CN1232599C - Nano transparent heat insulated composite coating material and equipment for testing effect of heat insulation for the material - Google Patents

Nano transparent heat insulated composite coating material and equipment for testing effect of heat insulation for the material Download PDF

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Publication number
CN1232599C
CN1232599C CN 200410014672 CN200410014672A CN1232599C CN 1232599 C CN1232599 C CN 1232599C CN 200410014672 CN200410014672 CN 200410014672 CN 200410014672 A CN200410014672 A CN 200410014672A CN 1232599 C CN1232599 C CN 1232599C
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China
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nano
water
wet pulp
resin
composite coating
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Expired - Fee Related
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CN 200410014672
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CN1563231A (en
Inventor
赵石林
韦亚兵
许仲梓
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The present invention relates to a nanometer transparent heat-insulating composite paint which can be applied to glass surfaces, transparent resin surfaces, metal surfaces and cement surfaces, and a device for testing the heat insulation effect of the paint. The paint is composed of polyurethane resin, polysiloxane resin, polyacrylic resin, nanometer tin/indium oxide (ITO) powder, nanometer tin/antimony oxide powder, additives a diluting agent, etc. The paint has the characteristics of strong adhesive force, transparence, infrared ray shielding, heat insulation, etc., and is particularly suitable for automobile glass and building glass.

Description

Nano transparent heat-insulation composite coating
Technical field:
The present invention relates to a kind of composite coating, relate in particular to a kind of glass that is applied to, resin, the nano transparent heat-insulation composite coating of metal and cement surface.
Background technology:
Study a kind of glass that is applied to, resin, metal and cement surface thermal insulating coating are the targets that domestic and international coating industry is pursued always with the effect of heat insulation that strengthens in automobile or the house.Existing for this reason patent application is that 99114454.6 Chinese patent " radioresistant insulating water paint " and application number are 03111863.1 Chinese patent " waterborne epoxy modified acrylic heat-reflecting insulating coating " as application number.They all are to adopt polymkeric substance and the compound thermal insulating coating of making of mineral filler, and what use in this coating composition is common inorganic heat-insulating powder, do not have a transparency though the coating of making has thermal insulation.
World patent WO0009446 (transparent conductive nano composite coating and preparation method) has told about a kind of preparation method of transparent conductive nano composite coating.This coating is the ITO nano-powder to be scattered in to make the ITO water slurry in the water earlier, mixes with membrane-forming agent such as polyvinyl alcohol and finally makes a kind of transparent conductive nano composite coating, and its coating property only has the transparency and electroconductibility, and not seeing has thermal insulation.World patent WO9919267 (thermal insulating coating) adopts the cholesterol class of energy reflected infrared to make thermofin, though have the transparency, its effect of heat insulation is limited.In addition, its sensitivity of effect of heat insulation determinator designed in the previous patent is limited, also brings difficulty for the sign of coating effect of heat insulation.
Summary of the invention:
Technical problem to be solved by this invention is: though though overcome in the prior art disclosed coating and thermal insulation is arranged and do not have the transparency or the transparency is arranged and the weak point of heat-proof quality difference, a kind of be applied to glass with the better transparency and thermal insulation has been proposed, resin, the nano composite dope of metal and cement surface.
