CN104177951A - Anti-dazzle coating composition, and preparation and application thereof - Google Patents
Anti-dazzle coating composition, and preparation and application thereof Download PDFInfo
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- CN104177951A CN104177951A CN201310199798.2A CN201310199798A CN104177951A CN 104177951 A CN104177951 A CN 104177951A CN 201310199798 A CN201310199798 A CN 201310199798A CN 104177951 A CN104177951 A CN 104177951A
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Abstract
A related anti-dazzle coating composition comprises a) a base material; b) a nanometer-level core shell structural microballoon which accounts for 1-10% by mass of the coating composition and used as an anti-dazzle modifier, wherein the core of the microballoon is one or more selected from nanometer SiO2, nanometer CaCO3 and nanometer poly(C1-C8 alkyl methacrylate), and the shell material is polystyrene and/or polymethyl methacrylate; and c) an other optional coating auxiliary agent. Compared with conventional anti-dazzle modified coating compositions, the coating composition helps to substantially reduce dazzle, and the transparency of a coating layer is substantially improved. The invention also relates to a preparation method of the coating composition and application of the coating composition to provide an anti-dazzle coating layer, and especially application to provide an anti-dazzle coating layer for road isolation strips or tunnels.
Description
Technical field
The present invention relates to a kind of anti-dazzle coating composition, relate in particular to a kind of tunnel anti-dazzle coating composition, the invention still further relates to preparation and the purposes of described coating composition.
Background technology
Light pollution is a kind of novel environmental pollution, can be detrimental to health, destroy ecology, increases traffic accident, hinders day justice observation, make troubles, waste energy etc. to people's life.Because coating has purposes very widely, be applied to the every aspect of life.Yet smooth coating surface also can produce light pollution harm.
, there is mountain range without stop in a lot of places in China, in mountain range, all can have very long tunnel, and some tunnels may reach one or two kilometer.In tunnel, interaction due to the lighting system of tunnel illuminating system and driving vehicle, the driver who drives can be subject to the catoptrical attack of coating surface of tunnel wall Smooth, can cause people's eyesight illusion, the visual field that can hide driver moment, makes it feel to have a dizzy spell, serious harm pedestrian and driver's sight function, cause officer's error rate to rise, traffic accident easily meets accident.This eyes are subject to the stronger stimulation of light pollution, the eye strain very easily causing and the namely dazzle harm of having a dizzy spell.
Existing tunnel is substantially all some frie retardant coatings with coating, does not also relate to special tunnel anti-dazzle coating.The present invention aims to provide a kind of anti-dazzle coating, and this application of paints can reduce the dazzle harm in tunnel driving in vcehicular tunnel, thereby reduces the generation of the unexpected traffic accident causing because of dazzle, ensures tunnel traffic safety.
Summary of the invention
In view of the above-mentioned problems in the prior art, the present inventor has carried out extensive and deep research for tunnel with anti-dazzle coating, to finding a kind of coating composition that can effectively reduce dazzle.Found that, by the nano level nucleocapsid structure microballoons such as nano level PBA/PS nucleocapsid structure microballoon, nano level PBA/PMMA nucleocapsid structure microballoon are joined in coating, can greatly reduce 60 ° of reflected light of coating, thereby greatly reduce dazzle, find that in addition so the transparency of the coating of acquisition improves greatly.The present invention is accomplished based on aforementioned discovery just.
Therefore, an object of the present invention is to provide a kind of anti-dazzle coating composition, this coating composition comprises the nucleocapsid structure microballoons such as nano level PBA/PS nucleocapsid structure microballoon, nano level PBA/PMMA nucleocapsid structure microballoon as anti-dazzle properties-correcting agent, not only greatly reduce dazzle, and the transparency of coating improves greatly.
Another object of the present invention is to provide a kind of method of preparing coating composition of the present invention.
A further object of the present invention is to provide the purposes of coating composition of the present invention in Anti Glare Coatings is provided, and the purposes of Anti Glare Coatings is especially provided in median or tunnel.
The technical scheme that realizes above-mentioned purpose of the present invention can be summarized as follows:
1. an anti-dazzle coating composition, comprises following component:
A) base-material,
B) account for the nano level nucleocapsid structure microballoon as anti-dazzle properties-correcting agent of coating composition 1-10 quality %, wherein the core in this microballoon is to be selected from one or more in lower group: nanometer SiO
2, nano-TiO
2, nanometer CaCO
3with poly-(methyl) vinylformic acid C of nanometer
1-C
8alkyl ester, and shell material is polystyrene and/or polymethylmethacrylate, and the median size of preferred described microballoon is 20-100nm, is preferably 30-80nm; And
C) other optional coatings additive(s).
2. according to the coating composition of the 1st, this coating composition is water-borne coatings.
3. according to the 1st or the coating composition of 2, wherein said base-material is acrylic resin, and urethane is especially the urethane of aqueous polyurethane form or its mixture.
4. according to the coating composition of any one in 1-3 item, wherein gather (methyl) vinylformic acid C
1-C
8alkyl ester is poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) vinylformic acid n-propyl and poly-(methyl) n-butyl acrylate.
5. according to the coating composition of any one in 1-4 item, wherein the median size of the core of nano level nucleocapsid structure microballoon is generally 10-40nm, is preferably 20-30nm.
