CN101538444A - Water-based nano heat insulating coating used for glass and preparation method thereof - Google Patents
Water-based nano heat insulating coating used for glass and preparation method thereof Download PDFInfo
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- CN101538444A CN101538444A CN200910098088A CN200910098088A CN101538444A CN 101538444 A CN101538444 A CN 101538444A CN 200910098088 A CN200910098088 A CN 200910098088A CN 200910098088 A CN200910098088 A CN 200910098088A CN 101538444 A CN101538444 A CN 101538444A
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Abstract
The invention belongs to the technical field of nano coatings, and particularly relates to a water-based nano heat insulating coating used for glass. The water-based nano heat insulating self-cleaning coating used for glass consists of the following components by weight: 45-55 portions of high molecular resin, 5-15 portions of nano ATO slurry, 0.1-1 portion of crosslinking agent, 0.1-0.8 portion of ultraviolet absorber and 5-10 portions of ethanol. The invention aims at overcoming the disadvantages in the prior art, and provides a heat insulating coating used for glass which has excellent heat insulating performance and transparency, weather resistance, simple and feasible production process, convenient construction and low production cost and a preparation method thereof.
Description
Technical field
The invention belongs to the nano paint technical field, be specifically related to be used for the water-based nano heat insulating coating of glass.
Background technology
In all kinds of energy consumptions, constructure heating and air-conditioning power consumption occupy quite great proportion.Door and window is as building enclosure transparent in the building construction and can opening, be Winter protection and summer the weakest heat insulation part.
The at present main energy-saving glass of using is a Low-E glass, claims low radiation coated glass again, good energy-conserving effect, use also maximum, but its apparatus expensive, energy consumption is higher, and need make double glazing unit and could keep its energy-saving effect.
Glass in the existing building is carried out the way of reducing energy consumption and have only two kinds of selections: the one, original glass of dismantling is changed energy-saving glass, and the 2nd, original glass is carried out energy-conservation upgrading.Sticking heat insulation safety film for building is a good method of upgrading to old glass energy-saving, but the defective that this way exists at present is that it costs an arm and a leg, and this makes its range of application restricted greatly.
The nano heat-insulating Clear paint is that a kind of glass that can allow not only keeps the high light transmittance while but also the high-tech product of effect of heat insulation is preferably arranged.Its ultimate principle is to utilize absorption and the reflection to infrared light of the nano level semiconductor material be entrained in wherein, intercepts the most of thermal radiation from sunlight and heating of house facility and human body self.Be widely used in the on glass of automobile and all kinds of buildingss, not only light transmission is good, and effect of heat insulation is good, and indoor/outdoor temperature-difference is reached about 3～8 ℃, and not turning on the aircondition also to reach the effect of " cool in summer and warm in winter ".With the nano heat-insulating Clear paint building doors and windows and glass curtain wall are carried out reducing energy consumption following advantage are arranged:
1, more economical faster.The heat insulation and heat control performance of nano heat-insulating Clear paint is close with Low-E glass, but with this coating glass is carried out the cost of reducing energy consumption only for changing 30% of Low-E glass.Original glass or ordinary insulating glass only need be coated just upgrade respectively behind the nano heat-insulating Clear paint heat-protecting glass or hollow heat-reflecting glass, and be easy and simple to handle, the technology cost is low.If can accomplish family expenses spary coating type packing, then easier popularization.
2, more environmental protection is more healthy.Be to utilize existing glass fully, can not produce building waste.Make body material with water soluble resin, can not produce poisonous and harmful and pollute.The nano heat-insulating Clear paint can intercept the ultraviolet ray more than 80%, can prevent indoor carpet, curtain, and fabric and paint etc. fades, and effectively protects office equipment such as indoor furniture, computer, prolongs its work-ing life.
3, slimmer and more graceful safer.The coating thickness of nano heat-insulating Clear paint only is 8 microns, one of percentage of too late hairline, and its weight almost can be ignored, and can not increase building load.In addition, because the more crisp frangible characteristic of glass, the high-altitude tragedy of hurting sb.'s feelings that drops occurs repeatedly, and the nano heat-insulating polymeric coating itself has certain elasticity and tearing toughness because cohesive force is strong, is expected effectively to solve the problem that the glass fragmentation is hurted sb.'s feelings.
