CN106380977A - Hydrophobic heat-insulation coating and preparation method therof - Google Patents

Hydrophobic heat-insulation coating and preparation method therof Download PDF

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Publication number
CN106380977A
CN106380977A CN201610795198.6A CN201610795198A CN106380977A CN 106380977 A CN106380977 A CN 106380977A CN 201610795198 A CN201610795198 A CN 201610795198A CN 106380977 A CN106380977 A CN 106380977A
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coating
agent
heat
water
insulating moulding
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梁敏锐
李宗强
谭铭卓
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GUANGDONG WEALTH ENVIRONMENTAL PROTECTION Co Ltd
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GUANGDONG WEALTH ENVIRONMENTAL PROTECTION Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04Homopolymers or copolymers of monomers containing silicon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/3045Treatment with inorganic compounds
    • C09C1/3054Coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06Treatment with inorganic compounds
    • C09C3/063Coating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Abstract

A hydrophobic heat-insulation coating comprises, by weight, 35-45% of an emulsion, 8-11% of a pigment, 4-7% of a heat-insulation functional filler, 10-12% of a body filler, 0.4-0.5% of a wetting agent, 1-1.5% of a dispersant, 0.5-0.6% of an antifoaming agent, 0.7-0.8% of a thickener, 1-2% of a film forming assistant, 7-10% of a hydrophobic agent, 0.3-2% of other assistants, and the balance of water. The heat-insulation functional coating prepared through coating hollow glass beads with TiO2 has the advantages of large heat resistance, low conductive coefficient, high photo-thermal reflectivity, effective reduction of radiative heat transfer and convective heat transfer and heat insulation effect, and nanometer anatase titanium dioxide has photocatalysis characteristic, effectively degrades formaldehyde, and plays a great role in solving of environment pollution and energy waste. The coating integrates the respective advantages of an aqueous coating, a hydrophobic coating and a heat insulation coating, and is a green and environmentally-friendly coating.

Description

A kind of hydrophobic insulating moulding coating and preparation method thereof
Technical field
The invention belongs to technical field of coatings is and in particular to a kind of new hydrophobic insulating moulding coating and preparation method thereof.
Background technology
With the consumption of available energy, energy-saving material causes the extensive concern of the mankind.Insulating moulding coating is to send out in recent years A kind of new energy-saving material that exhibition is got up, it passes through the energy of reflected sunlight effectively, reduces body surface to solar radiation The absorption of energy, thus play the effect of heat-insulation and heat-preservation.Insulating moulding coating, as a kind of functional coating, can reduce the table of object Face temperature, stop conduction of heat, improve working environment, improve safety.Show it in photocatalytic degradation first with in-depth study Aldehyde aspect also has certain effect.
Water paint is with emulsion etc. as adhesive, adds coalescents, thickening agent, dispersant, defoamer, color stuffing etc. Multiple material, a kind of coating that is agitated, grinding, modulate.It is nonpoisonous and tasteless with water as disperse medium, does not pollute ring Border, is a kind of green environmental friendly coatingses.
The resistance to water of common exterior wall latex paint, weather resisteant are not enough, are particularly affected by rainwater, sewage larger, greatly damage Do harm to the attractive in appearance of building.Using silicone acrylic emulsion, hydrophobic effect can be reached, the water-repelling agent of development is added in emulsion paint, The surface energy of paint film can be reduced further and enlarged surface roughness improves its surface hydrophobic, prevent moisture penetration, strengthen breast The stain resistance of shellac varnish.
The neat advantage of water paint, hydrophobic coating and three kinds of coating of insulating moulding coating of water-based hydrophobic heat insulating function coating collection, Possess good hydrophobic heat-proof quality, and can solve the problem that the problem of environmental pollution, energy waste, be a kind of green environmental friendly coatingses. With energy-saving and emission-reduction, the becoming increasingly conspicuous of environmental protection problem, water paint, particularly water-soluble multifunctional coating, are following coating It is a big focus in development.
Content of the invention
It is an object of the invention to provide a kind of new hydrophobic insulating moulding coating and preparation method thereof.
To achieve these goals, the present invention adopts following technical scheme:
A kind of hydrophobic insulating moulding coating, including following raw material by weight:Emulsion 35-45%, pigment 8-11%, heat-insulated Functional stuffing 4-7%, body constitution filler 10-12%, wetting agent 0.4-0.5%, dispersant 1-1.5%, defoamer 0.5-0.6%, Thickening agent 0.7-0.8%, coalescents 1-2%, water-repelling agent 7-10%, other auxiliary agents 0.3-2%, balance of distilled water.
Preferably, described emulsion is one or more of pure-acrylic emulsion, styrene-acrylic emulsion and silicone acrylic emulsion.Excellent further Selection of land, described emulsion is silicone acrylic emulsion.
Used in emulsion paint, Chinese white mainly has titanium dioxide, lithopone, zinc oxide powder etc..Wherein titanium dioxide application For extensive, it is a kind of preferable Chinese white, chemical substances, the organic solvent of majority can be resisted, heat-resisting, most important is with height Refractive index, strong covering power.Secondly, there is durability.It is widely used in coating, plastics, papermaking, ink, chemical fibre and cosmetic Product.