6. according to the coating composition of any one in 1-5 item, wherein said nano level nucleocapsid structure microballoon is SiO
2/ PS microballoon, SiO
2/ PMMA microballoon, PBA/PS microballoon, PBA/PMMA microballoon or its mixture, especially PBA/PS microballoon, PBA/PMMA microballoon or its mixture.
7. according to the coating composition of any one in 1-6 item, wherein the content of anti-dazzle properties-correcting agent accounts for the 0.5-10 quality % of coating composition total mass, preferably accounts for 2.0-7.0 quality %, more preferably accounts for 2.3-4.5 quality %.
8. according to the coating composition of any one in 1-7 item, wherein, when described nano level nucleocapsid structure microballoon is PBA/PS nano level nucleocapsid structure microballoon, PBA/PMMA nano level nucleocapsid structure microballoon or its mixture, the content of anti-dazzle properties-correcting agent accounts for the 2.3-4.5 quality % of coating composition total mass.
9. prepare according to the method for the coating composition of any one in 1-8 item for one kind, it is characterized in that forming before coating composition anti-dazzle properties-correcting agent is sneaked into, anti-dazzle properties-correcting agent is pre-dispersed by means of dispersion agent, then by mixing with other component of coating composition through pre-dispersed anti-dazzle properties-correcting agent of so obtaining.
10. the purposes in Anti Glare Coatings is provided according to the coating composition of any one in 1-8 item especially provides the purposes of Anti Glare Coatings in median or tunnel.
Accompanying drawing explanation
Fig. 1 is the nano level SiO of the embodiment of the present invention 5 preparations
2the transmission electron microscope photo of the pattern of/PS nucleocapsid structure microballoon.
Fig. 2 is the transmission electron microscope photo of pattern of PBA emulsion, PBA/PS and the PBA/PMMA nucleocapsid structure microballoon of the embodiment of the present invention 6 and embodiment 7 preparations, wherein a figure is the transmission electron microscope photo of PBA emulsion, b figure is the transmission electron microscope photo of PBA/PS nucleocapsid structure microballoon, and c figure is the transmission electron microscope photo of PBA/PMMA nucleocapsid structure microballoon.
Fig. 3 is that transmittance and glossiness are with the change curve of PBA/PS nucleocapsid structure microballoon addition.
Fig. 4 is that transmittance and glossiness are with the change curve of PBA/PMMA nucleocapsid structure microballoon addition.
Embodiment
According to an aspect of the present invention, provide a kind of anti-dazzle coating composition, said composition comprises following component:
A) base-material,
B) account for the nano level nucleocapsid structure microballoon as anti-dazzle properties-correcting agent of coating composition 1-10 quality %, wherein the core in this microballoon is to be selected from one or more in lower group: nanometer SiO
2, nano-TiO
2, nanometer CaCO
3with poly-(methyl) vinylformic acid C of nanometer
1-C
8alkyl ester, and shell material is polystyrene and/or polymethylmethacrylate; And
C) other optional coatings additive(s).
Filmogen in coating composition refers to the rear left all the components of volatile solvent volatilization in coating, and these are to form the material of filming.Filmogen is divided into again main film forming substance and the large class of auxiliary film forming matter two.Main film forming substance refers to the independent material that can be formed with some strength, continuous dry film, as inorganic substance such as various resins, dryness wet goods polymer and water glass, is to form the requisite composition of filming.Color filler, some auxiliary agent play booster action while forming filming, and they separately can not film forming, but their existence can make to film and more meet the requirement of effect, and film forming is had to booster action.
Anti-dazzle coating composition of the present invention comprises base-material.Base-material is the non-volatility part in coating composition, can form and film, and the pigment that can bond, that is the main film forming substance of coating.For the purpose of the present invention, any base-material of filming that can form all can use.Preferably, should to make gained coating composition be water-borne coatings in the selection of the base-material of coating composition of the present invention.
In a preferred embodiment of the invention, the base-material of coating composition of the present invention is acrylic resin, urethane or its mixture.
Acrylic resin is vinylformic acid and methacrylic acid, their ester class or homopolymer and the multipolymer of their other derivative (as acid amides and nitrile) through being polymerized.As described ester class, can mention methyl acrylate, ethyl propenoate, butyl acrylate, especially n-butyl acrylate and isobutyl acrylate, Octyl acrylate, especially 2-EHA, methyl methacrylate and n-BMA.As the comonomer that forms multipolymer, can mention vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, acrylamide etc.The present invention particularly preferably is, and acrylic resin is the multipolymer of the positive butyl ester of polyacrylic acid, polyisobutyl acrylate or vinylformic acid and n-butyl acrylate.To the present invention advantageously, acrylic resin is aqueous acrylic emulsion form.These acrylic resins, the especially preparation of these water-borne acrylic resin emulsions are well known in the art.For example, in order to prepare the copolymerization water miscible liquid of vinylformic acid and n-butyl acrylate, vinylformic acid and n-butyl acrylate can be carried out to letex polymerization according to take ammonium persulphate to order body part and drop rate as initiator in water medium at approximately 70 ℃.
