CN103087559A - Nanometer ultrathin conductive coating composition and preparation method thereof - Google Patents
Nanometer ultrathin conductive coating composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer ultrathin conductive coating composition and a preparation method thereof. Tetraethoxysilane oligomer and fluoroalkyl silane are taken as film forming matters, nanometer conductive zinc oxide is added to be served as a conductive filler, the nanometer ultrathin conductive coating composition with excellent performances, greenness and environment-friendliness and self-setting capability is prepared in low cost and through a simple process, and a nanometer ultrathin conductive coating with smoothness, good adhesive force, high hardness and excellent conductivity can be obtained after the nanometer ultrathin conductive coating composition is coated on the surface of a basic material and is solidified.
Description
Technical field
The invention belongs to technical field of coatings, relate to paint coatings, relate to particularly a kind of Nano ultrathin electric-conductive coating composition and preparation method thereof.
Background technology
Traditional coating adopts the materials such as saturated polyurethane (PU), acrylic resin, Synolac, fluoro-resin, epoxy resin as main film forming substance usually, exist that second-order transition temperature is high, film-forming temperature is high, can't self-vulcanizing, the shortcoming such as hardness is low.Solvent based coating is functional, can self-vulcanizing makes the paint film of various hardness, but high volatile volatile organism wherein can be to environment, and exists the high and problem such as waste energy of cost.Development along with science and technology, the kind of coating increases rapidly, in the various coating of open report, won as many merits such as the coating of main raw material weathering resistance is good, non-corrosibility good because having concurrently, high temperature resistant, electrical insulation capability good, ultrahigh hardness, sticking power are good, thermo-oxidative stabilities with tetraethoxy and paid attention to widely, and obtained generally in transparent, high hardness wear-resisting paint field and used.For example:
CN102194541B discloses preparation method of a kind of conductive film and products thereof.Described preparation method comprises the following steps: A) get one or both mixtures in tetraethoxy, 3-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane and vinyltrimethoxy silane in mole deal 1:1:1 ratio, obtain siliceous reactant; B) with steps A) in siliceous reactant mix with water and alcohol equal solvent for 2 times of above-mentioned siliceous reactant total mole numbers, and more than uniform stirring 12h, obtain work in-process coating; The electro-conductive material that C) will account for total mass 3%-50% joins and carries out uniform stirring in work in-process coating, obtains the coating finished product; D) coating being coated on film base material with coating method, is to heat 5-60min under the condition of 70 ℃-250 ℃ in temperature, thereby forms continuity hole conductive film at the film forming substrate surface.This invention can reduce the products production cost and improve transparence.
CN101157800B discloses a kind of preparation method of polyaniline/silicon composite, it is characterized in that, make tetraethoxy at the electrically conductive polyaniline surface generation hydrolytic condensation of mineral acid doping, preparation self-dispersion type conductive polyaniline/silicon composite material in weakly acidic solution.The characteristics of this matrix material are to have good electroconductibility and thermostability, and do not need just can be dispersed in dehydrated alcohol or water medium by any dispersion agent again, and form stable dispersion system.It both can with the macromolecular material blend of many water-soluble or pure dissolubilities, and be coated with or the method for evaporating is prepared the conductive polymer film of excellent performance by casting, also can be used as the coating that the filler preparation has antistatic or anti-corrosion function.
Conductive zinc oxide owing to having good dispersion property, the advantage that nontoxic, whiteness is high, physical and chemical stability is good and production cost is low by a large amount of for the preparation of transparent or light electrically conducting coating, the electrically conducting coating surface smoothing of making and color homogeneous.The drawbacks limit that but conductive effect is limited and addition is bigger than normal the direct application of conductive zinc oxide in a lot of fields, have not yet to see and adding the report that conductive zinc oxide is made electrically conducting coating with tetraethoxy in as the coating of main film forming substance.
Summary of the invention
One of the object of the invention is for the deficiencies in the prior art, a kind of Nano ultrathin electric-conductive coating composition is provided, it is with on the basis of tetraethoxy as main film forming substance, by add the electrically conducting coating that the conductive filler material nanometer conductive zinc oxide is made in composite formula, the coatingsurface of this electrically conducting coating smooth smooth, sticking power good, hardness is high, thin thickness, particularly conductivity is excellent.
Two of the object of the invention is to provide the preparation method of described Nano ultrathin electric-conductive coating composition.
Three of the object of the invention is to provide a kind of preparation method of Nano ultrathin conductive coating.