People such as Yao Chen have discussed the mechanism of heat insulation of nano heat-insulating Clear paint, thinking that to film to thermal-radiating iris action be semiconductor material absorbs and reflects coefficient result incident light, has only nano level semiconductor alloy powder could well solve heat-insulating problem.
Aspect the preparation of nano-ITO (Indium Ttin Oxides indium tin metal oxide compound) or nano ATO (AntimonyDoped Tin Oxide antimony-doped stannic oxide), solvent thermal-calcination method, ion-exchange dechlorination hydrolysis method, Isoamyl Acetate FCC azeotropic distillation drying are arranged, open the low temperature that virtuous high people explored the ITO nano powder, the preparation method who is easy to volume production: indium tin hydroxide is placed in the autoclave that is full of argon gas, under 300 ℃, the condition of 2MPa, just can make the nano particle of ITO.
Nano-ITO, ATO in coating system dispersion and stable be key one ring of heat-insulation transparent nano paint development, generally adopt ultrasonic dispersing method, ball milled etc., adopt ethylene glycol etc. as dispersion medium usually, be coupling agent with KH570 or stearyl alcohol.Human water coprecipitation methods such as the xuwei tinkling of pieces of jade prepare the ITO powder, have analyzed the influence of factors such as precipitation agent, reactant concn, calcining temperature and time to preparation process and product; People such as Chi Yanbo have studied dispersion, the stabilization process of ATO ultrafine powder in water, and the influence of the parameters such as kind, addition, dispersing mode of pH value, dispersion agent to preparation ATO water slurry has been discussed.
The homemade finely disseminated nano ATO water dispersion of humans such as Wang Jing also is to be vector resin with the aqueous polyurethane, dries by the fire 3-4 hour film forming down at 80 ℃, has prepared the good Clear coating of heat-proof quality.
People such as Chen Feixia discover with the heat-insulation transparent coating for preparing with nano-ITO and are being better than nano ATO aspect the obstruct infrared light, but ITO has hindered the popularization of nano-ITO coating more than the price of ATO costliness.
The dispersion of nano-ITO or ATO and stable aspect, except above-mentioned chemical method and physics method, also has electrochemical method, this method is based on nanoparticle surface and has iso-electric point, when the pH value by regulator solution makes it to differ maximum with iso-electric point, just can increase nanoparticle dispersive stability in similar " electrostatic double layer " structure of the formation at the interface of nanoparticle.
Chinese patent literature CN1563231A discloses a kind of glass that is applied to, transparent resin, the effect of heat insulation test set of the nano transparent heat-insulation composite coating of metal and cement surface and this coating thereof.Coating is by urethane resin, polyorganosiloxane resin, polyacrylic resin, nano-indium stannum oxide (ITO) powder, nano antimony tin oxide (ATO) powder, compositions such as coatings additive(s) and thinner.Characteristics such as this coating has strong adhesion, and is transparent, and the shielding infrared rays is heat insulation are particularly suitable for using on vehicle glass and the building glass.
Chinese patent literature CN1903958 discloses a kind of synthesized polyurethane glass heat insulating paint and preparation method thereof, this coating comprises 40-90% (weight) synthesis of polyurethane resin, 10-60% nano ATO slurry and thinner, the nano ATO solid content of slurry is 10-30%, particle diameter is 50-100nm, and the coating wet-film thickness is 20～400 microns.Its preparation method is: the nano ATO slurry that first solid content with 10-60% is 10-30% is added drop-wise in the aqueous polyurethane of 40-90%, and stirs 10-30 minute, gets synthesized polyurethane glass heat insulating paint.The glass made from this coating has higher visible light transmissivity, and the reflectivity to infrared rays (thermal radiation) is very high simultaneously, has the effect that blocking radiant heat directly sees through.The present invention promptly can be made into transparent heat insulating dope at normal temperatures by simple technology, compares with other coated glass, and cost greatly reduces, and can be widely used in covil construction.
But present nano ATO paint still exists, and stability is relatively poor and heat insulation, the technical problem of self-cleaning function and the coating transparency and weathering resistance contradiction.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of excellent adiabatic capacity and transparency of having concurrently simultaneously is provided, have good weatherability, production technique is simple, easy construction, glass heat-insulating coating that production cost is low and preparation method thereof.