Urethane for by vulcabond or polyisocyanates with two or more, isocyanato is to reactive group and reacts the general name of the macromolecular compound of generation as hydroxyl, sulfydryl and amino etc. compound, on its main chain with many repetitions-NHCOO-group.Conventional vulcabond has tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), poly methylene poly phenyl poly isocyanate (PAPI), xylylene diisocyanate (XDI) etc.For alcohol used, according to the difference of hydroxy component used, can be divided into PAUR and polyether(poly)urethane.
In the present invention, urethane is advantageously aqueous polyurethane form.
Aqueous polyurethane is also referred to as water dispersible polyurethane, aqueous polyurethane or waterbased urethane.Aqueous polyurethane divides and can be divided into aqueous polyurethane, polyurethane aqueous dispersion body and polyaminoester emulsion by outward appearance.
The preparation method of aqueous polyurethane can be divided into two kinds of outer emulsion process and internal emulsification methods conventionally.Outer emulsion process refers to and adopts additional emulsifying agent, under strong shear action, forcibly polyurethane particles is scattered in to the method in water.Internal emulsification method claims again self-emulsification, refers to that the hydrophilic radical that induces one in polyurethane molecular structure can make self to be dispersed into the method for emulsion without emulsifying agent.Internal emulsification method can be divided into again acetone method, prepolymer blend method, melting dispersion method, ketoimine/ketone connection nitrogen method and protection end group emulsion process.
In acetone method, the high viscosity base polyurethane prepolymer for use as of first synthetic contain-NCO end group, add acetone solution, make its reduced viscosity, then with carrying out chain extension containing ionic group chainextender, under high-speed stirring, by strong shearing force, make it to be scattered in water, after emulsification, underpressure distillation desolvation acetone, obtains aqueous polyurethane dispersing liquid.
In prepolymer blend method, first the synthetic performed polymer containing hydrophilic radical and end-NCO, when the relative molecular weight of performed polymer is not too high and viscosity hour, can not add or add a small amount of solvent, under high-speed stirring, be scattered in water, use again hydrophilic monomer (diamines or triamine) by its part chain extension, generate relatively to have divided and measure high aqueous polyurethane, finally obtain aqueous polyurethane dispersing liquid.
In the present invention, also can use the aqueous polyurethane of modification.Modification is mainly by two kinds of means of physics and chemistry, and by grafting, block, inside and outside crosslinked other polymer materials, the methods such as blend or formation interpenetrating polymer networks are carried out modification.The aqueous polyurethane of modification comprises acrylic ester modified water-soluble polyurethane, organic silicon modified aqueous polyurethane, epoxy resin modified aqueous polyurethane etc.
Acrylic ester modified water-soluble polyurethane is in urethane, to introduce the water-based emulsion that acrylic acid polymer segment obtains.The preparation of this class emulsion is well known in the art, and comprises blended cross linking reaction method, emulsion copolymerization method and composite emulsion polymerization method.
For composite emulsion polymerization method, a kind of technique is interpenetratingpolymernetworks technique.In this technique, in system, having a component at least is crosslinking structure, on molecular level, have an effect, as using acrylate monomer as the organic solvent of synthesis of polyurethane performed polymer, and then in polyaminoester emulsion, carry out the intercrossed network type emulsion that polymerization makes polymerization of acrylic modified polyurethane.
The another kind of technique of composite emulsion polymerization method is in aqueous polyurethane emulsion, to add acrylic monomer as acrylate carries out radical polymerization, forms the composite emulsion of so-called core-shell type acrylic ester modified water-soluble polyurethane.For example adopt acrylic monomer as urethane solvent, to make the acrylate modified polyaminoester emulsion of IPN structure as acrylate monomer.Or, the acrylic resin with pendant hydroxyl groups and the urethane acrylate that contains residual isocyanate base are carried out to graft reaction, through in amine and after, with water-dispersion, form self-emulsification aqueous system.
In the present invention, the solid content of aqueous polyurethane is advantageously 35-45 % by weight.When acrylic resin provides with water-based propionic ester, while especially providing with its water miscible liquid, its solid content is advantageously 50-60 % by weight.
In paint field, in order to reduce the luminous reflectance of coatingsurface, conventionally adopt and in coating, add light absorbing material effectively, as matting agent.The matting agent often using comprises the silicon-dioxide through special processing, comprises precipitation silica flatting agent, and silicate, as montmorillonite.Yet, utilize these matting agents as the anti-dazzle properties-correcting agent of anti-dazzle coating composition, can't obtain anti-dazzle effect of great satisfaction, and the transparency of filming that these matting agents obtain has much room for improvement.
According to the present invention, as the anti-dazzle properties-correcting agent of coating, use be nano level nucleocapsid structure microballoon, wherein the core in this microballoon is to be selected from one or more in lower group: nanometer SiO
2, nano-TiO
2, nanometer CaCO
3with poly-(methyl) vinylformic acid C of nanometer
1-C
8alkyl ester, and shell material is polystyrene and/or polymethylmethacrylate.