Technical scheme of the present invention is: a kind of nano transparent heat-insulation composite coating, and composition and weight part are as follows:
Macromolecule resin 30-65
Nano heat-insulating powder wet pulp 10-25
Coatings additive(s) 1-10
Thinner 15-60
Wherein said macromolecule resin is waterborne polyurethane resin, water-borne acrylic resin or polyorganosiloxane resin; Nano heat-insulating powder wet pulp be nano antimony tin oxide (ATO) water/pure wet pulp of particle size range 10-60nm, solid content 5-15% or solid content in the 10-20% scope, its particle diameter is in nano-indium stannum oxide (ITO) water/pure wet pulp of 10-60nm scope; Coatings additive(s) comprises a kind of of dispersion agent, flow agent, defoamer, film coalescence aid and thickening material at least, dispersion agent is a kind of polymer-type anionic dispersing agents, flow agent is acrylic copolymer or the polyether-modified polysiloxane of non-response type, defoamer is that non-silicone contains hydrophobic particles mineral oil mixture or modified polyorganosiloxane, film coalescence aid is ethylene glycol monobutyl ether/dipropylene glycol butyl ether mixture, thickening material is the water-soluble dispersion liquid of a kind of hydroxyl acrylic, thinner is water and/or alcohols, does not contain other organic solvents.Polyorganosiloxane resin in the macromolecule resin can be bought also and can make by oneself, preferred homemade polyorganosiloxane resin, its method for making is: adopting weight part is that 25 parts of siloxanyl monomers and weight part are 12 parts of tetraethoxys and 3 parts of toxilic acids, at weight part is to be that 56 parts of silicon sol and 1 part of Resins, epoxy carry out in-situ polymerization with weight part in 40 parts of alcohol solvents, obtains a kind of transparent clarifying high-molecular resin solution.Wherein nano heat-insulating powder wet pulp is tin-antiomony oxide (ATO) water-based wet pulp, can buy also and can make by oneself, preferred homemade tin-antiomony oxide (ATO) water-based wet pulp, its method for making is: with weight part is that 5-20 part nano antimony tin oxide (ATO), weight part are 30-50 part deionized water, weight part is 30-50 part alcohol, weight part is that 1-3 part dispersion agent and other auxiliary agent mix, on high speed dispersor, ball mill, disperse certain hour, can obtain nano antimony tin oxide (ATO) the water-based wet pulp of a kind of particle size range 10-60nm, solid content 5-15%.Nano-indium stannum oxide wherein (ITO) wet pulp, be a kind of ITO water/pure slurry, can buy also and can make by oneself, its method for making of preferred homemade tin indium oxide (ITO) water-based wet pulp is: with weight part is that 5-20 part nano-indium stannum oxide (ITO), weight part are 30-50 part deionized water, weight part is 30-50 part alcohol, weight part is that 1-3 part dispersion agent and other auxiliary agent mix, on high speed dispersor, ball mill, disperse certain hour, can obtain a kind of solid part in the 10-20% scope, its particle diameter is in the translucent homogeneous wet pulp of nano-indium stannum oxide (ITO) of 10-60nm scope.The preferred a kind of nano tin indium oxide ITO transparent heat-insulation composite coating of the present invention, its composition and weight part are as follows:
Polyorganosiloxane resin 30-65
Nano-indium stannum oxide (ITO) water/pure wet pulp 10-20
Coatings additive(s) 1-5
Thinner 15-60
Nano-indium stannum oxide wherein (ITO) water/pure wet pulp is in the solid content 10-20% scope, its particle diameter is in the 10-60nm scope, coatings additive(s) comprises the polyether-modified polysiloxane flow agent of non-response type, modified polyorganosiloxane defoamer and a kind of polymer-type anionic dispersing agents, and thinner is water and/or alcohols; The present invention is also preferred a kind of nano antimony tin oxide (ATO) transparent heat-insulation composite coating, its composition and weight ratio are as follows:
Waterborne polyurethane resin or water-borne acrylic resin 50-65
Nano antimony tin oxide (ATO) water/pure wet pulp 10-25
Coatings additive(s) 1-10
Thinner 15-20
Nano antimony tin oxide wherein (ATO) water/pure wet pulp particle size range 10-60nm, solid content 5-15%; Coatings additive(s) wherein comprises a kind of of thickening material, film coalescence aid, flow agent, defoamer at least, and thickening material is the water-soluble dispersion liquid of a kind of hydroxyl acrylic; Film coalescence aid is ethylene glycol monobutyl ether/dipropylene glycol butyl ether mixture; Flow agent is an acrylic copolymer, and defoamer is that non-silicone contains the hydrophobic particles mineral oil mixture, and thinner is a water.
Nano transparent heat-insulation composite coating preparation technology of the present invention is as follows: makes nano-ITO or nano ATO wet pulp earlier, adds the aqueous high molecular resin by prescription again, and coatings additive(s), thinner mixes and promptly makes nano transparent heat-insulation composite coating.