For one of achieving the above object, the present invention adopts following technical scheme:
A kind of Nano ultrathin electric-conductive coating composition comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 80-100, fluoroalkyl silane 1-15, nanometer conductive zinc oxide 0.01-5, solvent 10-50.
In Nano ultrathin electric-conductive coating composition of the present invention, described " nanometer " is nano level, understanding according to prior art, it means several nanometers to tens nanometers, 1nm-99nm for example, although the present invention is defined as " nanometer " level, it has also comprised submicron order, be the scope of hundreds of nanometer, the scope of 100-999nm for example.As preferably, in " Nano ultrathin electric-conductive coating composition " of the present invention, described nanometer is: 10-80nm.
In Nano ultrathin electric-conductive coating composition of the present invention, described " ultra-thin " means thickness range is 1-15 μ m.
The preferred SiO of tetraethoxy oligopolymer of the present invention
2Content be the tetraethoxy oligopolymer of 40wt%-80wt%, can select known tetraethoxy oligopolymer, such as the commercially available prod, perhaps according to the record of prior art and synthetic voluntarily.But for improving effect, the hydrolyzed solution of the preferred homemade tetraethoxy of the present invention.
Described SiO
2Content be 40wt%-80wt%, can be for example 40wt%-66.1wt%, 54.7wt%-73.4wt%, 49wt%-80wt%, 40wt%, 42.3wt%, 45wt%, 47.2wt%, 50wt%, 53.5wt%, 55wt%, 58.4wt%, 60wt%, 61.9wt%, 65wt%, 70wt%, 70.5wt%, 75wt%, 79.7wt%, 80wt%; Be preferably 50wt%-70wt%; 55wt%-65wt% more preferably.
The hydrolyzed solution of described homemade tetraethoxy is to be carried out the evenly rear hydrolysis acquisition of mixing of component of proportioning by following parts by weight: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2.
The parts by weight of described tetraethoxy oligopolymer are 80-100, can be for example 80-85,83.4-97.9,93-100,80,80.3,82,84,85,86.4,89.2,90,91.7,92.5,94,95,96.3,97.1,98,99.5,100; Be preferably 85-95; 88-92 more preferably.
The combination of a kind of in the preferred ten trifluoro octyltri-ethoxysilane of fluoroalkyl silane of the present invention, 17 fluorine decyl triethoxyl silanes, 17 fluorine decyl Trimethoxy silanes or at least two kinds; More preferably 17 fluorine decyl triethoxyl silanes.
The parts by weight of described fluoroalkyl silane are 1-15, can be for example 1-9.6,4.4-13.9,7.5-15,1,1.5,1.85,2,2.3,2.5,3,3.18,3.5,4,4.25,5,5.2,6,6.05,6.7,7,7.26,8,8.9,9,9.03,9.35,10,10.1,12.7,13,13.4,14,14.5,15; Be preferably 2-12; 5-10 more preferably.
The preferred nanometer conductive zinc oxide powder of nanometer conductive zinc oxide of the present invention, its median size is 10-80nm, the volume specific resistance of powder is minimum reaches 2.5 * 10
-3Ω cm.Described nanometer conductive zinc oxide can be selected known product, obtains such as commercially available, or is prepared according to prior art and obtains.its typical but non-limiting preparation method has a detailed description in patent CN1259244C, now be summarized as follows: (1) at first synthetic zinc subcarbonate presoma: the soluble salt of zinc and doped element (comprising aluminium, gallium, indium, yttrium, scandium, tin, germanium, silicon) is mixed with mixing solutions, concentration is 0.5mol/L-5.0mol/L, and the interpolation molar weight of doped element is the 0.1-10.0% of zinc and doped element integral molar quantity, (2) will be as the sodium carbonate of precipitation agent, in sodium bicarbonate or ammonium bicarbonate soln and step (1), the mixing salt solution of preparation is added drop-wise in water simultaneously, the concentration of precipitation agent is 0.5mol/L-4.0mol/L, keeping the temperature of reaction system in the dropping process is 40 ℃-75 ℃, the pH value is controlled in the 7.0-7.5 scope, when the white zinc subcarbonate precipitation that Uniform Doped is arranged generates, after dripping, precipitant solution replenish to drip again the sodium hydroxide solution of 0.5-4.0mol/L or ammonia soln to keep the constant of pH value, until the mixing salt solution of step (1) preparation is added dropwise to complete: ageing 0-4 hour, (3) dry after the precipitate and separate that step (2) is made, the powder of gained is calcined under the mixed atmosphere of hydrogen and argon gas, and calcining temperature is 400 ℃-700 ℃, and constant temperature time is 0-4 hour, can obtain final conductive zinc oxide powder after calcining.