In the present invention, poly-(methyl) vinylformic acid C
1-C
8alkyl ester refers to polymethyl acrylic acid C
1-C
8alkyl ester and/or polyacrylic acid C
1-C
8alkyl ester.C
1-C
8alkyl refers to the saturated hydrocarbyl with 1-8 carbon atom.As this C
1-C
8the example of alkyl, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl, Sec-Hexyl, n-heptyl, Zhong Gengji, n-octyl and 2-ethylhexyl.Preferred C
1-C
8alkyl is C
1-C
4alkyl, especially methyl, ethyl, n-propyl and normal-butyl.
In a preferred embodiment of the invention, poly-(methyl) vinylformic acid C
1-C
8alkyl ester is poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) vinylformic acid n-propyl and poly-(methyl) n-butyl acrylate, especially poly-(methyl) n-butyl acrylate.The median size of nano level nucleocapsid structure microballoon of the present invention is in nano-scale, and preferably this particle diameter is 30-100nm, preferably 50-80nm.
In the present invention, core is nanometer SiO
2, nano-TiO
2, nanometer CaCO
3with poly-(methyl) vinylformic acid C of nanometer
1-C
8the microballoon of alkyl ester has nucleocapsid structure, and core is nano silicon (SiO
2), nano-TiO
2, nanometer CaCO
3or poly-(methyl) vinylformic acid C of nanometer
1-C
8alkyl ester, and housing is respectively polystyrene and/or polymethylmethacrylate, the particularly polystyrene of grafting and/or the polymethylmethacrylate of grafting.
Advantageously, in nano level nucleocapsid structure microballoon of the present invention, the median size of core is generally 10-40nm, is preferably 20-30nm.
The preparation of nano level nucleocapsid structure microballoon of the present invention is well known in the art, and by known technology, can prepare.For example,, for synthetic kernel is nanometer SiO
2, nano-TiO
2or nanometer CaCO
3nano level nucleocapsid structure microballoon, can be first by nanometer SiO
2, nano-TiO
2or nanometer CaCO
3particle stabilized dispersion, then repolymerization, especially graft polymerization vinylbenzene and/or methyl methacrylate under these nanoparticles exist.For synthetic kernel is poly-(methyl) vinylformic acid C
1-C
8the nano level nucleocapsid structure microballoon of alkyl ester, can first letex polymerization obtain poly-(methyl) vinylformic acid C of nano level
1-C
8alkyl ester emulsion, and then add vinylbenzene and/or methyl methacrylate-grafted polymerization, form the shell of outside.In order to form the good shell of mechanical property, can, by the polymerization under linking agent exists as TMPTMA of vinylbenzene or methyl methacrylate, obtain crosslinked PS or PMMA.In order to form crosslinked shell, linking agent, as the quality usage ratio of TMPTMA and styrene monomer or MMA monomer is generally 0.5-1.5, is preferably 0.5-1.0.
In order to form mechanical property poly-(methyl) vinylformic acid C preferably
1-C
8alkyl ester core, can be by (methyl) vinylformic acid C
1-C
8alkyl ester monomer polymerization under linking agent exists as TMPTMA, poly-(methyl) vinylformic acid C that obtains being cross-linked
1-C
8alkyl ester.In order to form crosslinked poly-(methyl) vinylformic acid C
1-C
8alkyl ester butyl ester as positive in polyacrylic acid (PBA) core, linking agent is as TMPTMA and (methyl) vinylformic acid C
1-C
8alkyl ester, as the quality usage ratio of butyl acrylate is generally 0.5-1.5, is preferably 0.5-1.0.
As nano level nucleocapsid structure microballoon of the present invention, can especially mention SiO
2/ PS microballoon, SiO
2/ PMMA microballoon, PBA/PS microballoon, PBA/PMMA microballoon or its mixture.According to the present invention, particularly preferably use PBA/PS nano level nucleocapsid structure microballoon, PBA/PMMA nano level nucleocapsid structure microballoon or its mixture.
In anti-dazzle coating composition of the present invention, as components b) anti-dazzle properties-correcting agent, its consumption accounts for the 0.5-10 quality % of coating composition total mass of the present invention conventionally, preferably accounts for 2.0-7.0 quality %, more preferably accounts for 2.3-4.5 quality %.Especially, when described nano level nucleocapsid structure microballoon is PBA/PS nano level nucleocapsid structure microballoon, PBA/PMMA nano level nucleocapsid structure microballoon or its mixture, the content of anti-dazzle properties-correcting agent accounts for the 2.3-4.5 quality % of coating composition total mass.
Except as base-material a) of component with as components b) anti-dazzle properties-correcting agent, in coating composition of the present invention, also can comprise the coatings additive(s) that other preparation coating is used, comprise other anti-dazzle properties-correcting agent.When using these other coatings additive(s)s, its consumption conventional amount used of respectively doing for oneself.For example, the addition of these additives during based on 100 mass parts coating composition, is generally 0.1-5 mass parts, preferably 1-5 mass parts.
