of the nano-anatase titanium oxide of 5-100nm, content is 10-46%; 2. aqueous binders: water soluble resin or polymer emulsion or silicon sol and their mixture, total content are 26-35%; Described content is weight percentage.
That is to say, the present invention be a kind of be the water based emulsion type coating of main component with photocatalyst and aqueous binders, that is: the dispersion medium of coating is a water, base-material is an aqueous binders, add photocatalyst again as functional medium, play self-cleaning, anti-mildew, effect such as sterilize and purify air, form a kind of functional coating.
Photocatalyst adopts the nano-anatase titanium oxide that is of a size of 5-100nm, and content is 10-46% (accounting for the weight percent of coating total amount, as follows); This nano-anatase titanium oxide is because nano-scale causes quantum size effect: after absorbing UV-light, the surface can inspire stronger activating group----electron-hole pair, makes airborne hydrogen reduction and water oxidation, generates high-octane O in titania surface 2 -1With the OH active group, it is carbonic acid gas and water that its energy is enough to make microbiological degradation such as various organic spot that coating surface is infected with and mould, bacterium.Therefore, utilize the strong like this light-catalyzed reaction can be, play the effect of self-cleaning, anti-mildew, sterilization in coating surface decontamination, sterilization; Simultaneously, can be to airborne various organic substances and the oxynitride (NO that touches coating surface x), carbon monoxide (CO), sulfurous gas (SO 2), the toxic gas that discharges of furniture and fixtures material, the waste gas that produces of smoking etc. play the light-catalyzed reaction effect, and then air are carried out decontamination, sterilization, reach the effect that purifies air.Described ultraviolet effective area is wavelength X<380nm, and the sun, fluorescent lamp, high voltage mercury lamp, ultraviolet lamp etc. all can send the ultraviolet ray in this zone.So when using the nano-anatase titanium oxide photocatalyst, as long as indoor and outdoor has sunlight or fluorescent lamp, high voltage mercury lamp etc. just the photochemical catalysis effect can be arranged, play the effect of " disinfectant ", can use ultraviolet lamp as light source for some special place (as hospital, vault, warehouse, tunnel, culvert etc.), thereby obtain the effect of good self-cleaning, anti-mildew, sterilization, cleaning ambient air.
Aqueous binders can adopt water soluble resin or polymer emulsion or silicon sol and their mixture, as: series of acrylate emulsion (comprising pure third, vinegar third, phenylpropyl alcohol etc.), epoxy resin latex, organosilicon-modified acrylate emulsion, silicon sol etc., wherein one or more mix as binding agent and membrane-forming agent, and total content is 26-35%.
Except the constituent of above-mentioned key, color stuffing also is the essentially consist thing in the coating, can adopt ordinary titanium powder, kaolin, zinc oxide, lime carbonate, talcum powder, montmorillonite, mica powder, wollastonite, diatomite etc., wherein one or more mix, and its consumption is done suitable adjustment according to the consumption of photocatalyst.Formed coating this as white, also can add an amount of coloured mill base being deployed into required color according to the demand in market or user's requirement, as the aqueous color paste of ferric oxide, Tolylamine, the phthalein mountain valley with clumps of trees and bamboo, ultramarine etc.The type of mill base and consumption are decided on required painting color.Can make colored finished product and sell, the also on-the-spot preparation of the finished product of available white and coloured mill base.
On the basis of above batching, also to add various auxiliary agents (but being not limited in the following stated), to improve other performance of coating.Auxiliary agent can adopt general dispersion agent, flow agent, defoamer, thickening material, sanitas, antioxidant, softening agent, pH value conditioning agent, film coalescence aid etc.For example: the effect of dispersion agent is that photocatalyst and color stuffing are effectively disperseed; Flow agent can improve the flow leveling of coating and shrinkage cavity and " flake " that levelling property energy, elimination are filmed; The effect of defoamer is to eliminate the foam that is produced in coating material production, construction, the use, with the quality that guarantees to film; Thickening material can be adjusted the viscosity of slurry, plays thickening, stable effect and improve the rheological property of coating in the production of coating, storage, construction process; The effect of sanitas is to prevent becoming morally degenerate in coating storage, the transportation; Antioxidant can increase the antioxidant property of coating; Softening agent can increase the snappiness of coating; PH value conditioning agent can regulate the pH value of coating, to increase the stability of coating system; Film coalescence aid can make coating can be in wide temperature range film forming, promptly reduce the minimum film-forming temperature of coating.