In coating, conventional titanium dioxide mainly has two kinds of rutile, anatase.There is larger difference between the two, such as Table 1 below:
Table 1 rutile and anatase performance comparison
Pigment coefficient of refraction is higher, and the reflectance of film is also higher, and under the same terms, film coated surface temperature is also lower, can Improve the effect of heat insulation of coating.Wherein Rutile type titanium dioxide refractive index is higher and network structure is tight.Rutile-type is in height (shorter wavelength) radiation energy can be absorbed compared with anatase titanium dioxide greatly, in other words, for Rutile type titanium dioxide, there is very strong lethality UV- wavelength period in (350-400nm), it will be well below anatase thpe white powder, in this situation to the reflectance of ultraviolet Under, it will much less to ultraviolet light to be shared with the film forming matter of surrounding, resin etc., then the making of these Organic substances Just long with the life-span, in other words, the why weatherability of the usually said Rutile type titanium dioxide reason better than anatase titanium dioxide It is located, comprehensive analysis, Rutile type titanium dioxide is better than anatase titanium dioxide overall performance.
Preferably, described filler is ground calcium carbonate, precipitated calcium carbonate, Pulvis Talci, wollastonite in powder, mica powder, kaolinite One or more of soil, blanc fixe, bentonite, sierozem power, superfine alumina silicate, silica flour.
Used in emulsion paint, packing variety is a lot, and conventional has ground calcium carbonate, precipitated calcium carbonate, Pulvis Talci, silicon ash Stone powder, sericite in powder (mica powder), Kaolin, blanc fixe, bentonite, sierozem power, superfine alumina silicate, silica flour etc..No Congener filler, its proportion, density, oil absorption, granular size, distribution of particles and filler grain surface treatment etc. are not With, and ultraviolet resistance is degraded, acid rain resistant erosiveness has differences, therefore widely different at aspects such as guarantor's light, unfadings.Under Table 2 is the main performance feature of customary filler:
Table 2 customary filler varieties and characteristicses and key property
The present invention selects ground calcium carbonate (1000 mesh), kieselguhr (2500 mesh), Pulvis Talci (2500 mesh) and Kaolin (2500 mesh) is as filler.
Because a kind of biochemical deposit rock that kieselguhr is made up of the siliceous cell of diatom, quality is soft, porous and Gently, heat conductivity is 0.17w/m K, has good heat-insulating property.
The filler refractive index such as kieselguhr and Pulvis Talci is at a fairly low, not direct scattered light, but can improve two as extender pigment The scattering efficiency of titanium oxide, and exist compared with intense radiation heat-sinking capability in " atmospheric window " wave band (8~13 μm).Using diatom Soil and Pulvis Talci auxiliary titanium dioxide prepare insulating moulding coating, have excellent heat-proof quality, and product cost is relatively low.
Kaolinite soil property is soft, has excellent suspension, is easily dispersed in water.Most part of kaolin is all hexagon lamellar knot Structure, have containing unformed flakelike powder, have viscoplasticity, oil content during moistening, prevent pigment precipitate, also can make the screening of emulsion paint Gai Li, the stability of viscosity are improved.
Ground calcium carbonate is cheap, it is possible to decrease the cost of product.
Preferably, described thickening agent is hydroxyethyl cellulose (as Qp-30000), alkali swollen thickener (as TA-710) One or more of with association type polyurethane thickener (as RM-5000).In coating preparation early stage, can be previously added appropriate Cellulose, through the dispersed denseness that can greatly increase system of low speed, can greatly improve color stuffing dispersive process Cutting degree, contribute to color stuffing obtain at short notice fully dispersed.In coating preparation later stage adjusting coating viscosity, permissible Add alkali swollen thickener, with the viscosity of adjusting coating and levelability can be improved.
In coating, dispersant used has many kinds, in order to cost-effective, in water paint, generally will not use more expensive Dispersant, conventional can solve the dispersant flocculating.Advantage is:Good to color stuffing color developing, vividness is high, good luster.But In pure emulsion system, then preferably select and strengthen the dispersant that electric charge repels each other, such as electric neutrality amine salt, the dispersant of polycarboxylic acid salt, Its wettability, penetration are very strong.
Polycarboxylate, has excellent dispersibility to inorganic pigment, and after storage, mill base change is little, good wettability and low Foaming characteristic, good color developing, low-consuming.The present invention selects the dispersant SN-5040 of polycarboxylic acid salt.
Described wetting agent is NPE.
The present invention selects TiO2Coated hollow glass bead is function insulating moulding coating.
The heat conductivity of the coating containing hollow glass micropearl is slightly above conventional organic and unorganic glass microballon, is a bulb Shape hollow material, applies and can improve corrosion resistance, weatherability and the heat-proof quality of coating and the heat conduction of insulation material in coating Coefficient, with the increase of hollow glass micropearl content, heat conductivity is lower, and hollow glass micropearl can also improve coating simultaneously Reflectance, can be using hollow glass micropearl as filler, and the bottom using solar heat reflection paint coating (is connect with coated article Touch) in.
Hollow glass micropearl is applied in coating, after coating is dried, hollow beads close-packed arrays get up, and form one Complete hollow sealing coat, not only has good effect of heat insulation, also has excellent soundproof effect.But, hollow glass is micro- Pearl true density is only 250~400kg/m3, it is directly added in aqueous coating system, floated over coating on hollow glass micropearl is easy Surface forms conjunctiva and reduces the uniformity of coating.Therefore, realize it in painting by hollow glass micropearl surface is carried out with modification Dispersed in material system, it is currently to realize one of effective ways of hollow glass micropearl application and its functionalization.
