CN101851413B - Paint composition, anti-foul easy-cleaning product and preparation method thereof - Google Patents
Paint composition, anti-foul easy-cleaning product and preparation method thereof Download PDFInfo
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- CN101851413B CN101851413B CN 200910132930 CN200910132930A CN101851413B CN 101851413 B CN101851413 B CN 101851413B CN 200910132930 CN200910132930 CN 200910132930 CN 200910132930 A CN200910132930 A CN 200910132930A CN 101851413 B CN101851413 B CN 101851413B
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Abstract
The invention provides a paint composition which comprises an aqueous continuous liquid phase, silicon dioxide particles, fatty group polyurethane particles, and siloxane modified by fatty alcohol polyethenoxy ether and/or polyether, wherein the silicon dioxide particles are dispersed in the aqueous continuous liquid phase, and the volume average particle size of the silicon dioxide particles is less than 150 nm; the weight of the siloxane modified by the fatty alcohol polyethenoxy ether and/or polyether is higher than 0% and lower than 15%, based on the weight of the silicon dioxide particles; the pH value of the composition is not lower than 5; and the weight ratio of silicon dioxide particles to polyurethane is 4:1 to 9:1. The invention also provides an anti-foul easy-cleaning product with a coating formed by the composition and a preparation method thereof.
Description
Technical field
The present invention relates to a kind of coating composition, anti-foul easy-cleaning product and preparation method thereof; Relate in particular to a kind of anti-foul easy-cleaning product, particularly aluminium-plastic panel that is used on aluminium-plastic panel forming coating composition that anti-soil is prone to the cleaning coating, prepares the method for goods and have the coating that makes by said composition by said composition.
Background technology
Aluminium-plastic panel is a kind of novel finishing material that is used for indoor and outdoor, can be used for curtain wall, places such as direction board.Aluminium-plastic panel unites two into one with the light weight of plastics is inexpensive owing to the texture that metal is noble, be easy to processing characteristics, becomes a kind of emerging building and ornament materials rapidly, and extends to the advertising sign industry gradually.Aluminium-plastic panel mainly is made up of intermediary Vilaterm and two-layer up and down aluminium sheet.This structure makes aluminium-plastic panel have a lot of traditional decoration materials, glass for example, and ceramic tile, not available property such as timber, anticorrosive like shock resistance, weight is lighter etc.As a rule, be used for outdoor aluminium-plastic panel surface and also can apply one deck fluorocarbon coating, for example pvdf (PVDF) is used for indoor aluminium-plastic panel and then can applies one deck polyester coating.
But, generally, after through long-time the placement; Even those have applied PVDF, the aluminium-plastic panel surface with certain antifouling property all can be by dust, and greasy dirt etc. stain and dirty; Thereby the appearance that influence is decorated needs regularly these outdoor decoration materials to be carried out cleaning.Therefore, need to develop a kind of long-time anti-soil that has, keep the aluminium-plastic panel material that self cleans.
Summary of the invention
An object of the present invention is to provide a kind of aluminium-plastic panel with long-term anti-soil, performance easy to clean, another object of the present invention provides a kind of compsn that long-term anti-soil and performance easy to clean can be provided for aluminium-plastic panel.
The contriver unexpectedly finds, through at the specific anti-soil of aluminium-plastic panel surface-coated one deck inventor invention, be prone to the cleaning coating, can make the long-term anti-soil of aluminium-plastic panel and easy to clean.And, utilize existing composited aluminum and plastic decking finishing material production line, apply easy cleaning coating of the present invention continuously at the hard metal substrate surface, hot pressing subsequently can make long-term anti-soil and aluminium-plastic panel of the present invention easy to clean.Surprised especially is that coating composition of the present invention not only can form a uniform coating on the aluminium-plastic panel surface of ultra-low surface energy, and this coating can still be kept good long-term anti-soil, be prone to sanitary characteristics after standing above-mentioned hot pressing.
