CN102408806A - High-emission transparent heat-insulating paint in atmospheric window regions and preparation method thereof - Google Patents
High-emission transparent heat-insulating paint in atmospheric window regions and preparation method thereof Download PDFInfo
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- CN102408806A CN102408806A CN2011103433186A CN201110343318A CN102408806A CN 102408806 A CN102408806 A CN 102408806A CN 2011103433186 A CN2011103433186 A CN 2011103433186A CN 201110343318 A CN201110343318 A CN 201110343318A CN 102408806 A CN102408806 A CN 102408806A
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Abstract
The invention discloses a high-emission transparent heat-insulating paint in atmospheric window regions. The main material of the transparent heat-insulating paint is prepared from the following components in parts by weight: 30-70 parts of polymer emulsion, 10-30 parts of nano doped oxide powder, 2-30 parts of high-emission nano powder in atmospheric window regions, 1-10 parts of anionic dispersant, 2-20 parts of nonionic dispersant, 0.5-2 parts of defoaming agent, 0-5 parts of thickening agent, 1-2 parts of film forming assistant, 1-2 parts of antifreezing agent, 1-2 parts of leveling agent and 5-20 parts of distilled water. The invention also discloses a preparation method of the transparent heat-insulating paint, which comprises the following steps: after evenly mixing the components, regulating the pH value to 8.5-9.5 with a multifunctional assistant AMP-95 to obtain the high-emission-rate transparent heat-insulating paint in atmospheric window regions. The paint has high emission rate in atmospheric window regions, and can implement effective heat dissipation.
Description
Technical field
The present invention relates to a kind of coating, relate in particular to a kind of transparent heat insulating dope that is coated on building or the atmospheric window of glass for vehicle window outside surface zone high emission and preparation method thereof.
Background technology
From the thermal radiation viewpoint, the outer space can be similar to that to can be rated as a T be zero black matrix.If at temperature of atmospheric layer peripheral hardware black matrix (covering the point-blank sunshine) that is T=300K; Then it will little by little be cooled down.According to Stefan-Boltzman's law, can calculate the energy per unit area W that it is radiated the outer space:
W＝αT
4＝5.7×10
-8×300
4≈450W/m
2
This numerical value is very high refrigerating duty.In the outer space, utilize radial pattern coating, can obtain good effect of heat insulation.NASA (NASA) has just developed novel high radiation coating (Emisshield) technology in 1994, and uses it for X-33 and X-34 type orbiter.This product at room temperature has the radiant ratio up to 0.8-0.9, and its use temperature can reach 3000F even higher.
But within atmospheric layer, arrive the outer space because atmosphere has stopped the part ir radiation, its refrigeration can descend significantly.Because in the endoatmosphere, be not that space is all passed through in all radiation of earth transmission.The sizable part of radiation is absorbed and the surface that is transmitted into the earth again by earth atmosphere.
Atmospheric ir radiation is mainly derived from vapor in the atmosphere, carbonic acid gas, ozone and suspended particulates, and what wherein play a major role is water vapour and carbonic acid gas.In wavelength is the interval of 8～13.5 μ m; The infrared absorbance of water vapour and carbonic acid gas a little less than; Therefore; Ir radiation ability in this wave band also a little less than, so just make atmospheric layer very high perviousness arranged to the ir radiation of 8～13.5 μ m, we claim that wavelength is that the interval of 8～13.5 μ m is for " atmospheric window ".In the application of reality, can utilize so infrared window, reach the purpose of radiation refrigeration.
Fig. 1 representes that radiation power and the sky of the radiator in the atmospheric layer project radiation power and the relation between the wavelength on the radiator; Can know; When radiation heat loss and hot income are consistent; The temperature of radiator can reach Schwellenwert, and at limpid on high cloudless night, a black matrix can be cooled to than low 10～20 ℃ of surrounding environment temperature.And Fig. 2 and encloses the situation of ideal reflector for being perfect black body when radiator in other scopes in 8～13.5 mu m ranges, can know that the comparable black matrix of such radiator reduces to lower temperature.