As other coatings additive(s), can mention thickening material, film coalescence aid, stablizer, flow agent, defoamer, dispersion agent, pigment etc.As thickening material, can mention wilkinite, cellulose family (HEc, Mc), alkali swelling type (HAsE, AsE), association type polyurethanes (HEuR).As film coalescence aid, can mention ethylene glycol, propylene glycol, phenylcarbinol, butyl glycol ether, propylene glycol and alkoxide, as neopentyl glycol list isobutyl ester.As stablizer, can mention BYK-E410, the BYK-420 of German BYK company, the GN-935 of ROHM AND HAAS chemical reagents corporation.As flow agent, can mention BYK-310, BYK-333, BYK-345, the BYK-347 of German BYK company.As defoamer, can mention BYK-066N, the BYK-028 of German BYK company.As dispersion agent, can mention DisperBYK-2012, DisperBYK-190, DisperBYK-130, DisperBYK-115, the DisperBYK-154 of German BYK company, Sodium dodecylbenzene sulfonate (SDBS), polyoxyethylene glycol (PEG600), polyvinyl alcohol (PVA).
The application's coating composition also can comprise solvent.The selection of solvent is conventional, both can with an organic solvent, also can use aqueous solvent, especially water.Preferably, the selection of solvent makes coating composition of the present invention form water-borne coatings.
According to another aspect of the present invention, a kind of method of preparing anti-dazzle coating composition of the present invention is provided, it is characterized in that, being sneaked into, anti-dazzle properties-correcting agent forms before coating composition, anti-dazzle properties-correcting agent is pre-dispersed by means of dispersion agent, then by mixing with other component of coating composition through pre-dispersed anti-dazzle properties-correcting agent of so obtaining.The present invention adopts pre-dispersed processing, contributes to dispersed in coating composition of microballoon, reduces the reunion of microballoon.
Described pre-dispersed can carrying out in water also can carry out in the applicable organic solvent of coating composition of the present invention, can also in the water dispersion of base-material or water miscible liquid, carry out.Preferably that anti-dazzle properties-correcting agent of the present invention is pre-dispersed in water by means of dispersion agent.As the dispersion agent for pre-dispersed, can mention DisperBYK-2012, DisperBYK-190 and DisperBYK-130.In order to obtain desirable dispersion effect, conventionally need to stir.As selection, also can utilize ultrasonic wave that anti-dazzle properties-correcting agent is carried out pre-dispersed by means of dispersion agent.
The consumption of dispersion agent should make anti-dazzle properties-correcting agent of the present invention to be dispersed in dispersion medium.Advantageously, the consumption of dispersion agent is that every 100 mass parts coating compositions are used the dispersion agent of 1-3 part.
In accordance with a further aspect of the present invention, provide the purposes of coating composition of the present invention in Anti Glare Coatings is provided, the purposes of Anti Glare Coatings is especially provided in median or tunnel.
Use coating composition of the present invention to provide Anti Glare Coatings in median or tunnel, can greatly reduce dazzle, and it is transparent to film, therefore can be effectively for reducing the dazzle in median or tunnel.
Embodiment
For a more detailed description to the present invention with embodiment below.According to embodiments of the invention, are all only descriptions to the optimum embodiment of the present invention, do not form limiting the scope of the invention.
The umber of mentioning in each embodiment is all mass fraction or mass percent.
The preparation of reference example 1-varnish
The preparation of aqueous polyurethane emulsion: getting respectively molecular weight is 1000 (DL-1000, the polyether polyol of the molecular weight 1000 that propylene oxide ring-opening polymerization obtains, Yantai ten thousand China) and 400 (DL-400, the polyether polyol of the molecular weight 400 that propylene oxide ring-opening polymerization obtains, Yantai ten thousand China) polyether glycol 62.5g and 22.7g carry out composite, in gained polyether glycol mixture, add 62.5g diphenylmethanediisocyanate, at 70 ℃, stirring reaction is 120 minutes, obtain prepolymer, its isocyanate group NCO content is 5.8 % by mole.Then, in gained pre-polymerization mixture, add 8.52g hydrophilic modifying agent dimethylol propionic acid (DMPA) and the agent of 4.94g triethylamine neutralization reaction, then at 70 ℃, stir and react 60 minutes again, the chain extending reaction later stage is added the viscosity that 20-30ml acetone reduces performed polymer, obtains urethane.The weight-average molecular weight of this urethane is 7.1 ten thousand, and molecular weight distribution coefficient is 1.87.Gained urethane mechanical dispersion, in water, through excess pressure vacuum filtration 2h under 0.01KPa, is obtained to aqueous polyurethane emulsion, and the solid content of this emulsion is 38.1 quality %.
Get 100 parts and fall the aqueous polyurethane emulsion of described preparation in beaker by the preceding paragraph, successively add film coalescence aid neopentyl glycol list isobutyl ester (lark prestige Science and Technology Ltd.), stablizer BYK-420 (the modified urea that contains N-Methyl pyrrolidone, Germany BYK company), flow agent BYK-333 (polyether-modified polydimethylsiloxane, Germany BYK company) and defoamer BYK-028 (hydrophobic solid and the broken mixture of polysiloxane in polyglycol that steep, Germany BYK company), its addition is respectively 3 parts, 5 parts, 1 part and 1 part, rotating speed with 2500r/min in high speed dispersor disperses 45min, obtain water varnish.