First aspect of the present invention provides a kind of compsn, and said compsn comprises:
The continuous liquid phase of water-based;
Be dispersed in the silicon dioxide granule in the continuous liquid phase of said water-based, the volume average particle size of wherein said silicon dioxide granule is below 150 nanometers;
The aliphatic polyurethane particle; With
By the weight of said silicon dioxide granule, be higher than 0% and be lower than the AEO of 15 weight % and/or polyether-modified siloxanes;
Wherein, the pH of said compsn is not less than 5, and the weight ratio of said silicon dioxide granule and said urethane is in 4: 1 to 9: 1 scope.
Second aspect of the present invention provides a kind of method for preparing goods, and said method comprises compsn recited above is coated on the major surfaces of substrate.
The 3rd aspect of the present invention provides a kind of goods, and said goods comprise:
Substrate; With
The coating that on the major surfaces of said substrate, forms with compsn recited above.
Coating by compsn of the present invention forms can obviously be improved the easy cleaning function that has composited aluminum and plastic decking now; Make dust, flue gas etc. be difficult in this coatingsurface deposition; Use the water that does not contain sanitising agent just can easily remove the surface deposition dirt simultaneously; Prolong cleaning cycle, reduce the cleaning cost.
Description of drawings
Fig. 1 shows the structural representation according to the aluminium-plastic panel of one embodiment of this invention.
Embodiment
Among the present invention, only if specialize, term " aluminium-plastic panel " is meant and comprises the plastics sandwich layer, the matrix material of aluminium alloy layer.
Only if specialize, term " median size ", " particle size ", " size of particles ", " particle size " are meant the particulate diameter.
Only if specialize, term " nano silicon " is meant that median size is the silicon-dioxide below 150 nanometers.
Only if specialize, term " the continuous liquid phase of water-based " is meant the liquid of the water that contains 5% weight at least.
First aspect of the present invention provides a kind of compsn, and said compsn comprises:
The continuous liquid phase of water-based;
Be dispersed in the silicon dioxide granule in the continuous liquid phase of said water-based, the volume average particle size of wherein said silicon dioxide granule is below 150 nanometers, preferred 4-75 nanometer;
The aliphatic polyurethane particle; With
By the weight of said silicon dioxide granule, be higher than 0% and be lower than the AEO of 15 weight % and/or polyether-modified siloxanes;
Wherein, the pH of said compsn is not less than 5, and the weight ratio of said silicon dioxide granule and said urethane is in 4: 1 to 9: 1 scope.
Nano silicon has good anti-soil and easy clean-up performance.But the contriver finds, when the aqueous liquid dispersion that will contain nano silicon oxide is coated on the aluminium-plastic panel, is difficult to form effective coating, more is difficult to obtain evenly level and smooth coating of outward appearance, even formed coating, also is easy to come off.The contriver unexpectedly finds, adopts the compsn of above-mentioned prescription can be easily for example to form one on the aluminium-plastic panel on the surface of ultra-low surface energy firmly and the even level and smooth coating of outward appearance, and the anti-soil of coating and other performances are unaffected.And even through hot pressing, the coating that is formed by the present composition also can keep good anti-soil, easy clean-up performance.
Silicon-dioxide is known in the field.For example, can be purchased with the form (colloidal sol) that is scattered in the aqueous medium.For example, with trade(brand)name LUDOX from E.I.du Pont de Nemours & Co., Wilmington; DE, with trade(brand)name NYACOL from Nyacol Co., Ashland; MA; Or with trade(brand)name NALCO from Nalco Chemical Co., the colloidal sol of silicon-dioxide in water or alcohol solution that Naperville, IL buy.
Aliphatic poly ethenoxy group ethers and polyether modified siloxane can use as wetting agent in the present composition separately or together.Wetting agent also can combine other tensio-active agents to use.The wetting agent that is suitable for includes but not limited to the aliphatic poly ethenoxy group ether AEO-7 and the aliphatic poly ethenoxy group ether AEO-9 of the Dow Chemical Company; The polyether modified siloxane BYK346 of BYK company; Polyether-modified YSR 3286 BYK331; Polyether-modified YSR 3286 BYK378, polyether-modified YSR 3286 interpolymer BYK333.Its consumption is no more than 15 weight % by the weight of said silicon dioxide granule, preferred 3%-12%, more preferably 5%-10%.