Transparent heat insulating dope is a kind of coating that can after coating, form Clear coating, and this coating has very strong barrier property in the near-infrared region to sunlight.U.S. Pat 5518810 Infrared ray cutoff material and infrared cutoff powder use for same have just described a kind of tin-doped indium oxide powder and have been dispersed in the coating that forms in inorganic or the organic polymer; It is transparent at visible region; And can intercept the near infrared light of wavelength more than 1000nm, thereby reach heat insulation purpose.
In relevant transparent heat insulating dope patent---like application number is 200410014672.4 Chinese patent " the effect of heat insulation test set of nano transparent heat-insulation composite coating and this coating thereof ", and application number is 201010199580.3 Chinese patent " a kind of infrared shielding type glass heat-insulating coating and preparation method thereof "---all use the mixed nanometer oxide compound as functional stuffing.But,, but can't cool off effectively through thermal radiation because the mixed nanometer oxide compound makes coating constantly absorb infrared solar radiation to very strong sorption of infrared rays and lower infrared emittance thereof.Therefore; The coated surface of coating can rise to very high temperature under the irradiation of---especially summer noon sun---at sunlight; And after the sunlight direct projection finishes; Because coating is in the infrared light district---the low-launch-rate in atmospheric window zone especially, it is very slow that the temperature-fall period on the coated surface of coating also can carry out ground.Coating is in the condition of high temperature for a long time, can cause the increase of buildings or vehicle interior cooling load, influences the work-ing life of coating.
And if when coating has the high emission performance in atmospheric window zone; Just can be in sunlight direct projection cooling fast later; Effectively reduce coatingsurface in the time that comparatively high temps stopped, reduce buildings or vehicle interior cooling load, prolong coating work-ing life.
The high emission ability of coating is widely used in the opaque solar heat reflection coating to avoid the too much heat of coatingsurface accumulation; According to publication number is that the Chinese patent " solar heat radiation reflection coating " of CN 101812269 A is said, comprises the 20-70% filmogen by weight percentage, the 20-60% solvent; The 2-10% hollow minute particle; The infrared powder of 2-10%, 0.1-1% nano titanium oxide, the coating of 4-20% auxiliary agent gained; After coating film forming, reach the full spectrum solar heat reflection rate more than or equal to 85%, hemispherical emissivity at least more than or equal to 85%.Publication number is a reflective heat-insulation paint described in the Chinese patent " reflective heat-insulation paint and preparation method thereof " of CN 101565581A, and its full spectrum sun reflectivity is 0.87, and its hemispherical emissivity is 0.87.But these coating all are not transparent, can't satisfy the requirement of Clear paint.
Summary of the invention
The technical problem that the present invention will solve provides a kind of transparent heat insulating dope of atmospheric window high emission, and it can overcome lower and the deficiency that can't efficiently radiates heat of disclosed transparent heat insulating dope occurred in the prior art atmospheric window oral region emittance.
In order to solve the problems of the technologies described above; The present invention provides the transparent heat insulating dope of a kind of atmospheric window zone high emission, and the major ingredient of transparent heat insulating dope is grouped into by the one-tenth of following weight part: 5～20 parts of 30～70 parts of polymer emulsions, 10～30 parts of mixed nanometer oxidate powders, 2～30 parts of the nano-powders of atmospheric window oral region high emission, 1～10 part of anionic dispersing agent, 2～20 parts of non-ionic dispersing agents, 0.5～2 part of skimmer, 0～5 part of thickening material, 1～2 part of film coalescence aid, 1～2 part of frostproofer, 1～2 part of flow agent and zero(ppm) water.