Preparation process of the present invention is exemplified below (but being not limited in the following stated):
At first be ready to required various raw materials (all can directly on market, buy or the self-control of method routinely).Photocatalyst is the nano-anatase titanium oxide of 5-100nm; Aqueous binders is corresponding emulsion; The granularity of color stuffing is below 800 orders; Various auxiliary agents are then selected for use according to performance need.
Ready various raw materials routinely method on general high speed dispersor is disperseed, mixed.Operating process is generally: earlier an amount of water is added in the condiment bucket of high speed dispersor, add auxiliary agents such as dispersion agent, wetting agent, thickening material, defoamer, antioxidant, softening agent successively then under low speed (150~500 rev/mins); After mixing, photocatalyst and color stuffing are slowly added in the whirlpool that the dispersion machine impeller stirs, the slurry in this moment condiment bucket is thickening gradually again, should in time add water and regulate impeller and the condiment bucket at the bottom of distance, the whirlpool that impeller is stirred becomes shallow pot shape; After adding photocatalyst and color stuffing, should improve wheel speed (1000~1200 rev/mins) and proceed to stir, and measure slurry temperature and scraping blade fineness at any time, when slurry temperature is too high, stop to stir, row stirring again after the cooling for the treatment of, when the scraping blade fineness was qualified, dispersion step was finished; After this, under low speed, add auxiliary agents such as an amount of aqueous binders and flow agent, film coalescence aid, defoamer, sanitas, wetting agent, thickening material (the adding kind of auxiliary agent and order can suitably be adjusted according to the concrete prescription and the technology of product, also can add an amount of coloured mill base and mix colours) gradually; Add an amount of water high speed dispersion once more at last, and the potential of hydrogen of slurry is transferred to 8~9.5 with pH value conditioning agent.High speed dispersion finishes, and slurry can disperse to be in harmonious proportion through the three-roller regrinding, the discharging of sieving, and canning sealing gets final product.
This inside and outside surface (as: house, enclosure wall, tunnel, pipeline etc.) that can be used for various coagulation soil properties, metal matter or buildings such as wooden with nano-anatase titanium oxide as the aqueous functional latex coating of photocatalyst, also can be used for furniture, office accommodations, the vehicles etc., have wide range of applications.The effect that it not only has self-cleaning, anti-mildew, sterilizes and purify air, also have following characteristics simultaneously: the one, security is good, nano-anatase titanium oxide itself is nontoxic, in production, construction and the use of coating to environment and all kinds of animals and plants without any polluting and influence; The 2nd, prompt effect is good, and nano-anatase titanium oxide produces photocatalysis immediately under uviolizing; The 3rd, long-lasting good, the nano-anatase titanium oxide stable in properties, can not decompose, be " disinfectant " of a kind of catalyst type (promptly non-expendable), and other consumptive disinfectant can effect descend gradually along with the stripping of disinfectant.