TiO2It is most widely used a kind of important pigment in coating, hardly react with other materials under its room temperature, no It is dissolved in water, fat, is also insoluble in acid, alkali, the excellent weatherability of coating and glossiness can be given.Early in the nineties in last century, Scientist just has been proven that nano-TiO2There is photocatalysis characteristic, that is, under light action, nano-TiO2Can occur continuously to aoxidize Reduction reaction, final organic pollution is CO by solving2And water.
In cenosphere surface attached last layer TiO2Thin film, so can improve the whiteness of hollow glass micropearl.In addition TiO2 Thin film is high to the reflectivity of sunlight, can play reflected sunlight, this makes it possible to increase the usage amount of hollow glass micropearl, carries Its heat insulation and heat control ability high.
Using butyl titanate as forerunner, butyl titanate has very high chemism to water, and hydrolysis generates TiO2With positive four Butanoic acid.Hydrolysis product is nontoxic, easily removes with calcining through being dried.
From dehydrated alcohol as solvent, because butyl titanate has very high chemism to water, need water content pole Low solvent, dehydrated alcohol is in organic solvent now using the widest and convenient sources, low price, readily volatilized, nontoxic.
Glacial acetic acid does inhibitor, adds glacial acetic acid to adjust the pH of hydrolysis, can suppress the hydrolysis speed of butyl titanate Degree, makes reaction slowly carry out, and generates uniform colloidal sol.
Described TiO2Coated hollow glass bead is prepared by following steps:
(1) measure 25-30ml dehydrated alcohol and 8-10ml butyl titanate is added in there-necked flask, in temperature 26-30 DEG C Under the conditions of, turned with rotating speed 1800-1900/min stirring 8-10min is to uniform;
(2) add 2-3ml glacial acetic acid in there-necked flask, stir, add 8-10ml cenosphere, in temperature Under the conditions of 26-30 DEG C ,/min is turned with rotating speed 1800-1900, stirring 18-20min is to uniform;
(3) it is added in separatory funnel after 25-30ml dehydrated alcohol and 3-5ml water being mixed in beaker, in temperature 26- Under the conditions of 30 DEG C, it is slowly dropped in there-necked flask, time for adding is 15-20min;
(4)/min, stirring reaction 1h are turned with rotating speed 1800-1900;
(5), after standing 24-48h, product is put in 90-100 DEG C of baking oven and dries;
(6) after drying, product is placed in temperature in calcining furnace and is 400-600 DEG C, calcine 3 hours, obtain final product.
The present invention adopts sol-gal process to prepare TiO2Coated hollow glass bead, the preparation of colloidal sol is the key of technology, The quality of colloidal sol directly influences the performance of final resulting materials, and the colloidal sol therefore how preparing satisfaction requirement is research emphasis.
1) amount of water:The addition of water be less than stoichiometrically consumption required for relation when, with the increase of rate of water added, The time of colloidal sol can be gradually shortened, and when exceeding stoichiometric relationship aequum, aerosol time can gradually increase again, if this is because When adding the water yield few, hydrolysis of alkoxide speed relatively extends aerosol time slowly;If amount of water is more than stoichiometry, solution is to dilute Release, solution viscosity declines and makes plastic difficult, when stoichiometrically adding, the quality of plastic is good, and gelation time is relatively short.
2) rate of addition of water:Water hydrolysis solidification in the easy absorption air of alkoxide, therefore in Deca alkoxide solution, other Observe drop rate in the case of factor is consistent, find that drop rate significantly affects aerosol time, drop rate is faster, gelation rate Also fast, but speed easily causes that local hydrolyzes too fast soon and polymerization and gel generates precipitation, a part of sol solutionses hydrolyze simultaneously Finally result in and cannot obtain homogeneous gel, so uniform stirring also should be aided with reaction, to ensure to obtain homogeneous gel.
3) catalyst:, as catalyst, its catalytic mechanism is different for soda acid, thus the hydrolytie polycondensation to same system, often The different condensation polymer of generation structure, form.Research shows, the polycondensation reaction speed of acid catalytic systems is much larger than hydrolysis, water Solution is by H3The electrophilic mechanism of O+ causes polycondensation reaction to have started to before complete hydrolysis, thus the degree of cross linking of condensation polymer is low, gained Xerogel is transparent, compact structure;The hydrolysis of base catalysiss system are to be caused by the nucleophilic displacement of fluorine of OH-, and hydrolysis rate is more than Nucleophilic speed, hydrolysis is relatively more complete, and the gel of formation, mainly by polycondensation reaction control, forms macromolecule polyalcohol, has higher The degree of cross linking, the xerogel structure of gained is loose, translucent or opaque.The present invention adopts glacial acetic acid as catalyst.
4) hydrolysis temperature:Improve the temperature alkoxide favourable, low to hydrolysing activity to the hydrolysis of alkoxide, often carry out under heating Hydrolysis, to shorten the time needed for colloidal sol preparation and gelling;But hydrolysis temperature is too high, will there is the hydrolytic polymerization of multi-products Reaction, generates not volatile organic matter, affects gelling properties.Sometimes hydrolysis temperature also can affect the phase change of hydrolyzate, The stability of impact colloidal sol.Therefore in the case of guaranteeing to generate colloidal sol, take lower temperature as far as possible.The present invention adopts room Warm (28 ± 2 DEG C).