The present invention is achieved through the following technical solutions:
The water-borne heat-insulating self-cleaning nona coating that is used for glass, described coating composition and weight part are as follows:
Macromolecule resin 45～55,
Nano ATO slurry 5～15,
Linking agent 0.1～1,
Uv-absorbing agent 0.1～0.8,
Ethanol 5～10.
Described macromolecule resin is that waterborne polyurethane resin, water-borne acrylic resin or polyorganosiloxane resin are as matrix resin, the dispersity of ATO is 30% in the described nano ATO slurry, described linking agent is methacryloxypropyl trimethoxy silane KH570, and described uv-absorbing agent is UV-329.
The preparation method who is used for the water-borne heat-insulating self-cleaning nona coating of glass is to be 30% powders A TO KH570 aqueous solution Ball milling 48 hours with solid content, wherein dispersion agent KH570 accounts for 0.5%～2% of powders A TO weight, uses agate as ball-milling additive.
The slurry that more than makes is reconciled pH value to 7～8 and is made the nano ATO slurry, adds macromolecule resin, linking agent, uv-absorbing agent and ethanol then and mix in the nano ATO slurry, makes nano paint.
A kind of prioritization scheme of the present invention is to adopt mono-component aqueous polyurethane coating (WPU), and the synthetic part hydrophilic group of normally introducing in polyurethane structural of WPU makes and self disperses to form emulsion.
Further prioritization scheme of the present invention is to introduce hydrophilic radical in WPU, introduce in the PU molecular chain as hydrophilizing agent with the stronger dimethylol propionic acid (DMPA) of organic acid such as wetting ability, tartrate etc., it is in the neutralizing agent then with alkali and salify, in deionized water, disperse again, form the PU water miscible liquid by mechanical stirring.
Optimization scheme is the method that adopts nanoparticle WPU in-situ polymerization, being about to homodisperse ATO nanoparticle directly is keyed on the acrylic acid modified WPU molecular chain, form star shape branch copolymer, to obtain the heat-insulation transparent water-borne coatings of permanent stable dispersion, and improve the performance film, as cohesive strength etc.
The another kind of prioritization scheme of the present invention is with nano-TiO
2Stir and the ultrasonic wave effect is handled with the siloxanes coupling agent down, make slurry or dilute solution, add in the substrate resin solution or be coated with to tie to spray with the form of rare resin solution again after finishing and cohere one deck nano-TiO at nano paint of the present invention
2Layer is because nano-TiO
2Photocatalysis can decompose the organism that is attached to glass surface, so can play self-cleaning technique effect.
Description of drawings
Fig. 1 is the Electronic Speculum of coating of the present invention figure as a result
Fig. 2 is influence the as a result figure of ball milling time to slurry system pH value
Embodiment
The present invention is described further below in conjunction with accompanying drawing, but protection domain of the present invention not only is confined to following examples:
Embodiment 1～5:
The preparation of nano ATO slurry:
Add powders A TO, dispersion agent KH570 in water, 48h makes the nano ATO slurry with the 3000r/min ball milling, and keeping system temperature is about 30 ℃, re-adjustment system pH to 8, and wherein the ball milling time is to the influence of slurry system pH value as shown in Figure 2.The laser particle analyzer testing size disperses particle diameter and distribution, and TEM characterizes the form pattern of particle, and system is used centrifugal settling method research stability of slurry, and whether thermal weight loss and infrared spectroscopy proof KH570 keyed jointing.