According to some preferred embodiment of the present invention, wherein said compsn comprises the weight by said silicon dioxide granule in addition, is higher than 0% and be lower than at least a tensio-active agent of 15 weight %.Term " tensio-active agent " is meant that on a part existing hydrophilic (polarity) section has hydrophobic (nonpolar) section again and can reduce the capillary molecule of compsn.More preferably, by the weight of said silicon dioxide granule, total weight percentage of said tensio-active agent and said AEO or polyether-modified siloxanes is not more than 15 weight %.
According to some preferred embodiment of the present invention, wherein said compsn comprises the weight by said silicon dioxide granule in addition, the linking agent of 0.5 weight % to 20 weight %.More preferably, said linking agent is selected from tetraethylorthosilicise (TEOS) and/or its prepolymer.Linking agent is used for improving the degree of crosslinking of coating in the present invention.
The aliphatic polyurethane particle can be a water miscible liquid known in the field.For example be called the NeoRez R1005 that Co., Ltd buys from DSM with commodity, R960, R972, with the WF-55 that trade(brand)name Permutex buys from the meticulous coating of Si Taer ltd, WF-13-442, and the TC103 that patina worker ltd buys from the sky.
According to some preferred embodiment, the number-average molecular weight of aliphatic polyurethane described in the compsn of the present invention is more than 5,000, more preferably in 9,000 to 150,000 scope.The present invention has no special requirements to the MWD of aliphatic polyurethane, and the aliphatic polyurethane of MWD all can be used for the present invention arbitrarily.
Can contain the above water of at least 50% weight, 60% weight, 70% weight, 80% weight or 90% weight in the continuous liquid phase of water-based.Although can not contain organic solvent, particularly volatile organic solvent in the continuous liquid phase of water-based, if desired, in certain embodiments, also can contain organic solvent.Representative examples of organic comprises acetone and lower molecular weight ether and/or alcohol for example methyl alcohol, ethanol, Virahol, glycerine, terepthaloyl moietie, triethylene glycol and propyl alcohol, glycol monomethyl methyl or single ethyl ether, Diethylene Glycol first or ether, glycol dimethyl ether and triethylene glycol list first or single ether; Wherein more preferably ethanol, Virahol; And the wt ratio of alcohol and water preferably is lower than 1: 1, is beneficial to the stable of solution.The adding of ethanol equal solvent can further increase the wettability of solution, the especially wetting effect on aluminium-plastic panel.
According to some preferred embodiment, silicon dioxide granule accounts for the 0.1%-20% of composition total weight described in the compsn of the present invention, preferred again 0.2%-10%, more preferably 0.3%-8%.According to some preferred embodiment; The weight ratio of silicon dioxide granule and said urethane described in the compsn of the present invention is 4: 1-8: 1; More preferably 4.5: 1-7: 1 according to some preferred embodiment; The volume average particle size of aliphatic polyurethane particle is 10nm-1000nm in the compsn of the present invention, preferred again 15nm-500nm, more preferably 20nm-100nm.Silicon dioxide granule can have any size distribution, and for example, unimodal distribution or multimodal distribute and all can.
Composition solution of the present invention need not be generally neutral or alkalescence under the situation of acid adjusting, but also available acid for adjusting pH to 5.The pH value of compsn of the present invention is preferably 5-10, more preferably 5-9.
Compsn of the present invention can adopt conventional method, for example appropriate arbitrarily hybrid technology preparation.For example, can pass through the water dispersible nano-silicon dioxide particle, polyurethane particles, AEO or polyether-modified siloxanes add in entry and/or the organic solvent together or respectively, stir, and regulate the pH value to obtaining greater than 5.In the said process, can add a certain proportion of tensio-active agent as required, linking agent, and regulate used acid or the alkali of pH.