5) digestion time:The colloidal sol of tool mobility forms not flowable gel rubber system by further polycondensation reaction.Warp In ageing, the further agglomeration of polymer becomes granule submanifold to the sol solution that polycondensation reaction is formed, and they mutually collide Connect into big Particle Cluster, meanwhile, liquid phase is wrapped in solid skeleton and loses flowing, form gel.Ageing forms in gel process, Ostward ripening can occur, that is, sized particles cause the increase of mean diameter because of the difference of dissolubility.Digestion time is too short, Particle size is uneven on the contrary;Overlong time, particle growth, reunion, be difficult formed hyperfine structure it can be seen that, digestion time Selection extremely important to the microstructure of product.
6) calcining heat:Due to nano-TiO2Its crystal formation is different at different temperature, the TiO of sol-gal process preparation2Forge Part TiO when burning temperature more than 600 DEG C2Rutile-type is converted into by Detitanium-ore-type, and it is amorphous state that temperature is less than when 300 DEG C. Thus temperature should control at 500 DEG C about.
Further preferably, described TiO2The particle diameter of the hollow glass micropearl of cladding is 150 mesh.
Preferably, described water-repelling agent includes following raw material by weight:Paraffin 2-4 part, silicone oil 3-6 part, cloudy from Sub- surfactant 1-2 part, stearic acid 2-5 part, triethanolamine 2-5 part, emulsifying agent 2-5 part, water 30-50 part.
Preferably, described water-repelling agent includes following raw material by weight:2 parts of paraffin, 4 parts of silicone oil, dodecyl 1 part of benzene sulfonic acid sodium salt, 3 parts of stearic acid, 3 parts of triethanolamine, 3 parts of tween 85,30 parts of water.
It is further preferred that the preparation method of above-mentioned water-repelling agent, comprise the following steps:
(1) add water in reaction vessel, be heated to 70-90 DEG C, with mixing speed as 100-300r/min, stirring adds Enter anion surfactant, continue to be stirred until homogeneous;
(2) at 70-90 DEG C, add paraffin and silicone oil, with mixing speed as 100-300r/min, be stirred continuously to equal Even;
(3) it is cooled to 50-70 DEG C, sequentially add stearic acid, triethanolamine, emulsifying agent, with mixing speed as 500-700r/ Min, after insulated and stirred reaction 20-40min, cooling, obtain final product.
Preferably, described defoamer is silicone defoamer and mineral oil defoaming agent by weight for 1:1 compounds.
Preferably, described coalescents are benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol, Oleum Terebinthinae, alcohol ester-12 One or more of.It is further preferred that described coalescents are alcohol ester-12.The basic function of coalescents is to reduce Emulsion and the minimum film formation temperature of emulsion paint, enable emulsion paint application at a lower temperature.Preferably coalescents should meet with Lower requirement:
1. the vitrification point of polymer can be reduced, and have good intermiscibility, otherwise can affect the gloss appearance of paint film.
Dissolubility in water is little, is easily adsorbed by emulsion particle and has excellent coalescence performance.Faint water solublity, easily By the emulsifying of emulsion paint other component institute.
2. should have suitable evaporation rate, retain in the polymer before film forming, can volatilize completely after film forming.
The selection of coalescents and consumption, single its film-formation result of assessment, and the shelf characteric (viscosity to latex system Change and freeze-thaw stability), wet film performance (levelability, sag resistance and color developing), dry film performance (scrubbing resistance, stain resistant, resistance to Wait) all have an impact.
Alcohol ester-12 (as Texnaol) is that latex is birdsed of the same feather flock together the strong solvent of compound, and hydrolytic stability is very good, thus its Applied widely (can be used for including high ph-values pure third, phenylpropyl alcohol, vinegar third, in the middle of multiple emulsions such as silicon third and polyvinyl acetate), Coalescence performance is high, is a kind of ideal coalescents.Alcohol ester-12 has prominent solvent action, that is, have extremely strong gathering Knot ability.In the case of less consumption, can highly desirable reduce the minimum film formation temperature of emulsion paint, expand and use high glass The emulsion paint of change temperature classes polymer range at different ambient temperatures.Alcohol ester-12 compared with other coalescents, water Dissolubility little it is easy to be adsorbed by latex particle, micelle can be directly contacted with it is easier to swelling to micelle;Its rate of volatilization is low, becomes It is retained in before film in latex lacquer coat, solvent action will not be affected by the volatilization of water, and the seriality of film forming is more preferable;And it has Suitable volatility, vapors away in the short time after emulsion paint film forming completely, does not interfere with hard designed by latex paint formulation Degree and gloss.
Preferably, other auxiliary agents include pH adjusting agent, antistatic agent, hydrophobic slip agent, antirust agent, antifreezing agent, antifungus agent, One or more of antibacterial.
A kind of method preparing above-mentioned new hydrophobic insulating moulding coating, comprises the following steps:
(1) add appropriate distilled water in plastic containers, start dispersion machine ,/min is turned with rotating speed 350-400, low speed stirs Mix, be then slowly added to water-repelling agent, dispersant, wetting agent, thickening agent, defoamer in the following order, then stirring at low speed 4-6 is divided Clock is uniformly dispersed;
(2) it is slowly added to filler ,/min, high-speed stirred are turned with rotating speed 1800-1900, disperses 30-40 minute;
(3)/min stirring is turned with rotating speed 350-400, be slowly added to heat insulating function filler, stir 10-12 minute, dispersion is all Emulsion and other auxiliary agents is added, stirring 20 minutes is so as to mix homogeneously after even;
(4) add remaining distilled water and thickening agent, adjust the viscosity of product, and the pH value of adjusting coating.