Preferably, the particle diameter of nanometer conductive zinc oxide of the present invention is 10-40nm, can be for example 10-27.4nm, 14.2-36.9nm, 21-40nm, 10nm, 12.5nm, 13nm, 15nm, 16.7nm, 19nm, 20nm, 22.3nm, 25nm, 27nm, 28.1nm, 30nm, 31.8nm, 34.5nm, 35nm, 37.6nm, 39nm, 40nm; 10-30nm more preferably; 15-25nm more preferably.
Preferably, the volume specific resistance of nanometer conductive zinc oxide of the present invention is 5.0 * 10
-3-1.0 * 10
2Ω cm can be for example 5.0 * 10
-3-1.0 * 10
-1Ω cm, 7.5 * 10
-2-1.4 * 10
1Ω cm, 8.7 * 10
-1-1.0 * 10
2Ω cm, 5.0 * 10
-3Ω cm, 6.2 * 10
-3Ω cm, 1.0 * 10
-2Ω cm, 3.8 * 10
-1Ω cm, 0.5 * 10
0Ω cm, 1.0 * 10
1Ω cm, 4.9 * 10
1Ω cm, 1.0 * 10
2Ω cm.
The parts by weight of described nanometer conductive zinc oxide are 0.01-5, can be for example 0.01-0.86,0.64-3.9,2.7-5,0.01,0.02,0.05,0.1,0.5,0.8,1,1.03,1.26,1.5,1.85,2,2.3,2.41,2.5,2.6,2.78,2.9,3,3.18,3.45,3.5,3.7,3.91,4,4.25,4.5,4.63,4.8,5; Be preferably 0.05-4; 0.1-2 more preferably.
Solvent of the present invention is water or organic solvent.Described organic solvent is ethanol, acetone, dimethylbenzene, hexanaphthene, pimelinketone, ethyl acetate, propyl carbinol, Virahol, dimethyl formamide, N-BUTYL ACETATE, No. 200 solvent oils for example, can be the combination of a kind of in them or at least two kinds.Described solvent is preferably the combination of a kind of in water, ethanol, acetone or at least two kinds, and described combination is water/ethanol, water/acetone, ethanol/acetone, water/ethanol/acetone for example.
The parts by weight of described solvent are 10-50, can be for example 10-33.6,20.4-47.9,18.7-50,10,10.8,15,16.5,20,22.6,25,27.1,30,31,35,39.2,40,41.7,45,48.3,50; Be preferably 15-40; 20-30 more preferably.
Preferably, described Nano ultrathin electric-conductive coating composition of the present invention is as follows:
A kind of Nano ultrathin electric-conductive coating composition comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 85-95, fluoroalkyl silane 2-12, nanometer conductive zinc oxide 0.05-4, solvent 15-40.
Further preferred, described Nano ultrathin electric-conductive coating composition of the present invention is as follows:
A kind of Nano ultrathin electric-conductive coating composition comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 88-92, fluoroalkyl silane 5-10, nanometer conductive zinc oxide 0.1-2, solvent 20-30.
" comprising " of the present invention, mean it except described component, can also contain other components, these other components are given described Nano ultrathin electric-conductive coating composition with different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... make ".
For achieve the above object two, the present invention adopts following technical scheme:
A kind of preparation method of Nano ultrathin electric-conductive coating composition comprises the steps:
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 2wt%-30wt%.
Described 2wt%-30wt% can be for example 2wt%-10.7wt%, 6.3wt%-26.2wt%, 14.5wt%-30wt%, 2wt%, 2.5wt%, 3.7wt%, 5wt%, 7.8wt%, 9wt%, 10wt%, 12.4wt%, 13wt%, 15wt%, 16.8wt%, 18wt%, 20wt%, 20.3wt%, 21.5wt%, 23wt%, 25wt%, 27.6wt%, 28wt%, 29.1wt%, 30wt%; Be preferably 3wt%-20wt%; 5wt%-10wt% more preferably.
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 10-60min obtains ultra-sonic dispersion liquid.