Embodiment:
Embodiment 11) form: photocatalyst: nano-anatase titanium oxide 30% (adopt the sulfuric acid process self-control, granularity is 10~80nm) aqueous binders: acrylic ester emulsion 35% (the UCAR U-4552W of U.S.'s union carbide corporation [being called for short connection carbon],
Solid content 47%) color stuffing: light calcium carbonate 3%, talcum powder 2% (be the common product in market, granularity is that 800 orders are following) auxiliary agent: dispersion agent 1% (SN-5040 of Shenzhen Haichuan Company [being called for short Hai Chuan]), defoamer 0.3% (Hai Chuan
Nopco-8034), thickening material 3% (extra large river Modicol VD), sanitas 0.2% (extra large river Nopcoeide
SN-215), wetting agent 0.3% (extra large river Hyonic PE-100), (Yi Shi Man [is called for short flow agent 2%
Yi Shiman] Texanol), film coalescence aid 2% (commercially available propylene glycol), an amount of (the Tao Shi public affairs of pH value conditioning agent
The AMP-95 of department's [being called for short Tao Shi]) all the other are water.2) preparation process:
Earlier water (accounting for coating total amount 10%) is added in the condiment bucket of high speed dispersor, under low speed (200~300 rev/mins), add successively dispersion agent, wetting agent, thickening material 1/2nd, 2/3rds the mixing of defoamer, then photocatalyst, light calcium carbonate, talcum powder are slowly added in the condiment bucket, slurry in this moment condiment bucket is thickening gradually, should in time add an amount of water and regulate impeller and the condiment bucket at the bottom of distance, the whirlpool that impeller is stirred becomes shallow pot shape; After adding photocatalyst and color stuffing, should improve wheel speed (1000~1200 rev/mins) and proceed to stir, finish until dispersion step; Then, under low speed, add gradually flow agent, film coalescence aid, acrylic ester emulsion, defoamer 1/3rd, sanitas, thickening material 1/2nd, add an amount of pH value conditioning agent (making the pH value is 9.0) again; At last, add the water of surplus and improve wheel speed and carry out high speed dispersion once more.After disperseing to finish, slurry disperses to be in harmonious proportion through the three-roller regrinding, the discharging of sieving, and canning sealing gets product.3) performance and characteristics
1. the every fundamental property that has common exterior coating can play the effect of decorating and protecting.
2. has self-cleaning performance: under the irradiation of suitable ultraviolet ray (as the sun, high voltage mercury lamp etc.), the various organic dirts that the coating of degrading is infected with above, as the organism in butyraceous dirt and dust, printing ink, pigment dyestuff, fruit juice etc., wash away through natural wind and weather or artificial water, can reach cleaning effect.
3. the performance that has anti-mildew, sterilization: under suitable uviolizing, harmful microorganism such as the various moulds being infected with above the coating or generating of degrading, bacterium, and can remove the residual toxin of dead bacterium, play the effect of anti-mildew, sterilization.
4. has the performance that purifies air: under suitable uviolizing, touch the airborne various organic gass and the oxynitride (NO on its surface around the coating of degrading x), carbon monoxide (CO), sulfurous gas (SO 2) etc., play the atmospheric effect of environment purification.
5. do not produce obnoxious flavour, environmentally safe in construction and the use.4) scope of application
Be applicable to exterior wall finish of building, roof, balcony, tunnel of materials such as all kinds of mortars such as concrete, gypsum and timber etc., and the pipeline of metal material, fence, lamp bracket and lampshade, traffic mark board etc.
Embodiment 21) to form: photocatalyst: (adopt the sulfuric acid process self-control, granularity is 20~100nm) to nano-anatase titanium oxide 10%; Aqueous binders: acrylate and vinyl acetate emulsion 30% (connection carbon UCAR R-350Z, solid content 54~57%); Color stuffing: ordinary titanium powder 7.5%, light calcium carbonate 8%, talcum powder 3%, (it is normal to be market for montmorillonite 3%
See product, granularity is that 800 orders are following); Auxiliary agent: dispersion agent 0.6% (extra large river SN-5040), defoamer 0.3% (extra large river Nopco-8034), thickening material 0.3%
(connection carbon QP-15000H), sanitas 0.2% (extra large river Nopcocide SN-215), wetting agent 0.3% (sea
River Hyonic PE-100), flow agent 1% (Yi Shiman Texanol), film coalescence aid 2% (commercially available propylene glycol),
PH value conditioning agent an amount of (Tao Shi AMP-95); All the other are water.2) preparation process:
Earlier water (accounting for coating total amount 15%) is added in the condiment bucket of high speed dispersor, adding 2/3rds of dispersion agent, wetting agent, thickening material, defoamer under low speed (200~300 rev/mins) successively mixes, then photocatalyst, ordinary titanium powder, light calcium carbonate, talcum powder, montmorillonite are slowly added in the condiment bucket, slurry in this moment condiment bucket is thickening gradually, should in time add an amount of water and regulate impeller and the condiment bucket at the bottom of distance, the whirlpool that impeller is stirred becomes shallow pot shape; After adding photocatalyst and color stuffing, should improve wheel speed (1000~1200 rev/mins) and proceed to stir, finish until dispersion step; Then, under low speed, add gradually flow agent, film coalescence aid, polyvinyl acetate emulsion, defoamer 1/3rd, sanitas, add an amount of pH value conditioning agent (making the pH value is 8.5) again; At last, add the water of surplus and improve wheel speed and carry out high speed dispersion once more.After disperseing to finish, slurry disperses to be in harmonious proportion through the three-roller regrinding, the discharging of sieving, and canning sealing gets product.3) performance and characteristics
1. the every fundamental property that has common interior wall coating can play the effect of decorating and protecting.