The present invention adopts homemade test set in order to measure the effect of heat insulation of prepared nano transparent heat-insulation composite coating, test set as shown in Figure 3, wherein tub is of a size of 15cm * 14.5cm * 7.5cm, and the tub wall thickness is 1.1cm, and the thickness of foam thermal insulation layer is 1.5cm.It is made up of lighting source 1, sample 2, tub 4, foam thermal insulation layer 3, iron plate 5, baffle plate 6, mercurythermometer 7, thermocouple temperature measurement instrument 8, the temperature probe of thermocouple temperature measurement instrument 8 is close to the center position of iron plate 5 lower surfaces, mercurythermometer 7 is installed above base plate, baffle plate 6 is installed in the mercury bulb top, and the tub bottom is placed one and scribbled pitch-dark iron plate to increase the susceptibility of heat effect.At distance base plate 2cm place one mercurythermometer is installed and is measured the tub Inside Air Temperature, baffle plate is installed to prevent the light direct projection in the mercury bulb top.Sample is the thick simple glass of 3mm that scribbles nano transparent heat-insulation composite coating, and it is tightly covered on the wooden case, and coated surface upwards.Lighting source adopts 250w infrared lamp or 500w tungsten-iodine lamp.Infrared lamp is 30cm apart from height of specimen, and tungsten-iodine lamp is 40cm apart from height of specimen.Room temperature is constant to remain on 21 ℃ to guarantee the repeatability of experiment.
Beneficial effect of the present invention is:
With reference to the countries concerned's standard, the fundamental property of nano transparent insulating coating of the present invention is measured, the result proves that the formed coating hardness of coating of the present invention can reach the H level; Sticking power is 3 grades; Water tolerance, thermotolerance is good; Light transmission be in visible-range average transmittances greater than 80%, for the ultrared shielding rate of 1000-2500nm wavelength more than 75%; If make comparisons with the thermal insulation of blank glass, the glass that then scribbles nano transparent insulating coating can make the temperature in the testing cassete reduce by 5 degrees centigrade, so nano transparent heat-insulation composite coating of the present invention has strong adhesion, and is transparent, shielding infrared rays and characteristic such as heat insulation.
Description of drawings:
Fig. 1 is the influence figure of different tin indium oxide consumptions to the spectrum perviousness of filming.
Fig. 2 scribbles the temperature difference of air and the interior air of tub of blank glass in the tub of glass (3# sample) of nano transparent insulating coating down for tungsten-iodine lamp irradiation.
Fig. 3 is the effect of heat insulation test set.
Embodiment:
Describe the present invention with relevant figure, table below in conjunction with embodiment.But the invention is not restricted to given example.The nanometer wet pulp preparation technology of coating of the present invention is: with weight part is 5-20 part nano-indium stannum oxide (ITO) or tin-antiomony oxide (ATO), weight part is 30-50 part deionized water, weight part is 30-50 part alcohol, weight part is that 1-3 part dispersion agent and other auxiliary agent mix, at high speed dispersor, disperse certain hour on the ball mill, or on ultrasonic generator, disperse, make particle size range 10-60nm, the nano antimony tin oxide of solid content 5-15% (ATO) water-based wet pulp or solid part are in the 10-20% scope, its particle diameter is in nano-indium stannum oxide (ITO) wet pulp of 10-60nm scope.
It is as follows that the present invention provides an embodiment of nano-ITO transparent heat-insulation composite coating:
(1) polyorganosiloxane resin prescription and preparation
Component Siloxanes KH560 Tetraethoxy TEOS Toxilic acid Ethanol Resins, epoxy E-51 Silicon sol
Consumption 25 12 3 40 1 56
KH560, TEOS are placed in the three-necked flask, add toxilic acid, ethanol stirring half a minute, under agitation condition, slowly drip silicon sol, add Resins, epoxy E-51 after finishing.React and got transparent clarification resin solution in one hour.After one night of ageing, sealing is placed stand-by.