The invention has the beneficial effects as follows:With TiO2The compound heat insulating function coating itself that coated hollow glass bead is developed Thermal resistance is big, and electrical conductivity is low, high to the reflectance of photo-thermal, can effectively reduce radiant heat transfer and convection heat transfer' heat-transfer by convection, play heat-insulated guarantor Temperature effect.And nano level anatase titanium dioxide has photocatalysis characteristic, can effective degradation of formaldehyde, dirty to solving environment Contaminate, energy waste has immeasurable effect, is a kind of environmental type coating.
Brief description
Figure 1A is ageing time of repose is the 0 SEM electron-microscope scanning figure arriving 6h product.
Figure 1B is the SEM electron-microscope scanning figure that ageing time of repose 6 arrives 24h product.
Fig. 1 C is the SEM electron-microscope scanning figure that ageing time of repose 24 arrives 72h product.
Fig. 2A is the SEM electron-microscope scanning figure of 200 to 300 DEG C of products of calcining heat.
Fig. 2 B is the SEM electron-microscope scanning figure of 300 to 400 DEG C of products of calcining heat.
Fig. 2 C is the SEM electron-microscope scanning figure of 400 to 600 DEG C of products of calcining heat.
Fig. 2 D is the SEM electron-microscope scanning figure of 600 to 800 DEG C of products of calcining heat.
Fig. 3 is TiO2Coated hollow glass bead preparation technology flow chart.
Fig. 4 is hydrophobic insulating moulding coating preparation technology flow chart.
Specific embodiment
The traditional performance test of coating
(1) covering power (with reference to GB/T1726-79)
Coating covering power refers to colored paint even spread on a surface of an so as to the minimum that background color no longer presents is painted Amount, uses g/m2Represent.The present invention selects spread coating.This method is will to be painted with painting brush uniformly and quickly to brush in black and white lattice glass plate On (100mm × 200mm), till invisible black and white lattice.With Subtraction method, weigh coating weight used, and calculated with following formula Covering power X (in terms of wet paint film) in black and white panel
In formula:W1The cup of paint and the gross weight (g) of painting brush is filled before not brushing;
W2The cup of remaining paint and the gross weight (g) of painting brush is filled after brushing;
Area (the m of S black and white panel japanning2)
(2) abrasion resistance (with reference to GB/T9266-88)
Abrasion resistance refers to paint film under given conditions, when being finally wholly absent through repeatedly cleaning, the number of times being swabbed. In national standard, the concrete method of inspection is:Make the standard test plate (panel) of given size and thickness, put into the washability tester of standard, Instill washing medium, reciprocally clean back and forth, number of times scrubbed in record to instrument automatically simultaneously, when paint film is swabbed completely ( Grinning effect occurs), the data on instrument is washability number of times.
Take the model preparing coating by regulation, be placed on QFS type coating washability analyzer, and both sides are fixed, and make examination Sample is scrubbed by 450g load, simultaneously with soap lye (0.5%) moistening hairbrush.To stipulated number, take off test plate (panel), rinsed with water, see Examine whether paint film has breakage, show-through.
(3) resistance to water (with reference to GB/T9265-88)
The paint film of standard thickness is prepared on the cement asbestos board of given size, constant temperature and humidity maintenance is to requiring 7 day time. Colophonium with 1: 1 and mineral wax mixture edge sealing.2/3 is immersed in distilled water or tap water, after the time that the standard of immersion specifies, Check test plate (panel), have or not loss of gloss, variable color, foaming, wrinkling, the phenomenon such as come off, and dried recovery time, to judge with this to apply The resistance to water of material.
(4) alkali resistance (with reference to GB/T9265-88)
According to the standby test plate (panel) of standard gauge customization on standard-sized cement asbestos board, the test plate (panel) making is used 1: 1 paraffin With rosin blend back cover edge sealing.Then the calcium hydroxide saturated solution for 23 ± 2 DEG C by 2/3 immersion temperature of test plate (panel) area (to add the proportions aqueous slkali well of 0.12g calcium hydroxide to be sufficiently stirred in 100mL distilled water, the pH value of this solution 12-13 should be reached) in.After immersion terminates, take out test plate (panel) water and rinse well, get rid of the globule in plate face, then blotted with filter paper. Observe whether coating surface the phenomenons such as foaming, slight crack, peeling, efflorescence, softening and dissolution immediately.
(5) hardness of paint film
Using the hardness of Portable pencil method durometer test plate (panel), pencil hardness scope is by for 6B--6H.The plate making is put On level table, from the hardest pencil, fix pencil with holder so as to be in 45 degree with sample, nib direction away from Operator, and scratch to away from operator direction.Pencil hardness until scratching paint film is hardness of paint film.
(6) paint film appearance (with reference to GB/T9755-2001)
Visually inspect after dried coating film, as smooth in paint film, uniform, pin-free, no shrinkage cavity, no sag, no obvious brush mark, face Color is inconspicuous with reference colours difference, gloss meets the requirements, that is, be considered as outward appearance qualified.
(7) drying time (with reference to GB/T1728-79)
Coating is referred to as drying time from fluid layer to being completely formed solid paint film this period, and that is, coating is transformed into from sticky Time needed for solid coated film.Two stages can be divided into drying time, i.e. surface drying time (surface drying time) and do solid work the time (actual drying time).The present invention adopts fingers-touch method:Touched with finger and touch film coated surface, such as feel that some are tacky, but no paint viscous On finger, as dry tack free.