Second aspect of the present invention provides a kind of method for preparing goods, and said method comprises compsn recited above is coated on the major surfaces of substrate.The present invention can adopt various ordinary methods to carry out coating composition to the not special restriction of the selection of coating method, comprises the coating of line rod, roller coat; The coating of curtain formula, net roller coat cloth, spraying; Dip-coating, air-blade type coating etc., room temperature or heat drying solidify to form coating then.For example, can be coated on the aluminium-plastic panel surface, after baking and curing under the 120 degree conditions Celsius, can in substrate, form required coating with the line rod.
According to some preferred embodiment, use the wetting ability spreader that contacts with said substrate to apply said compsn in the method for the present invention, so that said compsn is coated in the said substrate.
According to some particularly preferred embodiment, the surface comprises at least a organic polymer described in the method for the present invention.More preferably, said organic polymer is to be selected from least a in the group of being made up of fluorocarbon polymer and polyester.
According to some preferred embodiment, substrate described in the method for the present invention comprises and is selected from least a in the group of being made up of curtain wall, identification plate and top ceiling, more preferably curtain wall or identification plate.
According to some preferred embodiment, substrate is processed by aluminium-plastic panel described in the method for the present invention.
According to some particularly preferred embodiment, substrate described in the method for the present invention is selected from curtain wall or the identification plate of being processed by aluminium-plastic panel.
The 3rd aspect of the present invention provides a kind of goods, and said goods comprise:
Substrate; With
The coating that on the major surfaces of said substrate, forms with compsn recited above.
According to some preferred embodiment, substrate described in the goods of the present invention comprises and is selected from least a in the group of being made up of curtain wall, identification plate and top ceiling, more preferably curtain wall or identification plate.
According to some preferred embodiment, substrate is processed by aluminium-plastic panel described in the goods of the present invention.The aluminium-plastic panel that has the coating that forms with the present composition not only has long-term anti-soil, is prone to the characteristics of cleaning, but also has kept original other performances of aluminium-plastic panel.Resulting anti-soil, being prone to cleaning aluminium-plastic panel finished product can National standard (GB/T17748-1999).
According to some particularly preferred embodiment, substrate described in the goods of the present invention is selected from curtain wall or the identification plate of being processed by aluminium-plastic panel.
Before use, can use layer protecting film at the outermost of goods of the present invention, polyethylene film for example scratches preventing.Can this protective membrane be removed in use.
Fig. 1 shows the aluminium-plastic panel according to one embodiment of this invention.Wherein 1 is the Vilaterm central layer, and 2 is bonding coat, and 3 is undercoat, and 4 is aluminium sheet, and 5 is fluorocarbon or polyester coatings, and 6 is anti-soil, the easy cleaning coating that is formed by the present composition, and 7 is polyethylene protective film.
Coat-thickness depends on the stain resistance for sample, the requirement of outward appearance and coating bonding force.Those skilled in the art can select suitable thickness according to actual needs on basis of the present invention.The ideal coating is done thick preferably below 1 μ m.Coating is too thick, apply easily inhomogeneous, thereby produce the rainbow of striated, coating's adhesion also can variation simultaneously.
Below, in conjunction with embodiment the present invention is carried out more detailed explanation.But, it is pointed out that the present invention is not limited to these embodiment.In following examples and comparative example, only if other regulation, all parts, ratio, per-cent all by weight, temperature all is meant degree centigrade.
Embodiment
Testing method:
The test of solution coating character:
Solution is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, if solution is nonwetting and be globule shape on the aluminium-plastic panel surface, this solution coating character is 1.If solution is most of wetting on the aluminium-plastic panel surface, but the part has nonwetting or the globule occurs, and the coating character of this solution is 3.If solution is wetting basically on the aluminium-plastic panel surface, but the edge section has nonwetting or droplet occurs, and the coating character of this solution is 5.If solution is complete wetting on the aluminium-plastic panel surface, coating appears fully and uniformly to be sprawled, and the coating character of this solution is 7.