The preparation of matrix resin:
Can be according to the synthetic WPU of following steps: in polyester glycol (Mn1000) and DMPA (wherein-COOH account for molecular chain mass ratio about 1.5%) adding three-necked bottle, vacuum hydro-extraction 2h under 120～130 ℃ of conditions, the cooling back adds TDI (NCO/-OH about 1.2 is advisable), logical nitrogen, be not higher than 80 ℃ of reactions to reaching theoretical NCO%, add the propenoic acid beta-hydroxy ethyl ester (HEA, molar weight is theoretical NCO%) of metering, continue the about 2h of reaction and obtain hydrophilic end thiazolinyl performed polymer, add triethylamine TEA neutralization.The neutral performed polymer slowly added in the deionized water disperse to obtain dispersion liquid just.Just adding methyl methacrylate (MMA) and AIBN in the dispersion liquid, under 60 ℃ of conditions, carry out radical polymerization 4h, promptly obtain acrylate modified WPU coating, correlated response mechanism is seen following reaction formula:
Conventional WPU is synthetic:
HO-R-OH+OCN-Ph-NCO→OCN-R`-NCO (1)
OCN-R`-NCO+CH
3-C(CH
2OH)
2-COOH→HO-R``-OH (WPU) (2)
Acrylic acid modified WPU is synthetic:
HO-R-OH+CH
3-C(CH
2OH)
2-COOH+OCN-Ph-NCO→OCN-R`-NCO (3)
OCN-R`-NCO+CH
2＝CH-COOCH
2CH
2-OH→CH
2＝CH-R``-CH＝CH
2 (4)
The preparation of heat-insulated transparent coating:
With above-mentioned ATO slurry and matrix resin according to the full and uniform mixing of weight part, optimize the glass heat-insulation transparent nano coating of processability excellence, in the first dispersion liquid of the end thiazolinyl performed polymer that in previous step matrix resin preparation process, obtains, add methyl methacrylate (MMA), AIBN, UV329 and KH570 have handled the nano ATO slurry, under 60 ℃ of conditions, carry out radical polymerization 4h, promptly obtain acrylate modified, keyed jointing the WPU coating of nano ATO, its Electronic Speculum as a result figure as shown in Figure 1, the result shows that the coating that the technical program makes has good dispersing property.
Nano-TiO
2Layer:
Contain TiO
2One deck nano-TiO is cohered in the WPU dispersion liquid spraying of 10% solid content
2Layer
The coating correlated performance characterizes:
Adopt ultraviolet-see light-near infrared spectrometer etc. that the spectrum property of made ITO or ATO Clear coating is detected.
Wherein, the prescription of embodiment 1～5 and condition such as following table:
| Embodiment | Waterborne polyurethane resin/weight part | Nano ATO slurry/weight part | The KH570/ weight part | The UV-329/ weight part | Ethanol/weight part |
| 1 | 45 | 10 | 0.1 | 0.2 | 5～10 |
| 2 | 40 | 10 | 0.1 | 0.2 | 5～10 |
| 3 | 20 | 10 | 0.1 | 0.2 | 5～10 |
| 4 | 50 | 10 | 0.1 | 0.2 | 5～10 |
| 5 | 40 | 10 | 0.1 | 0.2 | 5～10 |
The table with test results of embodiment 1～5 is as follows:
| Embodiment | Visible light transmissivity/% | Infrared rays rejection rate/% | UV-light rejection rate/% | Thickness/um |
| 1 | 70 | 65 | 94 | 20 |
| 2 | 60 | 70 | 94 | 30 |
| 3 | 30 | 85 | 94 | 20 |
| 4 | 72 | 65 | 94 | 20 |
| 5 | 65 | 70 | 94 | 20 |
Claims (5)
1, a kind of water-based nano heat insulating coating that is used for glass is characterized in that described coating is formed and weight part is as follows:
Macromolecule resin 45～55,
Nano ATO slurry 5～15,
Linking agent 0.1～1,
Uv-absorbing agent 0.1～0.8,
Ethanol 5～10.
2, the water-based nano heat insulating coating that is used for glass according to claim 1, it is characterized in that described macromolecule resin is a waterborne polyurethane resin, the dispersity of ATO is 30% in the described nano ATO slurry, and described linking agent is KH570, and described uv-absorbing agent is UV-329.
3, the water-borne heat-insulating self-cleaning nona coating that is used for glass according to claim 1 is characterized in that described coating is formed and weight part is as follows:
Waterborne polyurethane resin 45～55,
Nano ATO slurry 5～10,
KH570 0.1～0.8，
UV-329 0.1～0.5，
Ethanol 5～10.
4, the preparation method who is used for the water-borne heat-insulating self-cleaning nona coating of glass according to claim 1 is characterized in that described preparation method may further comprise the steps:
Be 30% powders A TO Ball milling 48 hours in the KH570 aqueous solution with solid content, wherein dispersion agent KH570 accounts for 0.5%～2% of powders A TO weight,
The slurry that more than makes is regulated pH value to 7～8 and is made the nano ATO slurry,
Mix adding macromolecule resin, linking agent, uv-absorbing agent and ethanol in the nano ATO slurry.
5, the preparation method who is used for the water-borne heat-insulating self-cleaning nona coating of glass according to claim 4 is characterized in that using in the described mechanical milling process agate as ball-milling additive.
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