Described 10-60min can be for example 10-46.4min, 33-54.9min, 21.8-60min, 10min, 12.5min, 15min, 19.4min, 20min, 25min, 28.3min, 30min, 31.7min, 35min, 40min, 43min, 45min, 47.5min, 50min, 51.1min, 55min, 56.2min, 60min; Be preferably 15-50min; 20-40min more preferably.
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer.
Described ultra-sonic dispersion liquid evenly mixes with the tetraethoxy oligopolymer, preferably adopts following three kinds of modes:
First kind of way:
1. prepare the raw material of the hydrolyzed solution of preparation tetraethoxy according to the ratio of following parts by weight: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2;
2. evenly mix removing tetraethoxy material in addition in aforementioned base materials, get the mixed solution I;
3. the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I, gets the mixed solution II;
4. drip tetraethoxy in the mixed solution II, mix.
The second way:
1. prepare the raw material of the hydrolyzed solution of preparation tetraethoxy according to the ratio of following parts by weight: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2;
2. ethanol, butylacetate, diethylene glycol monobutyl ether, water are mixed, drip acetic acid to PH=2, get mixing solutions;
3. under 60 ℃ of water bath with thermostatic control whipped states to step mixed solution and dripping tetraethoxy 2., drip tetraethoxy in 1.5h, then constant temperature stirs 1h, obtains water white transparency teos hydrolysis liquid;
4. drip triethylamine and regulate pH value to 6.5, namely obtain the tetraethoxy oligopolymer;
5. the ultra-sonic dispersion liquid that adds step (2) to obtain in the tetraethoxy oligopolymer mixes.
The third mode:
1. the component of following parts by weight is evenly mixed: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2 get the tetraethoxy oligopolymer;
2. the ultra-sonic dispersion liquid that adds step (2) to obtain in the tetraethoxy oligopolymer mixes.
First kind of way particularly preferably wherein.
(4) high speed dispersion 5-30min at the temperature of 20 ℃-100 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Described 20 ℃-90 ℃ can be for example 20 ℃-61.7 ℃, 34.1 ℃-86.9 ℃, 43.4 ℃-100 ℃, 20 ℃, 23.6 ℃, 25 ℃, 27.4 ℃, 30 ℃, 35 ℃, 37.3 ℃, 40 ℃, 43.6 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 61.7 ℃, 65 ℃, 69 ℃, 70 ℃, 72.5 ℃, 75 ℃, 76.2 ℃, 80 ℃, 84 ℃, 85 ℃, 89.3 ℃, 90 ℃; Be preferably 30 ℃-80 ℃; More preferably 40-70 ℃.
Described 5-30min can be for example 5-16.4min, 13-24.9min, 21.8-30min, 5min, 7.5min, 8.1min, 10min, 11.7min, 13min, 15min, 16.2min, 17min, 18min, 19.2min, 20min, 21min, 23.5min, 25min, 28.3min, 30min; Be preferably 10-25min; Most preferably be 15-20min.
The preferred rotating speed of described high speed dispersion is 800-4500rpm, can be for example 800-2000rpm, 1740-3506rpm, 2893-4500rpm, 800rpm, 930rpm, 1000rpm, 1004rpm, 1235rpm, 1500rpm, 1850rpm, 2000rpm, 2278rpm, 2500rpm, 2913rpm, 3000rpm, 3120rpm, 3370rpm, 3500rpm, 3785rpm, 4000rpm, 4165rpm, 4300rpm, 4419rpm, 5000rpm; More preferably 1500-2700rpm.
To sum up, the preparation method of a kind of Nano ultrathin electric-conductive coating composition of the present invention comprises the steps: after technical scheme optimization
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 3wt%-20wt%;
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 15-50min obtains ultra-sonic dispersion liquid;
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer;
(4) high speed dispersion 10-25min under the rotating speed of the temperature of 30 ℃-80 ℃ and 800-4500rpm, obtain the Nano ultrathin electric-conductive coating composition.
The preparation method of a kind of Nano ultrathin electric-conductive coating composition of the present invention, technical scheme comprise the steps: after further optimizing
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 5wt%-10wt%;
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 20-40min obtains ultra-sonic dispersion liquid;
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer:
1. prepare the raw material of the hydrolyzed solution of preparation tetraethoxy according to the ratio of following parts by weight: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2;
2. evenly mix removing tetraethoxy material in addition in aforementioned base materials, get the mixed solution I;
3. the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I, gets the mixed solution II;
4. drip tetraethoxy in the mixed solution II, mix;
(4) high speed dispersion 15-20min under the rotating speed of the temperature of 40 ℃-70 ℃ and 1500-2700rpm, obtain the Nano ultrathin electric-conductive coating composition.
