CN103897487A - Fluorine modified epoxy resin-base ink for thin-film solar cells and preparation method thereof - Google Patents
Fluorine modified epoxy resin-base ink for thin-film solar cells and preparation method thereof Download PDFInfo
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- CN103897487A CN103897487A CN201210588688.0A CN201210588688A CN103897487A CN 103897487 A CN103897487 A CN 103897487A CN 201210588688 A CN201210588688 A CN 201210588688A CN 103897487 A CN103897487 A CN 103897487A
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Abstract
The invention relates to a fluorine modified epoxy resin-base ink for thin-film solar cells and a preparation method thereof. The ink is prepared from the following components in percentage by mass: 0.5-5% of fluorine modified epoxy resin-base solution (the solid content of resin is 1-10%), 0.0001-0.1% of nano aluminum powder, 0.1-1% of viscosity regulator and the balance of solvent. The product can directly enhance the generating efficiency of the flexible or thin-film solar cell when being printed to the upper surface of the flexible or thin-film solar cell by an ink-jet printing technique.
Description
Technical field
The present invention relates to a kind of flexibility or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer and preparation method thereof, by using the surface of this ink printed at flexibility or thin-film solar cells incidence surface, directly improve the efficiency of flexibility or thin-film solar cells.
Background technology
Due to the special property of fluorine atom; fluoropolymer forms the leptospira structure of F atom at periphery parcel C-C main chain, and C-F key is highly stable, and bond energy is 485 kJ/mol; fluorine atom is very tight in the outer field arrangement of carbon skeleton, can form shielding protection to main chain and interior molecules.Protection C-C main chain is not destroyed by severe environmental conditions, and keeps the stability of height.On organo-fluorine polymer material molecule side group or side chain, contain the sterically hindered fluorine atom stronger compared with little and close power, make its surface free energy very low, show excellent waterproof and oilproof, stain resistant performance. therefore fluorocarbon coating has the special performance that some other coating hardly match, for example: fabulous weathering resistance, good chemical resistance, low friction, hydrophobic nature, oil repellency, uninflammability etc., it is applied in many Application Areass, more and more receives coating circle personage's concern.
Epoxy resin has excellent tack, thermostability, chemical-resistant, insulativity and physical strength etc., be widely used in coating, tackiness agent and prepare composite. itself is insoluble in water epoxy resin, also be difficult for disperseing in water, prepare aqueous epoxy emulsion and mainly contain at present 3 kinds of methods: mechanical process, phase inversion (solidifying agent emulsion process) and chemic modified method. wherein chemic modified method has plurality of advantages with respect to first two method: do not need additional emulsifying agent, water-fast solvent resistance is high, emulsion particle diameter little (nano level), stability in storage is good, state of cure is high, film is evenly fine and close. in recent years, utilize acrylic monomer to carry out graft modification epoxy resin, do not consume epoxy group(ing) and hydroxyl, the emulsion particle diameter obtaining is little, the good stability of emulsion, both there is the high-modulus of epoxy resin, high strength, chemicals-resistant and good preservative property, there is again acrylic resin gloss, fullness ratio, the features such as good weatherability.Aqueous epoxy resins has the advantages such as good sticking power, high-modulus, high strength, chemical-resistant and preservative property, utilize epoxy resin to carry out blending and modifying to fluorinated acrylate emulsion, can improve water-fast, resistance to solvent, sticking power and the mechanical property of coating, under the condition that does not affect service requirements, significantly reduce coating cost simultaneously.Wang Yifeng etc. pass through physical blending legal system for epoxy resin modification acrylate copolymer composite emulsion, fluorine-containing latex and epoxy emulsion are carried out blend by the total root of Qin etc., while finding film forming, resin can produce from layering, and the film obtaining like this has excellent surface property and good adhesion property.(1. glad, Wang Jingke, Zhang Qian of Wang Yue, Zhai He, Wang Fang, the modification with epoxide group fluorinated copolymer to epoxy coating, " polymer material science and engineering " 03 phase in 2012.2. the little dragon of Xu, Li Baosong, Wu Xuedong, the research of Hexafluorobutyl mathacrylate grafting epoxide powder coating, " coatings industry ", the 4th phase 56-59 page in 2010)
Effectively utilizing in the middle of project of sun power: solar photovoltaic utilization is research field with fastest developing speed in the last few years, most active.The making of general solar cell is mainly taking semiconductor material as basis, opto-electronic conversion reaction generating occurs after utilizing photoelectric material to absorb luminous energy.According to the difference of material therefor, solar cell can be divided into: 1, silicon solar cell; 2, taking inorganic salt if the multi-element compounds such as gallium arsenide III-V compound, Cadmium Sulfide, copper indium diselenide are as the solar cell of material; 3, the solar cell of preparing with functional high molecule material; 4, nano-crystalline solar battery etc.
What prior art working efficiency was the highest is taking III-V family semiconductor inorganic materials as raw-material product.For example: the quantum well of the single junction type of gallium arsenide/germanium falls into crystal structure, and its photoelectric transformation efficiency can reach >18 %; For example, and multiple junction quantum well falls into the solar cell of crystal structure: InGaP/gallium arsenide/germanium, its photoelectric transformation efficiency can be up to >30 %.Most widely used at present, taking silicon as main: comprise non-crystalline silicon, photoelectric transformation efficiency approximately 9 %; Polysilicon, photoelectric transformation efficiency approximately 14 %; Silicon single crystal, photoelectric transformation efficiency approximately 17 %.Although in price, VI family elements Si is more cheap than III-V family semiconductor GaAs, the price of its manufacture, compared with polymer organic solar batteries, or expensive many; And in application, the light weight again overall plasticization organic solar batteries of the anxiety of crack-free can be realized via the processing of printing, except price reduces, be more suitable for the demand of portable electronic product, and indoor or cloudyly all can normally use (this is that siliceous solar cell is beyond one's reach), its practicality and market application range are promoted more.