(8) adhesive force (with reference to GB/T1720-89)
The strong degree that paint film and coated article part surface are combined together by the effect of physics and chemical force, referred to as adheres to Power.
Survey adhesive force using drawing circle method.Product is applied on tinplate by regulation, after being completely dried, uses paint film adhesion Tester tests the adhesive force of paint film, and experimental result amplifies sem observation cuts with 4 times.
(9) resistance to impact (with reference to GB/T1732-93)
Measure the shock resistance of coating iron plate using paint film anti-impact force device, and the amplification sem observation paint film with 4 speeds There are the phenomenons such as flawless, wrinkle and peeling.
(10) glossiness (with reference to GB/T9754-88)
Using glossiness note, test paint film is tested parallel to three diverse locations in coating direction, seek gained The meansigma methodss of three values.
Coated by titanium dioxide hollow glass micropearl covered effect is tested
(1) micro structure of coated by titanium dioxide hollow glass micropearl, can observe its micro- knot by SEM electron-microscope scanning Structure.By cladding after with cladding before hollow glass micropearl scanning figure contrast, observe whether it has cladding, and determine if wrap Cover intact.
(2) phase composition of coated by titanium dioxide hollow glass micropearl, micro- with XRD analysis coated by titanium dioxide hollow glass The phase composition of pearl, analyzes the crystal formation of titanium dioxide by the diffraction maximum of XRD figure, and determination is anatase titanium dioxide or rutile-type dioxy Change titanium.
The test of coating heat-proof quality
The test of coating heat-proof quality, abroad after solar radiation the factor such as surface temperature, energy-conservation and durability Lai The effect of heat insulation of assessment coating.In China, for the test of coating heat-proof quality, there is presently no corresponding standard.Typically adopt Take two methods:One is the reflectance spectrum measuring coating, observes whether it has high reflectance in solar radiation SPECTRAL REGION;Two It is direct mensure, compare the temperature of coating lower surface under infrared light irradiation.
The present invention adopts direct measuring method (hot tank method of testing).Device is to be made a size of with polystyrene foam plastics The hot tank of 200mm × 200mm × 400mm.Hot tank wall thickness 100mm, opens the breach of one 150mm × 70mm in top centre, uses To place test plate (panel) to be measured.For reaching heat up stable, replacement sun exposure simulation test, and the actual measurement effect under sunlight Really, 500W infrared lamp is selected to make heater.
During test, using two thermocouples, the temperature of the front and back of assay plate respectively.
Test procedure is as follows:
1. model specification:The uralite of 150mm × 70mm × 5mm.Coating sample is painted on uralite, Film thickness is 300 μm about.
2. by after test plate (panel) to be measured numbering, it is placed on specified location in hot tank, the one of film faces down, and its geometric center is in bulb Under center.
3. adjust the distance between lamp and plate to 200mm, open regulated power supply, every 5min record model two sides temperature, Till test plate (panel) back temperature is basically unchanged.
4. take off test plate (panel), after being cooled to room temperature, retest once.
With reference to embodiment, the concrete technical scheme of the present invention is described further:
Embodiment 1
1.TiO2The preparation of coated hollow glass bead
TiO2The preparation process of coated hollow glass bead is as follows:
(1) measure 30ml dehydrated alcohol and 10ml butyl titanate is added in there-necked flask, under the conditions of 28 DEG C of temperature, with 1800 turns/min of rotating speed, 10min is to uniform for stirring;
(2) add 3ml glacial acetic acid in there-necked flask, stir, add 10ml cenosphere, in 28 DEG C of conditions of temperature Under, with 1800 turns/min of rotating speed, stir 20min to uniform;
(3) it is added in separatory funnel after 30ml dehydrated alcohol and 3ml water being mixed in beaker, be 28 DEG C of bars in temperature Under part, it is slowly dropped in there-necked flask, time for adding is 18min;
(4) with 1800 turns/min of rotating speed, stirring reaction 1h;
(5), after standing 24-48h, product is put in 100 DEG C of baking ovens and dries;
(6) after drying, product is placed in temperature in calcining furnace and is 500 DEG C, calcine 3 hours, obtain final product.
2. the preparation of new hydrophobic insulating moulding coating
As shown in table 3, its preparation process is as follows for the formula of new hydrophobic insulating moulding coating:
(1) add appropriate distilled water in plastic containers, start dispersion machine, with 400 turns/min of rotating speed, stirring at low speed, Then it is slowly added to water-repelling agent, dispersant, wetting agent, defoamer in the following order, then stirring at low speed is uniformly dispersed for 5 minutes;
(2) it is slowly added to filler, with 1800 turns/min of rotating speed, high-speed stirred, disperse 40 minutes;
(3) stirred for 400 turns/min with rotating speed, be slowly added to heat insulating function filler, stir 10 minutes, after being uniformly dispersed again Add emulsion and other auxiliary agents, stirring 20 minutes is so as to mix homogeneously;
(4) add remaining distilled water and thickening agent, adjust the viscosity of product, and the pH value of adjusting coating.