Improvement as the transparent heat insulating dope of atmospheric window of the present invention zone high emission:
Polymer emulsion is polyacrylate emulsion, benzene emulsion or organosilicon crylic acid latex;
Said mixed nanometer oxidate powder is that particle size range is at least a in 5～60nm antimony-doped stannic oxide, fluorine-doped tin dioxide, gallium-doped zinc oxide, Al-Doped ZnO and the tin indium oxide;
The nano-powder of atmospheric window zone high emission is silicon-dioxide, mullite powder, silit, aluminum oxide and the aluminosilicate (xAl that particle size range is 5～60nm
2O
3YSiO
2) at least a;
Anionic dispersing agent is Sodium hexametaphosphate 99, tripoly phosphate sodium STPP or polymer-type anionic dispersing agent;
Non-ionic dispersing agent is dispersion agent DP270 (being polyacrylate dispersant DP270);
Skimmer is 090 skimmer, SPA-202 skimmer, Dapro DF 7010 skimmers or tributyl phosphate;
Thickening material is a hydroxyethyl ether cellulose;
Film coalescence aid is an alcohol ester-12;
Frostproofer is a Ucar 35;
Flow agent is a polypropyleneoxide.
The present invention also provides the preparation method of the transparent heat insulating dope of above-mentioned atmospheric window zone high emission simultaneously, may further comprise the steps successively:
1) skimmer that, under stirring at low speed, is sequentially added into zero(ppm) water, anionic dispersing agent, non-ionic dispersing agent, 25～35% (weight ratio) stirs;
2) nano-powder that, in the mixture of step 1) gained, adds mixed nanometer oxidate powder and atmospheric window oral region high emission successively; After stirring; The skimmer that adds the thickening material and 35～45% (weight ratio) of 1/2～1/4 (weight ratio) again stirs, and gets mill base; Place high speed dispersor to disperse 30 minutes mill base;
3), under the state of stirring at low speed, film coalescence aid, frostproofer and flow agent are joined in the polymer emulsion;
4), with step 2) mill base of gained adds in the step 3) gains; Stirring at low speed then; Drip residue skimmer and remaining thickening material in the whipping process, and regulate PH to 8.5～9.5, the transparent heat insulating dope of atmospheric window zone high emission with multifunctional assistant AMP-95.
In the present invention, stirring at low speed is meant 300～400r/min; Step 2) be the nano-powder that adds mixed nanometer oxidate powder and atmospheric window oral region high emission successively in, the rotating speed of high speed dispersor is 3000～4000r/min.
Beneficial effect of the present invention is: the present invention passes through to add the nanoparticle in the atmospheric window high emission of rational proportion, thereby has following performance: higher in atmospheric window oral region emittance, can realize efficiently radiates heat.
Description of drawings
Do further explain below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is that radiation power and the sky of the radiator of expression in the atmospheric layer projects radiation power and the graph of a relation between the wavelength on the radiator;
Fig. 2 represent when radiator in 8～13.5 mu m ranges for perfect black body, and when in other scopes, enclosing the situation of ideal reflector, radiator radiation power and sky project radiation power and the graph of a relation between the wavelength on the radiator.
Embodiment
Part in following examples is weight part.
The transparent heat insulating dope of embodiment 1, a kind of atmospheric window zone high emission, by weight, the major ingredient of transparent heat insulating dope is made up of following component: 50 parts of polyacrylate emulsions; (particle diameter is 5～60nm) 15 parts to nanometer antimony-doped stannic oxide, and (particle diameter is 5～60nm) 15 parts to nano mullite powder, as 2 parts of the Sodium hexametaphosphate 99s of anionic dispersing agent; As 4 parts of the DP270 dispersion agents of non-ionic dispersing agent, 1 part of 090 skimmer is as 3 parts of the hydroxyethyl ether celluloses of thickening material; As 1 part of the polypropyleneoxide of flow agent; As the alcohol ester-12 1 of film coalescence aid part, as 1 part of the Ucar 35 of frostproofer, 7 parts of zero(ppm) water.
Its preparation method is for carry out following steps successively:
1), pre-mixing:
(be sequentially added into 0.3 part of 7 parts of zero(ppm) water, 2 parts of Sodium hexametaphosphate 99s, 4 parts of DP270 dispersion agents and 090 skimmer under 300～400r/min), stir (stirring 30 minutes) in stirring at low speed;
2), high speed dispersion:
In the mixture of step 1) gained, add 15 parts of 15 parts of nanometer antimony-doped stannic oxides and nano mullite powders successively; Stir after (stirring 30 minutes); Add 0.4 part of 1 part of hydroxyethyl ether cellulose and 090 skimmer again and stir (stirring 30 minutes), get mill base; Mill base is placed high speed dispersor, and (3000～4000r/min) disperseed 30 minutes.