2. has self-cleaning performance: under the irradiation of suitable ultraviolet ray (as fluorescent lamp, sterilization with ultraviolet lamp etc.), the various organic dirts that can degrade and be infected with on the metope, as the organism in butyraceous dirt and dust, printing ink, pigment dyestuff, fruit juice etc., only need manually to use scrub water, can reach cleaning effect.
3. the performance that has anti-mildew, sterilization: under suitable uviolizing, harmful microorganisms such as the various moulds of being infected with or generating on the metope of degrading, bacterium, and can remove the residual toxin of dead bacterium, play the effect of anti-mildew, sterilization.
4. has the performance that purifies air: under suitable uviolizing, the metope of degrading touches the airborne various organic gass on its surface, the toxic gas (as formaldehyde, phenol) that the furniture and fixtures material discharges, the smoke waste gas that produces, the peculiar smell that human body produces etc. on every side, plays the effect that purifies the air of a room.
5. do not produce obnoxious flavour, environmentally safe in construction and the use.4) scope of application
Be applicable to the inner wall of building facing of materials such as all kinds of mortars such as concrete, gypsum and timber, metal and ceiling etc.
Embodiment 31) to form: photocatalyst: (adopt the sulfuric acid process self-control, granularity is 5~60nm) to nano-anatase titanium oxide 46%; Aqueous binders: organosilicon-modified acrylate emulsion 32% (adopts acrylic ester emulsion and silicon sol blending method certainly
System, solid content 50~56%); Color stuffing: diatomite 1% (be the common product in market, granularity is that 800 orders are following); Auxiliary agent: dispersion agent 1% (extra large river SN-5040), defoamer 0.3% (extra large river Nopco-8034), thickening material 0.3%
(connection carbon QP-15000H), sanitas 0.2% (extra large river Nopcocide SN-215), wetting agent 0.6% (sea
River Hyonic PE-100), flow agent 1% (Yi Shiman Texanol), film coalescence aid 2% (commercially available propylene glycol),
PH value conditioning agent an amount of (Tao Shi AMP-95); All the other are water.2) preparation process:
Earlier water (accounting for coating total amount 10%) is added in the condiment bucket of high speed dispersor, adding 2/3rds of dispersion agent, wetting agent, thickening material, defoamer under low speed (200~300 rev/mins) successively mixes, then photocatalyst and diatomite are slowly added in the condiment bucket, slurry in this moment condiment bucket is thickening gradually, should in time add an amount of water and regulate impeller and the condiment bucket at the bottom of distance, the whirlpool that impeller is stirred becomes shallow pot shape; After adding photocatalyst and color stuffing, should improve wheel speed (1000~1200 rev/mins) and proceed to stir, finish until dispersion step; Then, under low speed, add gradually flow agent, film coalescence aid, organosilicon-modified acrylate emulsion, defoamer 1/3rd, sanitas, add an amount of pH value conditioning agent (making the pH value is 9.0) again; At last, add the water of surplus and improve wheel speed and carry out high speed dispersion once more.After disperseing to finish, slurry disperses to be in harmonious proportion through the three-roller regrinding, the discharging of sieving, and canning sealing gets product.3) performance and characteristics
1. the every fundamental property that has common exterior coating can play the effect of decorating and protecting.
2. has self-cleaning performance: under the irradiation of suitable ultraviolet ray (as the sun, high voltage mercury lamp etc.), the various organic dirts that the coating of degrading is infected with above, as the organism in butyraceous dirt and dust, printing ink, pigment dyestuff, fruit juice etc., wash away through natural wind and weather or artificial water, can reach cleaning effect.