Stain resistance test: sample is imbedded in the container that fills the standard ash, container is placed on the rocking equipment shakes about one minute, then sample taking-up and clean standard model are carried out aberration relatively.Aberration adopts ASTM E313 testing method to measure.Aberration is less than 1, and stain resistance is 7.Aberration is between 1 and 3, and stain resistance is 5.Aberration is between 3 and 5, and stain resistance is 3.Aberration is more than 5, and stain resistance is 1.
Coating adhesion test: use cross-hatching and 3M610 adhesive tape to verify adhesive force of coatings, the outward appearance of range estimation adhesive tape and coatingsurface according to ASTM F2252-03 (2008).Have no coating by tape stripping, then coating adhesion is 5;＜10% coating is by tape stripping, and then coating adhesion is 3;＞10% coating is by tape stripping, and then coating adhesion is 1.
Below embodiment and comparative example in adopt raw material, and originate and be listed below:
The nano silicon oxide 1115 of embodiment 1:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 3.1g 40%, 63.6g water.Keeping adding 150mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 5, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 2:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 64.2g water mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 5, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 3:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.1g 40%, 64.6g water mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 5, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 4:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.1g 40%, 64.6g water mixes.Keeping adding 500mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 5:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 1.4g 40%, 65.3g water mixes.Keeping adding 500mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 3.
The nano silicon oxide 1115 of embodiment 6:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 64.2g water mixes.Keeping adding 750mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 5, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 7:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 150mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 5, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 8:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 9:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 17.2g water, 47g ethanol mixes.Keeping adding 150mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 10:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, the 25g Virahol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 11:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 200mg wetting agent polyether modified siloxane BYK346, the tensio-active agent 1 of 2.5g 10%, 4-two (2-ethylhexyl)-sodium sulfonate (GR-5M) under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 12:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 150mg wetting agent polyether modified siloxane BYK346, the tensio-active agent 1 of 5g 10%, 4-two (2-ethylhexyl)-sodium sulfonate (GR-5M) under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 5, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 13:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1050 of embodiment 14:50% (particle diameter 20nm) 10g, the aliphatic polyurethane R1005 of 2.5g 40%, 62.5g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2327 of embodiment 15.40% (particle diameter 20nm) 12.5g, the aliphatic polyurethane R1005 of 2.5g 40%, 60g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1060 of embodiment 16:50% (particle diameter 60nm) 10g, the aliphatic polyurethane R1005 of 2.5g 40%, 62.5g water, 25g ethanol mixes.Keeping adding 500mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2329 of embodiment 17:40% (particle diameter 75nm) 12.5g, the aliphatic polyurethane R1005 of 2.5g 40%, 60g water, 25g ethanol mixes.Keeping adding 600mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 1115 of embodiment 18:15% (particle diameter 4nm) 16.6g, 15% nano silicon oxide 2326 (particle diameter 5nm) 16.7g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 19:15% (particle diameter 5nm) 16.6g, 50% nano silicon oxide 1050 (particle diameter 20nm) 5g, the aliphatic polyurethane R1005 of 2.5g 40%, 50.9g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 20:15% (particle diameter 5nm) 11.1g, 50% nano silicon oxide 1050 (particle diameter 20nm) 6.7g, the aliphatic polyurethane R1005 of 2.5g 40%, 54.7g water, 25g ethanol mixes.Keeping adding 500mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 21:15% (particle diameter 5nm) 22.2g, 50% nano silicon oxide 1050 (particle diameter 20nm) 3.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 47g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 22:15% (particle diameter 5nm) 22.2g, 40% nano silicon oxide 2329 (particle diameter 75nm) 4.2g, the aliphatic polyurethane R1005 of 2.5g 40%, 46.1g water, 25g ethanol mixes.Keeping adding 500mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 23:15% (particle diameter 5nm) 16.6g, 50% nano silicon oxide 1050 (particle diameter 20nm) 5g, the aliphatic polyurethane T103 of 3g 33%, 50.4g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 24:15% (particle diameter 5nm) 16.6g, 50% nano silicon oxide 1050 (particle diameter 20nm) 5g, the aliphatic polyurethane WF55 of 3g 31%, 50.4g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 25:15% (particle diameter 5nm) 22.2g, 50% nano silicon oxide 1050 (particle diameter 20nm) 3.