(2) transparent heat insulating dope prescription and preparation
Component Embodiment
1 2 3 4 5
The nano-ITO wet pulp 15 16 17 18 20
Ethanol 20 19 18 17 15
Water 15 15 15 15 15
Dispersion agent 1 1 1 1 1
Polyorganosiloxane resin 40 38 35 32 30
Flow agent 1 1 2 2 2
Defoamer 1 1 1 1 1
Propyl carbinol 8 10 12 15 17
Produce nano-indium stannum oxide (ITO) wet pulp earlier by prescription, under magnetic agitation, slowly add a certain amount of polyorganosiloxane resin, add an amount of thinner propyl carbinol and other proper assistant then, leave standstill 30min behind the continuation stirring 10min and get final product.
It is as follows that the present invention provides embodiment of nano ATO transparent heat-insulation composite coating:
Component Embodiment
6 7 8 9 10 11
Aqueous polyurethane (solid content 36.8%) 55 60.6 65
Water-based PU acrylic resin (40%) (SV-TN7072) 55 60 65
Nano ATO wet pulp (solid content 14.4%) 25 20.2 15 25 20 15
Thickening material WT-105A 1 0.6 0.5 1 0.5 0.5
Film coalescence aid (ethylene glycol monobutyl ether/dipropylene glycol butyl ether) 3 3 4 3 4 4
Flow agent 0.5 0.3 0.2 0.5 0.3 0.3
Defoamer 0.5 0.3 0.3 0.5 0.2 0.2
Water 15 15 15 15 15 15
Not only have transparent and thermal insulation by the formed coating of nano-ITO transparent heat-insulation composite coating of the present invention, also have good infrared shielding.Its transparency and thermal insulation such as Fig. 1, shown in Figure 2.The transparency of the formed coating of nano ATO transparent heat-insulation composite coating and thermal insulation and ITO transparent heat-insulation composite coating are approximate.
With reference to the countries concerned's standard, the fundamental property of nano transparent insulating coating to be measured, test result is as shown in table 1.
Fig. 1 be in filming different nano-indium stannum oxide consumptions to the influence of spectral transmittance, be respectively the spectrum that sees through of 1#~6# sample from inside to outside with same thickness, wherein the consumption of nano-indium stannum oxide reduces successively, wherein the content of nano-indium stannum oxide is 0.72 in pigment volume concentration (PVC) PVC successively, 0.53,0.34,0.22,0.13,0.07.As can be seen from the figure, six samples all have higher transmittance (80~90%) at visible region, and the tin indium oxide consumption improves, and visible light transmissivity slightly descends, but minimumly still are not less than 80%.To the blocking capability in infrared light district then along with the minimizing of tin indium oxide consumption has obvious reduction.Wherein 1#~3# (pigment volume concentration (PVC) PVC=0.72~0.34) for the ultrared shielding rate of 1000-2500nm wavelength more than 75%.
Fig. 2 scribbles the temperature difference of air and blank glass in glass (3# sample) box of nano transparent insulating coating for adopting Fig. 3 device under the tungsten-iodine lamp irradiation.When reaching balance, if make comparisons with the thermal insulation of blank glass, the glass that then scribbles nano transparent insulating coating can make the temperature in the testing cassete reduce by 5 degrees centigrade.
Fig. 3 is homemade effect of heat insulation test set, in order to measure the effect of heat insulation of prepared nano transparent insulating coating.As shown in the figure.Wherein tub is of a size of 15cm * 14.5cm * 7.5cm, and the tub wall thickness is 1.1cm.The thickness of foam thermal insulation layer is 1.5cm.The tub bottom is placed one and is scribbled pitch-dark iron plate to increase the susceptibility of heat effect, the temperature probe of thermocouple temperature measurement instrument is close to the center position of iron plate lower surface.At distance base plate 2cm place one mercurythermometer is installed and is measured the tub Inside Air Temperature, baffle plate is installed to prevent the light direct projection in the mercury bulb top.Sample is the thick simple glass of 3mm that scribbles nano transparent insulating coating, and it is tightly covered on the wooden case, and coated surface upwards.Lighting source adopts 250w infrared lamp or 500w tungsten-iodine lamp.Infrared lamp is 30cm apart from height of specimen, and tungsten-iodine lamp is 40cm apart from height of specimen.Room temperature is constant to remain on 21 ℃ to guarantee the repeatability of experiment.