Comparative example 1
Getting 10 parts of deionized waters adds in the 250ml there-necked flask of being furnished with agitator and prolong, then under agitation add wherein 1 part of dispersion agent DisperBYK-2012 (containing the high-molecular block copolymer solution of pigment affinity groups, Germany BYK company), in gained mixture, add dazzle properties-correcting agent C803 (SiO afterwards
2), its addition is 3 parts, gained mixture is used at 60 ℃ to the ultrasonic dispersion of numerical control supersonic instrument 60min, obtains through pre-dispersed dazzle properties-correcting agent.The ultrasonic frequency that ultrasonic dispersion adopts is 40KHz, and ultrasonic power is 200W.Under agitation, the dazzle properties-correcting agent through pre-dispersed so obtaining is all added to the water varnish of 100 parts of reference examples, 1 preparation that is arranged in beaker, then on high speed dispersor, with 2500r/min, disperse 30min, obtain coating composition.Use subsequently this coating composition to apply and test.
C803 is the silica flatting agent of U.S. W. R. Grace & Co, and median size is 3.7 μ m, and silica particles and inside are distributed with certain hole.
Comparative example 2
Repeat comparative example 1, difference is: the dazzle properties-correcting agent C803 of 3 parts is replaced with to the light diffusing agent MP90 of 3 parts.MP90 is the microballoon that methyl methacrylate and n-butyl acrylate copolymerization obtain, median size be 5-10 μ m (Dongguan San He Chemical Co., Ltd., MP-90).The consistency of this microballoon and aqueous polyurethane is good.
Comparative example 3
Repeat comparative example 1, difference is: the dazzle properties-correcting agent C803 of 3 parts is replaced with to the nanometer SiO of 5 parts
2hydrogel; And nanometer SiO
2hydrogel, without pre-dispersed processing, directly adds in water varnish.
Described nanometer SiO
2hydrogel is the HS-25 nanometer SiO of Zhejiang Province Yuda Chemical Co., Ltd
2hydrogel.
Comparative example 4
Repeat comparative example 1, difference is: the dazzle properties-correcting agent C803 of 3 parts is replaced with to the precipitation SiO of 3 parts
2.
Described precipitation SiO
2obtain in the following way: by the HS-25 nanometer SiO of Zhejiang Province Yuda Chemical Co., Ltd
2hydrogel in air dry oven at 110 ℃ precipitation dry after, through mortar, being ground to median size is 5-10 μ m.
Embodiment 5
SiO
2the preparation of/PS nano level nucleocapsid structure microballoon
1. silane coupling agent is processed nanometer SiO
2
By 15g nanometer SiO
2powder (particle diameter 20nm left and right, Guangzhou Jing Rui novel material company limited) vacuum-drying 24h at 105 ℃, add in there-necked flask, γ-methacryloxypropyl trimethyl silane (the KH-570 that adds again 200ml toluene (chemical reagents corporation of traditional Chinese medicines group) and 3g, Dow corning company), utilize the Soxhlet extractor 4h that refluxes at 120 ℃, cooling, filter, washing and dry, obtain the nanometer SiO of silanization
2powder.The mean particle size of this powder is 21nm, and this granularity is measured by dynamic light scattering (DLS).
2. nanometer SiO
2particle grafted PS SiO processed
2/ PS nano level nucleocapsid structure microballoon
In four-hole boiling flask, add 2
gthe nanometer SiO of prepared silanization
2powder, then adds 385ml deionized water, ultrasonic dispersion 3h.Then add while stirring 15g sodium lauryl sulphate (SDS, chemical reagents corporation of traditional Chinese medicines group) and 3g assistant for emulsifying agent Pentyl alcohol (chemical reagents corporation of traditional Chinese medicines group) pre-emulsification 0.5h at 80 ℃.Through 2 hours constant speed, drip monomer styrene St (St, Beijing Chemical Plant) with trimethylolpropane trimethacrylate (TMPTMA, Shanghai You Peng Chemical Co., Ltd.) 1: 1 mixing solutions 30g, meanwhile go through 2 hours constant speed and drip 0.3g APS (ammonium persulphate, traditional Chinese medicines chemical reagent group) aqueous solution in 15g water, drips and to carry out at 80 ℃, after being added dropwise to complete at 80 ℃ insulation reaction 1h, cooling discharging, obtains SiO
2/ PS nano level nucleocapsid structure microballoon.Granularity and distribution coefficient that this microballoon is measured by dynamic light scattering (DLS) are as shown in table 1, and transmission electron microscope photo is shown in Fig. 1.
Repeat comparative example 1, difference is: the dazzle properties-correcting agent C803 of 3 parts is replaced with to 3 parts by the fall SiO of described preparation of the preceding paragraph
2/ PS nano level nucleocapsid structure microballoon.