3), (under 300～400r/min) the state, 1 part of alcohol ester-12 1 part, 1 part of Ucar 35 and polypropyleneoxide is joined in 50 parts of the polyacrylate emulsions in stirring at low speed;
4), with step 2) mill base adds in the step 3) gains after the dispersion of gained; Stirring at low speed is (300～400r/min) 30 minutes then; Drip 2 parts of 0.3 part of remaining 090 skimmer and remaining thickening materials (hydroxyethyl ether cellulose) in the whipping process, and regulate PH to 9, filter and (cross 400 eye mesh screens through AMP-95; Purpose is the impurity that possibly exist in order to remove), the transparent heat insulating dope of atmospheric window zone high emission.
The transparent heat insulating dope of embodiment 2, a kind of atmospheric window high emission, by weight, the major ingredient of transparent heat insulating dope is made up of following component: 50 parts of benzene emulsions; (particle diameter is 5～60nm) 15 parts to fluorine-doped tin dioxide, and (particle diameter is 5～60nm) 15 parts to nano mullite powder, as 2.5 parts of the Sodium hexametaphosphate 99s of anionic dispersing agent; As 5 parts of the DP270 dispersion agents of non-ionic dispersing agent, 1 part of 090 skimmer is as 3 parts of the hydroxyethyl ether celluloses of thickening material; As 1 part of the polypropyleneoxide of flow agent; As the alcohol ester-12 1 of film coalescence aid part, as 1 part of the Ucar 35 of frostproofer, 6 parts of zero(ppm) water.
Its preparation method is for carry out following steps successively:
1), pre-mixing:
(be sequentially added into 0.3 part of 6 parts of zero(ppm) water, 2.5 parts of Sodium hexametaphosphate 99s, 5 parts of DP270 dispersion agents and 090 skimmer under 300～400r/min), stir (stirring 30 minutes) in stirring at low speed;
2), high speed dispersion:
In the mixture of step 1) gained, add 15 parts of 15 parts of fluorine-doped tin dioxides and nano mullite powders successively, after stir (stirring 30 minutes), add 0.4 part of 1 part of hydroxyethyl ether cellulose and 090 skimmer again and stir (stirring 30 minutes), get mill base; Place high speed dispersor to disperse 30 minutes (3000～4000r/min) mill base.
3), (under 300～400r/min) the state, 1 part of alcohol ester-12 1 part, 1 part of Ucar 35 and polypropyleneoxide is joined in 50 parts of the benzene emulsions in stirring at low speed;
4), with step 2) mill base adds in the step 3) gains after the dispersion of gained; Stirring at low speed is (300～400r/min) 30 minutes then; Drip 2 parts of 0.3 part of remaining 090 skimmer and remaining thickening materials (hydroxyethyl ether cellulose) in the whipping process; And through AMP-95 adjusting PH to 9, filter, get the transparent heat insulating dope of atmospheric window zone high emission.
The transparent heat insulating dope of embodiment 3, a kind of atmospheric window high emission, by weight, the major ingredient of transparent heat insulating dope is made up of following component: 50 parts of benzene emulsions; (particle diameter is 5～60nm) 7 parts to nano-indium stannum oxide, and (particle diameter is 5～60nm) 8 parts to nanometer antimony-doped stannic oxide, and (particle diameter is 5～60nm) 15 parts to nano mullite powder; As 2.5 parts of the Sodium hexametaphosphate 99s of anionic dispersing agent, as 5 parts of the DP270 dispersion agents of non-ionic dispersing agent, 1 part of 090 skimmer; As 3 parts of the hydroxyethyl ether celluloses of thickening material, as 0.5 part of the polypropyleneoxide of flow agent, as the alcohol ester-12 1 of film coalescence aid part; As 1 part of the Ucar 35 of frostproofer, 6 parts of zero(ppm) water.