The formula of table 3 new hydrophobic insulating moulding coating
Above-mentioned new hydrophobic insulating moulding coating is pressed national standard and is detected, acquired results data such as table 4:
Table 4 new hydrophobic insulating moulding coating performance table
Embodiment 2
In the case of ensureing that other raw materials are constant, investigate the impact to hydrophobic insulating moulding coating performance for the emulsion, as table 5 institute Show:
The impact to coating property for table 5 emulsion
As can be seen that insulating moulding coating obtained by silicone acrylic emulsion is higher than not only other two kinds of products on traditional performance in table 5, And its heat-proof quality is also good than the coating that other two kinds of emulsions are obtained.Comprehensively draw, in heat insulating function coating, select silicon third breast Liquid, the performance such as the raising heat-proof quality of coating that can be bigger, hardness of paint film, adhesive force.
Embodiment 3
In the case of ensureing that other raw materials are constant, investigate the impact to hydrophobic insulating moulding coating performance for the defoamer, as table 6 institute Show:
Table 6 defoamer defoaming effect contrasts
By experiment, in the situation only selecting silicone defoamer, the defoaming effect of coating is undesirable, only continues Increase defoamer and could make the complete froth breaking of coating.Equally, when only selecting mineral oil defoaming agent, coating defoaming effect is also paid no attention to Think.Used by the synthesis of two kinds of defoamer, on the premise of defoamer consumption is less, coating has obtained perfect froth breaking knot Really.Therefore, the present invention selects silicone defoamer and mineral oil defoaming agent (1:1) synthesis of (weight ratio) uses.
Embodiment 4
TiO2Coated hollow glass bead preparation method is investigated
(1) collosol and gel hydrolytic process water and butyl titanate volume ratio
According to theoretical value 1:1 addition.It is converted into volume, with the addition volume of butyl titanate as 10ml, theoretical addition The volume of water should be 2.1ml.The volume of fixing butyl titanate, with water do variable be separately added into 1.5ml, 2.1ml, 3ml, 4ml, 5ml, 6ml and 7ml do comparative tests.
Shown by experimental phenomena, add the increase of volume with water, colloidal sol is from having obvious lamination to being no layered uniformly Colloidal sol, is no layered when water increases to 4-5ml, and precipitation when volume is more than 5ml.Determine the body adding water through experiment The long-pending volume ratio with butyl titanate is 1:2.
(2) add hollow glass micropearl volume
Equally doing comparative tests adds volume as 10ml with butyl titanate, and hollow glass micropearl is separately added into for variable 5ml, 10ml, 15ml and 20ml do comparative tests.
Shown by experimental phenomena, when adding volume to be more than 10ml, layering in colloidal sol, and hollow glass micropearl has not been able to all Even be dissolved in sol solutionses, the top section of sol solutionses is hollow glass micropearl.Experimentally determined addition hollow glass micropearl Volume is 10ml.
(3) it is aged time of repose
By ageing time of repose (0h, 6h, 12h, 24h, 48h, the 60h and 72h) calcining different to collosol and gel product Temperature is all 500 DEG C, and calcination time is 3h, by shown in the SEM electron-microscope scanning image such as Fig. 1 (A, B, C) of observation product.Permissible Observe:
Figure 1A is ageing time of repose is 0 scanning figure arriving 6h product, hollow glass micropearl smooth surface, and surface is not wrapped Cover.
Figure 1B is the scanning figure that ageing time of repose 6 arrives 24h product, and there is a small amount of cladding on hollow glass micropearl surface.
Fig. 1 C is that ageing time of repose 24 arrives 72h product scanning figure, in the surface almost all cladding of hollow glass micropearl And uniformly.
It is found that when being aged time of repose about 24h, the surface almost all cladding TiO of glass microballoon2.And with Its covered effect difference of prolongation the time is little.It is 24 to 48 hours that this single choice determines digestion time.
(4) calcining heat
By being all 24 products arriving 48h to digestion time, calcine again after being dried, under different calcining heats (200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C), calcination time is swept by the product SEM Electronic Speculum observing gained for 3h Tracing is as shown in Fig. 2 (A, B, C, D).It is observed that
Fig. 2A is the scanning figure of 200 to 300 DEG C of calcining heat, and hollow glass micropearl smooth surface is uncoated.
Fig. 2 B is the scanning figure of 300 to 400 DEG C of calcining heat, a small amount of TiO of hollow glass micropearl Surface coating2, and Cladding is uneven.
Fig. 2 C is the scanning figure of 400 to 600 DEG C of calcining heat, and hollow glass micropearl surface almost all coats, and surface is wrapped Cover uniformly.
Fig. 2 D is the scanning figure of 600 to 800 DEG C of calcining heat, and the deformation of hollow glass micropearl almost all is broken to be sintered into Block.
By contrast it is found that calcining heat is when 500 about, TiO2Modify the covered effect of hollow glass micropearl relatively Good, when temperature is at 400 DEG C, still there is the hollow glass micropearl Surface coating of part uneven.And have data to show, molten The TiO of sol-gel preparation2Modify hollow glass micropearl calcining heat when reaching 500 DEG C, it 90% is Detitanium-ore-type TiO2, when Temperature has more than 90% Detitanium-ore-type TiO when reaching 600 DEG C2It is converted into rutile TiO2.Due to nano-anatase TiO2 There is the characteristic of photocatalytic degradation Organic substance.
Two kinds of situations of summary, the present invention selects calcining heat to be 500 DEG C, takes its photocatalysis characteristic.
Embodiment 5
In the case of ensureing that other raw materials are constant, investigate TiO2Coated hollow glass bead percentage composition to hydrophobic The impact of heat-insulation property of heat-insulation coating.