Table 1
Embodiment 6
The preparation of PBA/PS nano level nucleocapsid structure microballoon
Condenses (the OP-10 of the alkylphenol using 5g as emulsifying agent and oxyethane, Beijing Chemical Plant) and 15g sodium lauryl sulphate add pre-emulsification 0.5h in 400g distilled water, then go through and by constant pressure funnel, drip the solution of 0.35g ammonium sulfate APS in 30g distilled water wherein in 2 hours, meanwhile go through and by constant pressure funnel, drip n-butyl acrylate (BA in 2 hours, Beijing Chemical Plant) with 1: 1 mixture 40g of linking agent trimethylolpropane trimethacrylate (TMPTMA), after dropwising, at 80 ℃, keep 2h to react in gained mixture, obtain PBA water miscible liquid, does it pass through? the median size of measuring is 20nm, its transmission electron microscope photo see a in Fig. 2 figure (in figure size must with 20nm herein about equally).Then, at 80 ℃, solution to the APS that adds again 0.15g in gained PBA water miscible liquid in 10g distilled water, and with the constant speed dropping monomer St of 5ml/h and 1: 1 mixing solutions 30g of TMPTMA, after being added dropwise to complete at 80 ℃ insulation reaction 1h, obtain crosslinked PBA/PS nano level nucleocapsid structure microballoon.Granularity and distribution coefficient that this microballoon is measured by dynamic light scattering (DLS) are as shown in table 2, and transmission electron microscope photo is shown in b figure in Fig. 2.
Repeat comparative example 1, difference is: 3 parts of dazzle properties-correcting agent C803 are replaced with to 3 parts by the fall PBA/PS nano level nucleocapsid structure microballoon of described preparation of the preceding paragraph.
Embodiment 7
The preparation of PBA/PMMA nano level nucleocapsid structure microballoon
Condenses (the OP-10 of the alkylphenol using 5g as emulsifying agent and oxyethane, Beijing Chemical Plant) and 15g sodium lauryl sulphate add pre-emulsification 0.5h in 400g distilled water, then go through and by constant pressure funnel, drip the solution of 0.35g ammonium sulfate APS in 30g distilled water wherein in 2 hours, meanwhile go through and by constant pressure funnel, drip n-butyl acrylate (BA in 2 hours, Beijing Chemical Plant) with 1: 1 mixture 40g of linking agent trimethylolpropane trimethacrylate (TMPTMA), after dropwising, at 80 ℃, keep 2h to react in gained mixture, obtain PBA water miscible liquid, does it pass through? the median size of measuring is 20nm.Then, at 80 ℃, solution to the APS that adds again 0.15g in gained PBA water miscible liquid in 10g distilled water, and with the constant speed dropping monomer M MA of 5ml/h and 1: 1 mixing solutions 30g of TMPTMA, be added dropwise to complete rear 80 ℃ of insulation reaction 1h, obtain crosslinked PBA/PMMA nano level nucleocapsid structure microballoon.Granularity and distribution coefficient that this microballoon is measured by dynamic light scattering (DLS) are as shown in table 2, and transmission electron microscope photo is shown in the c in Fig. 2.
Repeat comparative example 1, difference is: 3 parts of dazzle properties-correcting agent C803 are replaced with to 3 parts by the fall PBA/PMMA nano level nucleocapsid structure microballoon of described preparation of the preceding paragraph.
Table 2
The coating that comparative example 1-4 and embodiment 5-7 are obtained utilizes manual spray gun to carry out spraying coating process at substrate surface, and the coating thickness obtaining is 10 μ m.To test its 60 ° of glossiness and transmittance and the resistance to acids and bases of respectively filming.Glossiness is recorded by the German BYK A-4430 of company vancometer; Transmittance is recorded by WGT-S transmittance/mist degree tester, and resistance to acids and bases records according to < < GB1763-79 (88) the chemical reagent resistance assay method > > standard of filming.The results are shown in following table 3.
Table 3
From table 3, SiO
2/ PS, PBA/PS and PBA/PMMA nano level nucleocapsid structure microballoon have guaranteed good transparency when comparing with each comparative example and all can effectively improve anti-dazzle performance.
Embodiment 8
Repeat embodiment 6, difference is: the umber of dazzle properties-correcting agent is replaced with respectively to 1 part, 5 parts, 7 parts and 10 parts by 3 parts.Use respectively subsequently thus obtained these coating compositions to apply and test.Test result is drawn in Fig. 3.
Embodiment 9
Repeat embodiment 7, difference is: the umber of dazzle properties-correcting agent is replaced with respectively to 1 part, 5 parts, 7 parts and 10 parts by 3 parts.Use respectively subsequently thus obtained these coating compositions to apply and test.Test result is drawn in Fig. 4.
Claims (10)
1. an anti-dazzle coating composition, comprises following component:
A) base-material,
B) account for the nano level nucleocapsid structure microballoon as anti-dazzle properties-correcting agent of coating composition 1-10 quality %, wherein the core in this microballoon is to be selected from one or more in lower group: nanometer SiO
2, nano-TiO
2, nanometer CaCO
3with poly-(methyl) vinylformic acid C of nanometer
1-C
8alkyl ester, and shell material is polystyrene and/or polymethylmethacrylate, and the median size of preferred described microballoon is 20-100nm, is preferably 30-80nm;
C) other optional coatings additive(s).
2. according to the coating composition of claim 1, this coating composition is water-borne coatings.
3. according to the coating composition of claim 1 or 2, wherein said base-material is acrylic resin, and urethane is especially the urethane of aqueous polyurethane form or its mixture.
4. according to the coating composition of any one in claim 1-3, wherein gather (methyl) vinylformic acid C
1-C
8alkyl ester is poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) vinylformic acid n-propyl and poly-(methyl) n-butyl acrylate, especially poly-(methyl) n-butyl acrylate.
5. according to the coating composition of any one in claim 1-4, wherein the median size of the core of nano level nucleocapsid structure microballoon is generally 10-40nm, is preferably 20-30nm.