For achieve the above object three, the present invention adopts following technical scheme:
A kind of preparation method of Nano ultrathin conductive coating comprises and solidifies 5-15min after being coated on base material under 60-100 ℃.
Described base material can be the material of any preparation coated with conductive coating, such as timber, metal, plastics, glass, stupalith etc.
Described 60 ℃-100 ℃ can be for example 60 ℃-91.7 ℃, 74.1 ℃-86.9 ℃, 63.4 ℃-100 ℃, 60 ℃, 61.7 ℃, 63.6 ℃, 65 ℃, 67.3 ℃, 69 ℃, 70 ℃, 72.5 ℃, 74 ℃, 76.2 ℃, 79 ℃, 80 ℃, 82.5 ℃, 85 ℃, 88.3 ℃, 90 ℃, 91.6 ℃, 95 ℃, 97.5 ℃, 100 ℃; Be preferably 70 ℃-90 ℃; More preferably 75-85 ℃.
Described 5-15min can be for example 5-9.4min, 6.3-14.9min, 11.8-15min, 5min, 6min, 6.2min, 7min, 7.5min, 8.1min, 9.3min, 10min, 10.8min, 11.7min, 12min, 13min, 14.5min, 15min; Be preferably 6-14min; Most preferably be 8-12min.
The preparation method of a kind of Nano ultrathin conductive coating of the present invention is solidified 6-14min after comprising the steps: to be coated on base material after technical scheme optimization under 70-90 ℃.
Solidify 8-12min after comprising the steps: to be coated on base material after the preparation method of a kind of Nano ultrathin conductive coating of the present invention, technical scheme further optimize under 75-85 ℃.
After Nano ultrathin electric-conductive coating composition of the present invention is coated on substrate surface and curing, obtain ultra-thin, smooth, continuous, smooth coating (coating planeness≤3 μ m), the sticking power of coating (measuring according to GB/T9286-1998) is 0 grade, pencil hardness (measuring according to GB/T6739-1996) is 5H-6H, thickness (measuring according to GB/T1764-1989) is 1-15 μ m, and the resistivity of electrically conducting coating (adopting the two electrical measurement four point probe testers of RTS-9 to measure) is 10
-1-10
3Ω cm.
The present invention adopts tetraethoxy oligopolymer, fluoroalkyl silane as filmogen, add nanometer conductive zinc oxide as conductive filler material, but make the Nano ultrathin electric-conductive coating composition of excellent performance, environmental protection self cure with cheap cost and simple technique, its be coated on substrate surface and solidify after can obtain smooth smooth, sticking power good, hardness is high, conductivity is excellent Nano ultrathin conductive coating.
Below in conjunction with embodiment, the present invention is described in further detail.But following embodiment is only simple and easy example of the present invention, does not represent or limit the scope of the present invention, and protection scope of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
The following examples can make those skilled in the art more fully understand the present invention, but are not limited to this.
Embodiment 1:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 40wt%.
Prepare in accordance with the following steps the Nano ultrathin electric-conductive coating composition:
(1) 5g nanometer conductive zinc oxide (the Al doping is the 1.0mol% of integral molar quantity) is added in ethanol, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 15wt%;
(2) 15g ten trifluoro octyltri-ethoxysilane are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 30min obtains ultra-sonic dispersion liquid;
(3) 67.3g ethanol, 13.5g butylacetate, 15.7g diethylene glycol monobutyl ether, 8.4g acetic acid, 10g triethylamine, 13.2g water are evenly mixed, get the mixed solution I;
(4) the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I that step (3) obtains, and gets the mixed solution II;
(5) drip the 304g tetraethoxy in the mixed solution II that obtains to step (4), mix;
(6) adopt high speed dispersor with the rotating speed high speed dispersion 30min of 4000rpm at the temperature of 60 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Adopt method of roll coating that the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on plank, solidify 10min under 80 ℃, obtain ultra-thin, smooth, continuous, smooth coating.The coating planeness is 2 μ m, and thickness is 14 μ m, and pencil hardness is 6H, and sticking power is 0 grade, and resistivity is 5.67 * 10
-1Ω cm.
Embodiment 2:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 80wt%.