3. the performance that has anti-mildew, sterilization: under suitable uviolizing, harmful microorganism such as the various moulds being infected with above the coating or generating of degrading, bacterium, and can remove the residual toxin of dead bacterium, play the effect of anti-mildew, sterilization.
4. has the performance that purifies air: under suitable uviolizing, touch various organic gass and oxynitride (NO in its surperficial air around the coating of degrading x), carbon monoxide (CO), sulfurous gas (SO 2) etc., play the atmospheric effect of environment purification.
5. do not produce obnoxious flavour, environmentally safe in construction and the use.4) scope of application
Be applicable to exterior wall finish of building, roof, balcony, tunnel of materials such as all kinds of mortars such as concrete, gypsum and timber etc., and the pipeline of metal material, fence, lamp bracket and lampshade, traffic mark board etc.It is self-cleaning, anti-mildew, the effect of sterilizing and purifying air are better than embodiment one, but cost is also higher.
Embodiment 41) form (form by two components, before construction, be in harmonious proportion in proportion): component one: photocatalyst: (adopt the sulfuric acid process self-control, granularity is 20~100nm) to nano-anatase titanium oxide 29%;
Aqueous binders: epoxy resin latex 26% (the PY 340-2 of Ciba company);
Water 45%.Component two: solidifying agent (HZ3982 of Ciba company).2) preparation process:
Earlier epoxy resin latex is added in the condiment bucket of high speed dispersor, under low speed (200~300 rev/mins), photocatalyst is slowly added in the condiment bucket, slurry in this moment condiment bucket is thickening gradually, should in time regulate the distance at the bottom of impeller and the condiment bucket, and the whirlpool that impeller is stirred becomes shallow pot shape; After adding photocatalyst, should improve wheel speed (1000~1200 rev/mins) and proceed to stir, finish until dispersion step; Then, under low speed, slowly add entry and make its emulsification, and controlled temperature is at 10~40 ℃.After the emulsification evenly, canning sealing gets final product.Solidifying agent is canned separately, and (component two is 25.7% with the ratio of component one) mediation is used in proportion before construction.3) performance and characteristics
1. have stronger sticking power, the intensity height, wear resistance, snappiness are good, and chemical resistance and anti-water, oil, acid, alkali, organic solvent are strong, and certain insulativity is arranged, and can play better protecting effect and certain decoration function.
2. has self-cleaning performance: under the irradiation of suitable ultraviolet ray (as the sun, high voltage mercury lamp, fluorescent lamp, sterilization with ultraviolet lamp etc.), the various organic dirts that the coating of degrading is infected with above, through natural wind and weather, or manually water washes away, cleans, and can reach cleaning effect.
3. the performance that has anti-mildew, sterilization: under suitable uviolizing, harmful microorganism such as the various moulds being infected with above the coating or generating of degrading, bacterium, and can remove the residual toxin of dead bacterium, play the effect of anti-mildew, sterilization.
4. the performance that has environment purification: under suitable uviolizing, touch its surperficial liquid or airborne various organism around the coating of degrading, play the effect of environment purification.4) scope of application
Be applicable to the building surface or the terrace of materials such as concrete, metal, as factory, warehouse, road, airport, machine room, pipeline, storage tank, appearance jar etc.

Claims (1)

1, a kind of aqueous functional coatings that has self-cleaning, anti-mildew, sterilizes and purify air effect is characterized in that containing in the coating following component: 1. photocatalyst: be of a size of the nano-anatase titanium oxide of 5-100nm, content is 10-46%; 2. aqueous binders: water soluble resin or polymer emulsion or silicon sol and their mixture, total content are 26-35%; Described content is weight percentage.
CN 02112793 2002-03-20 2002-03-20 Aqueous functional coatings possessing effects of self-cleaning, anti mold, sterilization and purifying air Expired - Fee Related CN1216951C (en)

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CN1302079C (en) * 2004-01-15 2007-02-28 中山大学 Light-catalyzed air-cleaning water environmental protection paint for inner wall
CN100580032C (en) * 2004-01-30 2010-01-13 美礼联化工英国控股有限公司 Coating composition having surface depolluting properties
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