Table 1 transparent heat insulating dope fundamental property assay
Interventions Requested Assay Reference standard
Paint film color and outward appearance The little indigo plant of paint film is transparent, and is smooth, bright GB 1729-79
Hardness (pencil) H GB/T 6739-1996
Sticking power, level (drawing the circle method) 3 GB/T 1720-79
Wear resistance, 200r/750g 1.0mg GB 1768-79
Shock strength, cm 50 GB/T 1732-93
Snappiness, mm 2 GB/T 1731-93
Water tolerance, water immersion test 24h No considerable change GB/T 1733-93
Thermotolerance Under 100 ± 2 ℃, paint film does not have bubbling, wrinkling, cracking, variable color behind the baking 3h GB 1735-79

Claims (5)

1, a kind of nano transparent heat-insulation composite coating is characterized in that composition and weight part are as follows:
Macromolecule resin 30-65
Nano heat-insulating powder wet pulp 10-25
Coatings additive(s) 1-10
Thinner 15-60
Wherein said macromolecule resin is waterborne polyurethane resin, water-borne acrylic resin or polyorganosiloxane resin; Nano antimony tin oxide water/pure wet pulp that wherein said nano heat-insulating powder wet pulp is particle size range 10-60nm, solid content 5-15% or solid content in the 10-20% scope, its particle diameter is in the nano-indium stannum oxide water/pure wet pulp of 10-60nm scope.
2, nano transparent heat-insulation composite coating according to claim 1, coatings additive(s) wherein comprises a kind of of dispersion agent, flow agent, defoamer, film coalescence aid and thickening material at least, dispersion agent is a kind of polymer-type anionic dispersing agents, flow agent is acrylic copolymer or the polyether-modified polysiloxane of non-response type, defoamer is that non-silicone contains hydrophobic particles mineral oil mixture or modified polyorganosiloxane, film coalescence aid is ethylene glycol monobutyl ether/dipropylene glycol butyl ether mixture, and thickening material is the water-soluble dispersion liquid of a kind of hydroxyl acrylic.
3, nano transparent heat-insulation composite coating according to claim 1, thinner are water and/or alcohols, do not contain other organic solvents.
4, nano transparent heat-insulation composite coating according to claim 1 is characterized in that composition and weight part are as follows:
Polyorganosiloxane resin 30-65
Nano-indium stannum oxide water/pure wet pulp 10-20
Coatings additive(s) 1-5
Thinner 15-60
Wherein the particle size range of nano-indium stannum oxide water/pure wet pulp is in 10-60nm, solid content is 10-20%, coatings additive(s) comprises the polyether-modified polysiloxane flow agent of non-response type, modified polyorganosiloxane defoamer and a kind of polymer-type anionic dispersing agents, and thinner is water and/or alcohols.
5, nano transparent heat-insulation composite coating according to claim 1 is characterized in that composition and weight part are as follows:
Waterborne polyurethane resin or water-borne acrylic resin 50-65
Nano antimony tin oxide water/pure wet pulp 10-25
Coatings additive(s) 1-10
Thinner 15-20
Nano antimony tin oxide water wherein/pure wet pulp particle size range 10-60nm, solid content 5-15%; Coatings additive(s) wherein comprises a kind of of thickening material, film coalescence aid, flow agent, defoamer at least, and thickening material is the water-soluble dispersion liquid of a kind of hydroxyl acrylic; Film coalescence aid is ethylene glycol monobutyl ether/dipropylene glycol butyl ether mixture; Flow agent is an acrylic copolymer, and defoamer is that non-silicone contains the hydrophobic particles mineral oil mixture, and thinner is a water.
CN 200410014672 2004-04-16 2004-04-16 Nano transparent heat insulated composite coating material and equipment for testing effect of heat insulation for the material Expired - Fee Related CN1232599C (en)

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CN108504218A (en) * 2018-04-23 2018-09-07 合肥协耀玻璃制品有限公司 A kind of self-cleaning coating and preparation method thereof for glass curtain wall
CN109207000A (en) * 2018-06-07 2019-01-15 太仓萃励新能源科技有限公司 A kind of preparation method of nano-negative ion clear dope
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