Prepare in accordance with the following steps the Nano ultrathin electric-conductive coating composition:
(1) 0.01g nanometer conductive zinc oxide (the Al doping is the 2.0mol% of integral molar quantity) is added in ethanol, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 2wt%;
(2) 10g 17 fluorine decyl triethoxyl silanes are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 60min obtains ultra-sonic dispersion liquid;
(3) 33.6g ethanol, 7.4g butylacetate, 5g diethylene glycol monobutyl ether, 8.1g acetic acid, 9.3g triethylamine, 7.2g water are evenly mixed, get the mixed solution I;
(4) the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I that step (3) obtains, and gets the mixed solution II;
(5) drip the 152g tetraethoxy in the mixed solution II that obtains to step (4), mix;
(6) adopt high speed dispersor with the rotating speed high speed dispersion 25min of 2000rpm at the temperature of 80 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Adopt the obliterating method that the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on sheet glass, solidify 15min under 60 ℃, obtain ultra-thin, smooth, continuous, smooth coating.The coating planeness is 1 μ m, and thickness is 12 μ m, and pencil hardness is 6H, and sticking power is 0 grade, and resistivity is 4.73 * 10
1Ω cm.
Embodiment 3:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 50wt%.
(1) 2.6g nanometer conductive zinc oxide (the Ga doping is the 1.0mol% of integral molar quantity) is added in ethanol, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 10wt%;
(2) 5g 17 fluorine decyl Trimethoxy silanes are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 40min obtains ultra-sonic dispersion liquid;
(3) 26.7g ethanol, 4g butylacetate, 5.1g diethylene glycol monobutyl ether, 6g acetic acid, 8g triethylamine, 10.5g water are evenly mixed, get the mixed solution I;
(4) the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I that step (3) obtains, and gets the mixed solution II;
(5) drip the 243.2g tetraethoxy in the mixed solution II that obtains to step (4), mix;
(6) adopt high speed dispersor with the rotating speed high speed dispersion 20min of 1500rpm at the temperature of 90 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Employing is scraped coating method the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on plastic plate, solidifies 5min under 100 ℃, obtains ultra-thin, smooth, continuous, smooth coating.The coating planeness is 3 μ m, and thickness is 6 μ m, and pencil hardness is 5H, and sticking power is 0 grade, and resistivity is 2.14 * 10
1Ω cm.
Embodiment 4:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 60wt%.
(1) 3g nanometer conductive zinc oxide (the Sc doping is the 0.5mol% of integral molar quantity) is added to the water, is uniformly dispersed and makes the nanometer conductive zinc oxide dispersion liquid that concentration is 30wt%;
(2) 1.5g ten trifluoro octyltri-ethoxysilane are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 10min obtains ultra-sonic dispersion liquid;
(3) 44.8g ethanol, 12g butylacetate, 11g diethylene glycol monobutyl ether, 8.8g water are evenly mixed, drip acetic acid 17.3g to pH=2, get mixing solutions;
(4) under 60 ℃ of water bath with thermostatic control whipped states to the mixed solution and dripping 202.7g tetraethoxy of step (3), drip tetraethoxy in 1.5h, then constant temperature stirs 1h, obtains water white transparency teos hydrolysis liquid;
(5) drip triethylamine 9.5g to pH value=6.5 in the teos hydrolysis liquid of step (4), obtain the tetraethoxy oligopolymer;
(6) the ultra-sonic dispersion liquid that adds step (2) to obtain in the tetraethoxy oligopolymer that obtains to step (5) mixes;
(7) adopt high speed dispersor with the rotating speed high speed dispersion 5min of 800rpm at the temperature of 70 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Adopt the showering method that the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on ceramic plate, solidify 6min under 85 ℃, obtain ultra-thin, smooth, continuous, smooth coating.The coating planeness is 2 μ m, and thickness is 5 μ m, and pencil hardness is 5H, and sticking power is 0 grade, and resistivity is 3.41 * 10
2Ω cm.
Embodiment 5:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 70wt%.
(1) 4g nanometer conductive zinc oxide (the Y doping is the 2.0mol% of integral molar quantity) is added to the water, is uniformly dispersed and makes the nanometer conductive zinc oxide dispersion liquid that concentration is 20wt%;
(2) 2g 17 fluorine decyl triethoxyl silanes are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 50min obtains ultra-sonic dispersion liquid;
(3) 38.4g ethanol, 8.2g butylacetate, 14.5g diethylene glycol monobutyl ether, 10.5g acetic acid, 11g triethylamine, 7.5g water are evenly mixed, get the mixed solution I;
(4) the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I that step (3) obtains, and gets the mixed solution II;
(5) drip the 173.8g tetraethoxy in the mixed solution II that obtains to step (4), mix;
(6) adopt high speed dispersor with the rotating speed high speed dispersion 10min of 4500rpm at the temperature of 40 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Adopt spraying method that the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on tinplate, solidify 8min under 70 ℃, obtain ultra-thin, smooth, continuous, smooth coating.The coating planeness is 2 μ m, and thickness is 8 μ m, and pencil hardness is 5H, and sticking power is 0 grade, and resistivity is 1.85 * 10
1Ω cm.