Its preparation method is for carry out following steps successively:
1), pre-mixing:
(be sequentially added into 0.3 part of 6 parts of zero(ppm) water, 2.5 parts of Sodium hexametaphosphate 99s, 5 parts of DP270 dispersion agents and 090 skimmer under 300～400r/min), stir (stirring 30 minutes) in stirring at low speed;
2), high speed dispersion:
In the mixture of step 1) gained, add 15 parts of 8 parts of nanometer antimony-doped stannic oxides, 7 parts of nano-indium stannum oxides and nano mullite powders successively; Stir after (stirring 30 minutes); Add 0.4 part of 1 part of hydroxyethyl ether cellulose and 090 skimmer again and stir (stirring 30 minutes), get mill base; Place high speed dispersor to disperse 30 minutes (3000～4000r/min) mill base.
3), (under 300～400r/min) the state, 0.5 part of alcohol ester-12 1 part, 1 part of Ucar 35 and polypropyleneoxide is joined in 50 parts of the benzene emulsions in stirring at low speed;
4), with step 2) mill base adds in the step 3) gains after the dispersion of gained; Stirring at low speed is (300～400r/min) 30 minutes then; Drip 2 parts of 0.3 part of remaining 090 skimmer and remaining thickening materials (hydroxyethyl ether cellulose) in the whipping process; And through AMP-95 adjusting PH to 9, filter, get the transparent heat insulating dope of atmospheric window zone high emission.
The transparent heat insulating dope of embodiment 4, a kind of atmospheric window high emission, by weight, the major ingredient of transparent heat insulating dope is made up of following component: 50 parts of polyacrylate emulsions; (particle diameter is 5～60nm) 15 parts to nanometer antimony-doped stannic oxide, and (particle diameter is 5～60nm) 10 parts to nano mullite powder, and (particle diameter is 5～60nm) 5 parts to nano silica powder; As 2 parts of the Sodium hexametaphosphate 99s of anionic dispersing agent; As 4 parts of the DP270 dispersion agents of non-ionic dispersing agent, 1 part of 090 skimmer is as 3 parts of the hydroxyethyl ether celluloses of thickening material; As 1 part of the polypropyleneoxide of flow agent; As the alcohol ester-12 1 of film coalescence aid part, as 1 part of the Ucar 35 of frostproofer, 7 parts of zero(ppm) water.
Its preparation method is for carry out following steps successively:
1), pre-mixing:
(be sequentially added into 0.3 part of 7 parts of zero(ppm) water, 2 parts of Sodium hexametaphosphate 99s, 4 parts of DP270 dispersion agents and 090 skimmer under 300～400r/min), stir (stirring 30 minutes) in stirring at low speed;
2), high speed dispersion:
In the mixture of step 1) gained, add 15 parts of nanometer antimony-doped stannic oxides, 10 parts of nano mullite powders successively; 5 parts of nano silica powders; Stir after (stirring 30 minutes); Add 0.4 part of 1 part of hydroxyethyl ether cellulose and 090 skimmer again and stir (stirring 30 minutes), get mill base; Place high speed dispersor to disperse 30 minutes (3000～4000r/min) mill base.
3), (under 300～400r/min) the state, 1 part of alcohol ester-12 1 part, 1 part of Ucar 35 and polypropyleneoxide is joined in 50 parts of the polyacrylate emulsions in stirring at low speed;
4), with step 2) mill base adds in the step 3) gains after the dispersion of gained; Stirring at low speed is (300～400r/min) 30 minutes then; Drip 2 parts of 0.3 part of remaining 090 skimmer and remaining thickening materials (hydroxyethyl ether cellulose) in the whipping process; And through AMP-95 adjusting PH to 9, filter, get the transparent heat insulating dope of atmospheric window zone high emission.
The transparent heat insulating dope of Comparative Examples 1, a kind of atmospheric window zone high emission, by weight, in the component of the major ingredient of its transparent heat insulating dope: with the nano mullite powder of alternative 15 parts of 15 parts nanometer antimony-doped stannic oxides; That is, total consumption of nanometer antimony-doped stannic oxide is 30 parts; All the other are with embodiment 1.