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 47g water, 25g ethanol mixes.At the wetting agent AEO AEO-7 that keeps adding under the stirring condition 2.5g 10%, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 26:15% (particle diameter 5nm) 22.2g, 50% nano silicon oxide 1050 (particle diameter 20nm) 3.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 47g water, 25g ethanol mixes.At the wetting agent AEO AEO-9 that keeps adding under the stirring condition 2.5g 10%, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 27:15% (particle diameter 5nm) 22.2g, 50% nano silicon oxide 1050 (particle diameter 20nm) 3.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 47g water, 25g ethanol mixes.Keeping adding the polyether-modified YSR 3286 BYK331 of 250mg wetting agent under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 28:15% (particle diameter 5nm) 22.2g, 50% nano silicon oxide 1050 (particle diameter 20nm) 3.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 47g water, 25g ethanol mixes.Keeping adding the polyether-modified YSR 3286 interpolymer of 250mg wetting agent BYK333 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 29:15% (particle diameter 5nm) 11.1g, 50% nano silicon oxide 1050 (particle diameter 20nm) 6.7g, the aliphatic polyurethane R1005 of 2.5g 40%, 54.7g water, 25g ethanol mixes.Keeping adding the polyether-modified YSR 3286 BYK378 of 500mg wetting agent under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 30:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition; Phosphoric acid with 10% under the maintenance stirring condition is regulated pH to 5; The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 31:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition; Phosphoric acid with 10% under the maintenance stirring condition is regulated pH to 5; Add the 25mg tetraethoxy; The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of embodiment 32:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, add the 250mg tetraethoxy, the solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The result that the experimental data of table 1 and table 2 records for the compsn according to embodiment 32.Can find out that by result shown in the table 1 anti-soil of the present invention's preparation, easy cleaning aluminium-plastic panel finished product meet concerned countries standard (GB/T17748-1999).The result of table 2 shows, resulting anti-soil, is prone to the fundamental property that cleaning aluminium-plastic panel top coat has kept uncoated aluminium-plastic panel coating, and shown superior oil rub resistance characteristic.
The easy clean aluminium-plastic panel end properties of table 1 (testing) by GB/T17748-1999 is listed
The coating performance of easy clean aluminium-plastic panel of table 2 and uncoated aluminium-plastic panel relatively
| Project | The coating aluminium-plastic panel | Uncoated aluminium-plastic panel |
| Salt fog resistance | No change | No change |
| Anti-paper xerotripsis property (100 times) | No change | No change |
| Petrol-resistance | No change | No change |
| Protective membrane viscosity (no glue is residual) | Through, no glue is residual | Through, no glue is residual |
| Resistance to oily stain (5 circulation after Δ E) | Δ E:0.94-1.15 only can see little oil/ash | There is big gauging/ash on Δ E:3.38 surface |
The nano silicon oxide 2326 of embodiment 33:15% (particle diameter 5nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition; Phosphoric acid with 10% under the maintenance stirring condition is regulated pH to 5; Add the 1g tetraethoxy; The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 7, and coating adhesion is 5.
The nano silicon oxide 2326 of comparative example 1:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyacrylic ester BYK354 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 1.
The nano silicon oxide 2326 of comparative example 2:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.Keeping adding 1000mg wetting agent polyacrylic ester BYK354 under the stirring condition.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 7, and the coating stain resistance is 1, and coating adhesion is 3.
The nano silicon oxide 2326 of comparative example 3:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.At the wetting agent APG Triton BG-10 that keeps adding under the stirring condition 2.5g 10%.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 3.
The nano silicon oxide 2326 of comparative example 4:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.At the wetting agent THIXCIN PEG-40 that keeps adding under the stirring condition 2.5g 10%.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 3.
The nano silicon oxide 2326 of comparative example 5:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.At the wetting agent SAS SAS60 that keeps adding under the stirring condition 2.5g 10%.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 1.