Embodiment 6:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 65wt%.
(1) 1.3g nanometer conductive zinc oxide (the In doping is the 1.0mol% of integral molar quantity) is added to the water, is uniformly dispersed and makes the nanometer conductive zinc oxide dispersion liquid that concentration is 5wt%;
(2) 12g 17 fluorine decyl Trimethoxy silanes are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 15min obtains ultra-sonic dispersion liquid;
(3) 14.5g ethanol, 8.7g butylacetate, 8.7g diethylene glycol monobutyl ether, 11.6g acetic acid, 4.35g triethylamine, 23.2g water, tetraethoxy 29g are evenly mixed, generate tetraethoxy oligopolymer 100.05g;
(4) the ultra-sonic dispersion liquid that adds step (2) to obtain in the tetraethoxy oligopolymer that obtains to step (4) mixes;
(5) adopt high speed dispersor with the rotating speed high speed dispersion 15min of 2700rpm at the temperature of 30 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Adopt brushing method that the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on tinplate, solidify 14min under 75 ℃, obtain ultra-thin, smooth, continuous, smooth coating.The coating planeness is 1 μ m, and thickness is 15 μ m, and pencil hardness is 6H, and sticking power is 0 grade, and resistivity is 6.52 * 10
2Ω cm.
Embodiment 7:
The present embodiment adopts homemade tetraethoxy oligopolymer, wherein SiO
2Content be 70wt%.
(1) 5g nanometer conductive zinc oxide (the Al doping is the 10.0mol% of integral molar quantity) is added in ethanol, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 3wt%;
(2) 7g 17 fluorine decyl triethoxyl silanes are joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 20min obtains ultra-sonic dispersion liquid;
(3) 38.4g ethanol, 8.2g butylacetate, 14.5g diethylene glycol monobutyl ether, 10.5g acetic acid, 11g triethylamine, 7.5g water are evenly mixed, get the mixed solution I;
(4) the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I that step (3) obtains, and gets the mixed solution II;
(5) drip the 173.8g tetraethoxy in the mixed solution II that obtains to step (4), mix;
(6) adopt high speed dispersor with the rotating speed high speed dispersion 25min of 2500rpm at the temperature of 20 ℃, obtain the Nano ultrathin electric-conductive coating composition.
Employing is scraped coating method the Nano ultrathin electric-conductive coating composition that the present embodiment obtains is coated on plastic plate, solidifies 12min under 90 ℃, obtains ultra-thin, smooth, continuous, smooth coating.The coating planeness is 1 μ m, and thickness is 11 μ m, and pencil hardness is 6H, and sticking power is 0 grade, and resistivity is 1.79 * 10
-1Ω cm.
Should be noted that and understand, in the situation that do not break away from the desired the spirit and scope of the present invention of accompanying claim, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Applicant's statement, above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a Nano ultrathin electric-conductive coating composition, is characterized in that, comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 80-100, fluoroalkyl silane 1-15, nanometer conductive zinc oxide 0.01-5, solvent 10-50.
2. composition according to claim 1, is characterized in that, comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 85-95, fluoroalkyl silane 2-12, nanometer conductive zinc oxide 0.05-4, solvent 15-40.
3. composition according to claim 1 and 2, is characterized in that, comprises the feed composition of following parts by weight: tetraethoxy oligopolymer 88-92, fluoroalkyl silane 5-10, nanometer conductive zinc oxide 0.1-2, solvent 20-30.
4. one of according to claim 1-3 described compositions, is characterized in that SiO in described tetraethoxy oligopolymer
2Content be 40wt%-80wt%; Be preferably 50wt%-70wt%; 55wt%-65wt% more preferably.
5. one of according to claim 1-4 described compositions, it is characterized in that, described fluoroalkyl silane is the combination of a kind of in ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl triethoxyl silanes, 17 fluorine decyl Trimethoxy silanes or at least two kinds; Be preferably 17 fluorine decyl triethoxyl silanes.