Through ultraviolet-visible-near infrared spectrometer test; The visible light transmissivity of the coating of embodiment 1,2,3,4 gained transparent heat insulating dopes preparation is more than or equal to 80%; Wavelength 1000-2500nm infrared light district transmitance is less than 10%; Test according to the JC/T235-2008 standard, atmospheric window zone full spectrum hemispherical emissivity is more than or equal to 0.8.This transparent heat insulating dope all is transparence, that is, be applied in body surface according to conventional thickness after, can see through this dope layer, see object clearly.
Through ultraviolet-visible-near infrared spectrometer test; The visible light transmissivity of the coating of Comparative Examples 1 gained transparent heat insulating dope preparation is 80%～85%; Wavelength 1000-2500nm infrared light district transmitance is less than 10%; Test according to the JC/T235-2008 standard, atmospheric window zone full spectrum hemispherical emissivity is merely 0.45.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (7)
1. the transparent heat insulating dope of atmospheric window zone high emission, the major ingredient that it is characterized in that transparent heat insulating dope is grouped into by the one-tenth of following weight part: 5～20 parts of 30～70 parts of polymer emulsions, 10～30 parts of mixed nanometer oxidate powders, 2～30 parts of the nano-powders of atmospheric window oral region high emission, 1～10 part of anionic dispersing agent, 2～20 parts of non-ionic dispersing agents, 0.5～2 part of skimmer, 0～5 part of thickening material, 1～2 part of film coalescence aid, 1～2 part of frostproofer, 1～2 part of flow agent and zero(ppm) water.
2. the transparent heat insulating dope of atmospheric window according to claim 1 zone high emission, it is characterized in that: said polymer emulsion is polyacrylate emulsion, benzene emulsion or organosilicon crylic acid latex.
3. the transparent heat insulating dope of atmospheric window according to claim 2 zone high emission is characterized in that: said mixed nanometer oxidate powder is that particle size range is at least a in 5～60nm antimony-doped stannic oxide, fluorine-doped tin dioxide, gallium-doped zinc oxide, Al-Doped ZnO and the tin indium oxide.
4. the transparent heat insulating dope of atmospheric window according to claim 3 zone high emission is characterized in that: the nano-powder of said atmospheric window zone high emission be particle size range be 5～60nm silicon-dioxide, mullite powder, silit, aluminum oxide and aluminosilicate at least a.
5. the transparent heat insulating dope of atmospheric window according to claim 4 zone high emission, it is characterized in that: said anionic dispersing agent is Sodium hexametaphosphate 99, tripoly phosphate sodium STPP or polymer-type anionic dispersing agent; Said non-ionic dispersing agent is dispersion agent DP270.
6. the transparent heat insulating dope of atmospheric window according to claim 5 zone high emission is characterized in that:
Said skimmer is 090 skimmer, SPA-202 skimmer, Dapro DF 7010 skimmers or tributyl phosphate;
Said thickening material is a hydroxyethyl ether cellulose;
Said film coalescence aid is an alcohol ester-12;
Said frostproofer is a Ucar 35;
Said flow agent is a polypropyleneoxide.
7. like the preparation method of the transparent heat insulating dope of any one atmospheric window zone high emission in the claim 1～6, it is characterized in that may further comprise the steps successively:
1), under stirring at low speed, be sequentially added into zero(ppm) water, anionic dispersing agent, non-ionic dispersing agent, 25～35% skimmer stirs;
2), in the mixture of step 1) gained, add the nano-powder of mixed nanometer oxidate powder and atmospheric window oral region high emission successively, after stirring, add 1/2～1/4 thickening material and 35～45% skimmer again and stir, mill base; Place high speed dispersor to disperse 30 minutes mill base;
3), under the state of stirring at low speed, film coalescence aid, frostproofer and flow agent are joined in the polymer emulsion;
4), with step 2) mill base adds in the step 3) gains after the dispersion of gained; Stirring at low speed then; Drip residue skimmer and remaining thickening material in the whipping process, and regulate PH to 8.5～9.5, get the transparent heat insulating dope of atmospheric window zone high emission with multifunctional assistant AMP-95.
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