The nano silicon oxide 2326 of comparative example 6:15% (particle diameter 4nm) 33.3g, the aliphatic polyurethane R1005 of 2.5g 40%, 39.2g water, 25g ethanol mixes.At the wetting agent 1 that keeps adding under the stirring condition 2.5g 10%, 4-two (2-ethylhexyl)-sodium sulfonate GR-5M.Obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 1.
The nano silicon oxide 2326 of comparative example 7:15% (particle diameter 4nm) 33.3g, the cycloaliphatic polyurethane T106 of 3g 33%, 38.7g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 3, and the coating stain resistance is 7, and coating adhesion is 1.
The nano silicon oxide 2326 of comparative example 8:15% (particle diameter 4nm) 33.3g, the cycloaliphatic polyurethane WF292 of 2.2g 46%, 39.5g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 3, and the coating stain resistance is 7, and coating adhesion is 1.
The nano silicon oxide 2326 of comparative example 9:15% (particle diameter 4nm) 33.3g, the cycloaliphatic polyurethane R9000 of 3g 34%, 38.7g water, 25g ethanol mixes.Keeping adding 250mg wetting agent polyether modified siloxane BYK346 under the stirring condition, obtain the solution of clear at last.Keep stirring at least three ten minutes.The solution that obtains at last is coated on the aluminium-plastic panel surface with the line rod of 6 μ m, and baking and curing is one minute under 120 degree conditions.The coating solution coating character that finally obtains is 5, and the coating stain resistance is 1, and coating adhesion is 1.
Embodiment and comparative example's test result is summarized in following table 3.
Table 3 embodiment and comparative example's test result
| The solution coating character | The coating stain resistance | | |
| Embodiment | |||
| 1 | 5 | 7 | 5 |
| |
5 | 7 | 5 |
| |
5 | 7 | 5 |
| |
7 | 7 | 5 |
| |
7 | 7 | 3 |
| |
7 | 5 | 5 |
| |
5 | 7 | 5 |
| Embodiment 8 | 7 | 7 | 5 |
| Embodiment 9 | 7 | 7 | 5 |
| Embodiment 10 | 7 | 7 | 5 |
| Embodiment 11 | 7 | 7 | 5 |
| Embodiment 12 | 7 | 5 | 5 |
| Embodiment 13 | 7 | 7 | 5 |
| Embodiment 14 | 7 | 7 | 5 |
| Embodiment 15 | 7 | 7 | 5 |
| Embodiment 16 | 7 | 7 | 5 |
| Embodiment 17 | 7 | 7 | 5 |
| Embodiment 18 | 7 | 7 | 5 |
| Embodiment 19 | 7 | 7 | 5 |
| Embodiment 20 | 7 | 7 | 5 |
| Embodiment 21 | 7 | 7 | 5 |
| Embodiment 22 | 7 | 7 | 5 |
| Embodiment 23 | 7 | 7 | 5 |
| Embodiment 24 | 7 | 7 | 5 |
| Embodiment 25 | 7 | 7 | 5 |
| Embodiment 26 | 7 | 7 | 5 |
| Embodiment 27 | 7 | 7 | 5 |
| Embodiment 28 | 7 | 7 | 5 |
| Embodiment 29 | 7 | 7 | 5 |
| Embodiment 30 | 7 | 7 | 5 |
| Embodiment 31 | 7 | 7 | 5 |
| |
7 | 7 | 5 |
| Embodiment 33 | 7 | 7 | 5 |
| The comparative example 1 | 1 | ||
| The comparative example 2 | 7 | 1 | 3 |
| The comparative example 3 | 3 | ||
| The comparative example 4 | 3 | ||
| The comparative example 5 | 1 | ||
| The comparative example 6 | 1 | ||
| The comparative example 7 | 3 | 7 | 1 |
| The comparative example 8 | 3 | 7 | 1 |
| The comparative example 9 | 5 | 1 | 1 |
Claims (14)
1. compsn, said compsn comprises:
The continuous liquid phase of water-based;
Be dispersed in the silicon dioxide granule in the continuous liquid phase of said water-based, the volume average particle size of wherein said silicon dioxide granule is below 150 nanometers;
Aliphatic polyurethane particle, the number-average molecular weight of wherein said aliphatic polyurethane are more than 5,000 and volume average particle size is 10nm to 1000nm; With
By the weight of said silicon dioxide granule, be higher than 0% and be lower than the AEO of 15 weight % and/or polyether-modified siloxanes;
Wherein, the pH of said compsn is not less than 5, and the weight ratio of said silicon dioxide granule and said urethane is in 4: 1 to 9: 1 scope.