6. one of according to claim 1-5 described compositions, is characterized in that, the particle diameter of described nanometer conductive zinc oxide is 10-40nm; Be preferably 10-30nm; 15-25nm more preferably;
Preferably, the volume specific resistance of described nanometer conductive zinc oxide is 5.0 * 10
-3-1.0 * 10
2Ω cm.
7. one of according to claim 1-6 described compositions, it is characterized in that, described solvent is the combination of a kind of in water, ethanol, acetone, dimethylbenzene, hexanaphthene, pimelinketone, ethyl acetate, propyl carbinol, Virahol, dimethyl formamide, N-BUTYL ACETATE, No. 200 solvent oils or at least two kinds; Be preferably the combination of a kind of in water, ethanol, acetone or at least two kinds.
8. the preparation method of one of according to claim 1-7 described compositions, is characterized in that, described method comprises the steps:
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 2wt%-30wt%;
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 10-60min obtains ultra-sonic dispersion liquid;
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer;
(4) high speed dispersion 5-30min at the temperature of 20 ℃-90 ℃, obtain the Nano ultrathin electric-conductive coating composition;
Preferably, described method comprises the steps:
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 3wt%-20wt%;
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 15-50min obtains ultra-sonic dispersion liquid;
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer;
(4) high speed dispersion 10-25min under the rotating speed of the temperature of 30 ℃-80 ℃ and 800-4500rpm, obtain the Nano ultrathin electric-conductive coating composition;
Further optimize selection of land, described method comprises the steps:
(1) nanometer conductive zinc oxide is added in solvent, be uniformly dispersed and make the nanometer conductive zinc oxide dispersion liquid that concentration is 5wt%-10wt%;
(2) fluoroalkyl silane is joined in the nanometer conductive zinc oxide dispersion liquid that step (1) makes, ultra-sonic dispersion 20-40min obtains ultra-sonic dispersion liquid;
(3) the ultra-sonic dispersion liquid that step (2) is obtained evenly mixes with the tetraethoxy oligopolymer;
(4) high speed dispersion 15-20min under the rotating speed of the temperature of 40 ℃-70 ℃ and 1500-2700rpm, obtain the Nano ultrathin electric-conductive coating composition.
9. preparation method according to claim 8, is characterized in that, the ultra-sonic dispersion liquid described in step (3) evenly mixes with the tetraethoxy oligopolymer, in the following way:
1. prepare the raw material of the hydrolyzed solution of preparation tetraethoxy according to the ratio of following parts by weight: tetraethoxy 0.5-1, ethanol 0.1-0.6, butylacetate 0.05-0.8, diethylene glycol monobutyl ether 0.03-0.9, acetic acid 0.04-0.9, triethylamine 0.05-0.5, water 0.025-2;
2. evenly mix removing tetraethoxy material in addition in aforementioned base materials, get the mixed solution I;
3. the ultra-sonic dispersion liquid that step (2) is obtained joins in the mixed solution I, gets the mixed solution II;
4. drip tetraethoxy in the mixed solution II, mix.
10. the preparation method of a Nano ultrathin conductive coating, is characterized in that, described method comprise the described composition of one of claim 1-7 is coated on base material after, solidify 5-15min under 60-100 ℃, obtain described Nano ultrathin conductive coating;
Preferably, described method comprises and solidifies 6-14min after the described composition of one of claim 1-7 is coated on base material under 70-90 ℃.
Further preferably, described method comprises and solidifies 8-12min after the described composition of one of claim 1-7 is coated on base material under 75-85 ℃.
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| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772723A (en) * | 2014-01-17 | 2014-05-07 | 苏州斯贝孚光伏科技有限公司 | Method for non-vacuum preparation of nano thin film by taking metallic compound as precursor |
| CN103772723B (en) * | 2014-01-17 | 2017-08-04 | 苏州斯贝孚光电科技有限公司 | Using metallic compound as the antivacuum method for preparing nano thin-film of presoma |
| CN103915134A (en) * | 2014-04-17 | 2014-07-09 | 江南石墨烯研究院 | Method for preparing environment-friendly graphene-based conductive carbon paste |
| CN110820029A (en) * | 2019-11-18 | 2020-02-21 | 贵州航天南海科技有限责任公司 | Aluminum alloy conductive oxide film protective agent |
| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
| CN114045478B (en) * | 2021-10-13 | 2024-07-02 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
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