With TiO2Coated hollow glass bead is heat insulating function filler, and its addition is respectively 0%, 2%, 4%, 6% and 8%, PVC value prepares insulating moulding coating for 40%, measures its heat-proof quality such as table 7 below.
7 five kinds of coating property contrasts of table
Table 7 is different TiO2The performance comparison of the coating of coated hollow glass bead content.Can be drawn by table, when TiO2When the addition of coated hollow glass bead reaches 8%, the heat-proof quality highest of coating, but the resistance to impact of coating by Decline in the increase of cenosphere content.And addition its heat-proof quality and addition when 4% are that temperature difference is several for 6% It is little, differ 2 DEG C with addition for 8%, but its resistance to impact is higher than them.Be building coating in view of coating, its Resistance to impact aspect requires higher, from the addition for 4%.

Claims (9)

1. a kind of hydrophobic insulating moulding coating is it is characterised in that include following raw material by weight:Emulsion 35-45%, pigment 8- 11%th, heat insulating function filler 4-7%, body constitution filler 10-12%, wetting agent 0.4-0.5%, dispersant 1-1.5%, defoamer 0.5-0.6%, thickening agent 0.7-0.8%, coalescents 1-2%, water-repelling agent 7-10%, other auxiliary agents 0.3-2%, balance of steaming Distilled water.
2. new hydrophobic insulating moulding coating according to claim 1 is it is characterised in that described emulsion is pure-acrylic emulsion, benzene One or more of acrylic emulsion and silicone acrylic emulsion.
3. new hydrophobic insulating moulding coating according to claim 1 is it is characterised in that described pigment is rutile titanium dioxide Powder;Described body constitution filler is ground calcium carbonate, precipitated calcium carbonate, Pulvis Talci, wollastonite in powder, mica powder, Kaolin, precipitated sulfur One or more of sour barium, bentonite, sierozem power, superfine alumina silicate, silica flour;Described thickening agent is hydroxy ethyl fiber One or more of element, alkali swollen thickener and association type polyurethane thickener;Described dispersant is electric neutrality amine salt, gathers One or more of metal carboxylate.
4. new hydrophobic insulating moulding coating according to claim 1 is it is characterised in that described heat insulating function filler is TiO2 The hollow glass micropearl of cladding, it is prepared by following steps:
(1) measure 25-30ml dehydrated alcohol and 8-10ml butyl titanate is added in there-necked flask, in temperature 26-30 DEG C condition Under ,/min is turned with rotating speed 1800-1900, stirring 8-10min is to uniform;
(2) add 2-3ml glacial acetic acid in there-necked flask, stir, add 8-10ml cenosphere, in temperature 26-30 Under the conditions of DEG C ,/min is turned with rotating speed 1800-1900, stirring 18-20min is to uniform;
(3) it is added in separatory funnel after 25-30ml dehydrated alcohol and 3-5ml water being mixed in beaker, in temperature 26-30 DEG C Under the conditions of, it is slowly dropped in there-necked flask, time for adding is 15-20min;
(4)/min stirring is turned with rotating speed 1800-1900, react 1h;
(5), after standing 24-48h, product is put in 90-100 DEG C of baking oven and dries;
(6) after drying, product is placed in temperature in calcining furnace and is 400-600 DEG C, calcine 3 hours, obtain final product.
5. new hydrophobic insulating moulding coating according to claim 1 it is characterised in that described water-repelling agent include following by weight The raw material of amount part meter:Paraffin 2-4 part, silicone oil 3-6 part, anion surfactant 1-2 part, stearic acid 2-5 part, triethanolamine 2- 5 parts, emulsifying agent 2-5 part, water 30-50 part.
6. new hydrophobic insulating moulding coating according to claim 1 is it is characterised in that described defoamer disappears for silicone Infusion and mineral oil defoaming agent are by weight for 1:1 compounds.
7. new hydrophobic insulating moulding coating according to claim 1 it is characterised in that described coalescents be benzyl alcohol, One or more of ethylene glycol, propylene glycol, ethylene glycol, Oleum Terebinthinae, alcohol ester-12.
8. a kind of new hydrophobic insulating moulding coating according to claim 1 is it is characterised in that other auxiliary agents include pH regulator One or more of agent, antistatic agent, hydrophobic slip agent, antirust agent, antifreezing agent, antifungus agent, antibacterial.
9. a kind of method preparing above-mentioned new hydrophobic insulating moulding coating is it is characterised in that comprise the following steps:
(1) add appropriate distilled water in plastic containers, start dispersion machine ,/min is turned with rotating speed 350-400, stirring at low speed, Then it is slowly added to water-repelling agent, dispersant, wetting agent, thickening agent, defoamer, then stirring at low speed 4-6 minute in the following order It is uniformly dispersed;
(2) it is slowly added to filler ,/min, high-speed stirred are turned with rotating speed 1800-1900, disperses 30-40 minute;
(3)/min stirring at low speed is turned with 350-400, be slowly added to heat insulating function filler, stir 10-12 minute, after being uniformly dispersed Add emulsion and other auxiliary agents, stirring 20 minutes is so as to mix homogeneously;
(4) add remaining distilled water and thickening agent, adjust the viscosity of product, and the pH value of adjusting coating.
CN201610795198.6A 2016-08-31 2016-08-31 Hydrophobic heat-insulation coating and preparation method therof Pending CN106380977A (en)

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Application publication date: 20170208