6. according to the coating composition of any one in claim 1-5, wherein said nano level nucleocapsid structure microballoon is SiO
2/ PS microballoon, SiO
2/ PMMA microballoon, PBA/PS microballoon, PBA/PMMA microballoon or its mixture, especially PBA/PS microballoon, PBA/PMMA microballoon or its mixture.
7. according to the coating composition of any one in claim 1-6, wherein the content of anti-dazzle properties-correcting agent accounts for the 0.5-10 quality % of coating composition total mass, preferably accounts for 2.0-7.0 quality %, more preferably accounts for 2.3-4.5 quality %.
8. according to the coating composition of any one in claim 1-7, wherein, when described nano level nucleocapsid structure microballoon is PBA/PS nano level nucleocapsid structure microballoon, PBA/PMMA nano level nucleocapsid structure microballoon or its mixture, the content of anti-dazzle properties-correcting agent accounts for the 2.3-4.5 quality % of coating composition total mass.
9. prepare according to the method for the coating composition of any one in claim 1-8 for one kind, it is characterized in that forming before coating composition anti-dazzle properties-correcting agent is sneaked into, anti-dazzle properties-correcting agent is pre-dispersed by means of dispersion agent, then by mixing with other component of coating composition through pre-dispersed anti-dazzle properties-correcting agent of so obtaining.
10. the purposes in Anti Glare Coatings is provided according to the coating composition of any one in claim 1-8 especially provides the purposes of Anti Glare Coatings in median or tunnel.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189782A (en) * | 2016-08-08 | 2016-12-07 | 雷春生 | A kind of preparation method of light fixture glare proof glass coating |
| CN106380569A (en) * | 2016-09-27 | 2017-02-08 | 华南理工大学 | Water-based polyurethane anti-glare coating material and preparation method thereof |
| CN107540236A (en) * | 2017-09-15 | 2018-01-05 | 重庆市中光电显示技术有限公司 | Anti-blue light anti-dazzle protective glass for touch-screen and preparation method thereof |
| CN107868266A (en) * | 2017-11-28 | 2018-04-03 | 上海道助电子科技有限公司 | A kind of low quick-fried surface treatment method and UV film forming materials |
| CN108359376A (en) * | 2018-02-28 | 2018-08-03 | 深圳市航天新材科技有限公司 | Anti-dazzle imitative ceramic masking liquid composition of a kind of long acting antibiotic and preparation method thereof |
| CN109354934A (en) * | 2018-10-23 | 2019-02-19 | 青岛大学 | A kind of anti-dazzle class coating material, preparation method and its application |
| CN110531447A (en) * | 2019-08-16 | 2019-12-03 | 深圳市摩码科技有限公司 | A kind of anti-dazzle protective film and preparation method thereof |
| CN111040617A (en) * | 2019-12-26 | 2020-04-21 | 合肥乐凯科技产业有限公司 | Anti-dazzle hardening film for polaroid |
| CN113667393A (en) * | 2021-08-31 | 2021-11-19 | 武汉中科先进技术研究院有限公司 | Anti-glare organic-inorganic hybrid antifogging coating and preparation thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010111362A (en) * | 2000-06-10 | 2001-12-17 | 성재갑 | Coating composition for protecting dazzling effect |
| CN101679798A (en) * | 2007-05-16 | 2010-03-24 | Lg化学株式会社 | Composition for anti-glare film and anti-glare film prepared using the same |
| CN102245693A (en) * | 2008-10-14 | 2011-11-16 | 帝斯曼知识产权资产管理有限公司 | Stain resistant particles |
-
2013
- 2013-05-27 CN CN201310199798.2A patent/CN104177951B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010111362A (en) * | 2000-06-10 | 2001-12-17 | 성재갑 | Coating composition for protecting dazzling effect |
| CN101679798A (en) * | 2007-05-16 | 2010-03-24 | Lg化学株式会社 | Composition for anti-glare film and anti-glare film prepared using the same |
| CN102245693A (en) * | 2008-10-14 | 2011-11-16 | 帝斯曼知识产权资产管理有限公司 | Stain resistant particles |
Non-Patent Citations (2)
| Title |
|---|
| 徐滨士等: "《中国材料工程大典 第17卷 材料表面工程 下》", 31 January 2006 * |
| 杨光福等: "PET /SiO2纳米复合材料的光学性能和结晶成核行为", 《高分子材料科学与工程》 * |
Cited By (13)
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| CN106189782A (en) * | 2016-08-08 | 2016-12-07 | 雷春生 | A kind of preparation method of light fixture glare proof glass coating |
| CN106380569A (en) * | 2016-09-27 | 2017-02-08 | 华南理工大学 | Water-based polyurethane anti-glare coating material and preparation method thereof |
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| CN107868266A (en) * | 2017-11-28 | 2018-04-03 | 上海道助电子科技有限公司 | A kind of low quick-fried surface treatment method and UV film forming materials |
| CN108359376A (en) * | 2018-02-28 | 2018-08-03 | 深圳市航天新材科技有限公司 | Anti-dazzle imitative ceramic masking liquid composition of a kind of long acting antibiotic and preparation method thereof |
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