2. compsn according to claim 1, wherein said compsn also comprises the weight by said silicon dioxide granule, is higher than 0% and be lower than the tensio-active agent of 15 weight %.
3. compsn according to claim 1, wherein said compsn also comprises the weight by said silicon dioxide granule, the linking agent of 0.5 weight % to 20 weight %.
4. compsn according to claim 1, the number-average molecular weight of wherein said aliphatic polyurethane is in 9,000 to 150,000 scope.
5. according to each described compsn among the claim 1-3, the continuous liquid phase of wherein said water-based is made up of organic solvent and water.
6. compsn according to claim 5, wherein said solvent are ethanol and/or Virahol, and the wt ratio of ethanol and/or Virahol and water is lower than 1: 1.
7. compsn according to claim 3, wherein said linking agent are selected from tetraethylorthosilicise and/or its prepolymer.
8. method for preparing goods, said method comprise each described compsn in the claim 1 to 7 are coated on the major surfaces of substrate.
9. method according to claim 8 wherein uses the wetting ability spreader that contacts with said substrate to apply said compsn, so that said compsn is coated in the said substrate.
10. according to Claim 8 or 9 described methods, wherein said surface comprises at least a organic polymer.
11. method according to claim 10, wherein said organic polymer are to be selected from least a by in fluorocarbon polymer and/or the polyester.
12. according to Claim 8 or 9 described methods, wherein said substrate comprises and is selected from least a in the group of being made up of curtain wall, identification plate and top ceiling.
13. goods, said goods comprise:
Substrate; With
Use the coating that on the major surfaces of said substrate, forms according to each described compsn in the claim 1 to 7.
14. goods according to claim 13, wherein said substrate is an aluminium-plastic panel.
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| CN102719123B (en) * | 2012-07-05 | 2014-07-16 | 上海多纶化工有限公司 | External application anti-drop antifogging agent composition of agricultural film |
| CN105440825B (en) * | 2014-09-01 | 2018-10-12 | 上海三银制漆有限公司 | The aqueous fluorocarbon coating and its preparation method and application of resistance to greasy dirt |
| CN106700563A (en) * | 2015-07-13 | 2017-05-24 | 中国科学院化学研究所 | Printing plate material cleaning and repairing liquid for ink-jet printing direct-to-plate, and preparation method thereof |
| TW202006079A (en) * | 2018-06-28 | 2020-02-01 | 日商日東電工股份有限公司 | Antifouling polymer composite |
| CN110922872A (en) * | 2018-09-20 | 2020-03-27 | 3M创新有限公司 | Glass soot-resistant coating composition, soot-resistant coating dispersion and articles comprising same |
| CN109943217A (en) * | 2019-03-26 | 2019-06-28 | 江苏炫智新材料科技有限公司 | A kind of preparation method of the anti-graffiti ceiling board of durability hydrophobic oleophobic |
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| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN1690146A (en) * | 2004-04-27 | 2005-11-02 | 拜尔材料科学有限责任公司 | UV-curable coating composition |
| CN1717457A (en) * | 2002-02-04 | 2006-01-04 | 旭化成株式会社 | Antifouling water-based coating composition |
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| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN1717457A (en) * | 2002-02-04 | 2006-01-04 | 旭化成株式会社 | Antifouling water-based coating composition |
| CN1690146A (en) * | 2004-04-27 | 2005-11-02 | 拜尔材料科学有限责任公司 | UV-curable coating composition |
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