Solar cell is a gordian technique, can advance more clean Energy production.But the Cost Problems of solar cell, has reduced the economic competitiveness of heliotechnics.For overcoming this problem, thin-film solar cells is the technology of current widespread use, can reduce in a large number the usage quantity of expensive semiconductor material, but the absorbing amount of thin-film solar cells is lower, and Performance Ratio is not gone up traditional solar cell.
Thin-film solar module is to be made up of glass substrate, metal level, transparency conducting layer, electrical function box, glueing material, semiconductor layer etc.Organic and inorganic composite solar battery is the solar cell based on organic conjugate polymer-inorganic nano-crystal composite system, because of while tool organic polymer material good film-forming property, level structure and band gap are easy to regulate, can prepare low cost, big area, flexible solar battery device and inorganic nano-crystal material high stability by wet method, high mobility, can construct the advantages such as ordered nano-structure, and become the study hotspot of area of solar cell in recent years.Metal nanoparticle can direct light enter solar cell better, prevents light escape.In traditional " thick film " solar cell, nanoparticle does not have any effect, is all by this film because all light absorbs, and this just relies on its thickness.But for film, nanoparticle just can be brought into play great role.Their scattering has increased light and has rested on the time in film, makes the light of overall absorption reach a kind of level, and traditional solar cell can match in excellence or beauty.
Aluminium and Nano silver grain are in the frequency spectrum of visible part, and focused ray enters solar cell well.But optical resonance also can cause nanoparticle absorb light, this efficiency that just means solar cell can be lower.Nano grain of silver sub-resonance is just in time in the crucial absorption spectrum part of solar cell, so the absorption of light is appreciable.Aluminum nanoparticles resonance has exceeded the crucial spectra part of solar cell.Loss to energy is less, and in addition, aluminum particulate is easy to passivation, although can change shape and size, after passivation, nanoparticle attribute change is very little.Nanoparticle has rough surface, and scattered beam can enter wide spectrum wavelength region more.This can bring larger absorption, thereby improves the whole efficiency of battery.
Ink-jet printing technology can form thin film layer by the uniform deposition of liquid organic materials, and therefore, this technology can solve large photoactivation thing dimensional problem in theory better.Drop on demand ink jet technique, can be accurately by deposition of material in position in the desired amount.Because ink-jet system is very high to the utilization ratio of material, can reduce manufacture production cost.
Summary of the invention
The object of this invention is to provide a kind of flexibility or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer and preparation method thereof, by using the surface of this ink printed at flexibility or thin-film solar cells incidence surface, directly improve the efficiency of flexibility or thin-film solar cells.And flexibility or thin-film solar cells that tool was processed through this ink have self-cleaning effect.
For achieving the above object, the technical solution used in the present invention is as follows:
Fluorine modified epoxy base ink for thin-film solar cells of the present invention, comprises the following component of following mass percent:
Solution (resin solid content 1-10%) 0.5-5% of fluorine modified epoxy base resin;
Nanometer aluminium powder 0.0001-0.1%;
Viscosity-controlling agent 0.1-1%;
Surplus is solvent.
Described fluorine modified epoxy refers to the polyacrylic acid perfluoro alkyl ethyl of epoxide group, containing one or more the mixing in the polyacrylic acid perfluoro alkyl ethyl with epoxide group of nano imvite, Hexafluorobutyl mathacrylate epoxy resin containing nano-powder, dihydroxyphenyl propane epoxy-Hexafluorobutyl mathacrylate resin, dihydroxyphenyl propane epoxy-vinylformic acid perfluoro alkyl ethyl resin.
Described viscosity-controlling agent is METHYLPYRROLIDONE or poly-3 methyl thiophene.
Described solvent is one or more in alcohol, ester, ether, amine, acid amides, ketone or hydrocarbon.
Be preferably and in ink, at least contain that to account for ink mass percent be 20% ketone, 20% ester, 10% ether.
Described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, or one or more in the fluorinated alohol of above-mentioned alcohol.
Described ketone is acetone, cyclohexanone, one or more in methylethylketone, first isopropyl acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N-Methyl pyrrolidone.
Described ester is one or more in alcohol ether-ether, methyl acetate, ethyl acetate, acetic acid 1-methoxyl group-2-propyl ester, propyl acetate, butylacetate, methyl propionate or ethyl propionate, glycol ethers acetic ester, butyl glycol acetate.
Described ether is one or more in diethyl ether, dipropyl ether, tetrahydrofuran (THF), dioxan, ethylene glycol ethyl ether or ethylene glycol monomethyl ether.
Fluorine modified epoxy base ink for thin-film solar cells of the present invention, comprises the steps:
(1) by fluorine modified epoxy solution, viscosity-controlling agent and solvent, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; The one flexibility that both must need after strainer filterings more than 300 orders or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer for above emulsion.
For adapting to above industrial requirement, we have invented fluorine modified epoxy fundamental mode nanometer aluminium powder ink.This ink passes through ink jet printing device, both can be used in the backlight place of thin-film solar cells, also can be used in the light inlet film surface of thin-film solar cells, also can be used in the middle layer of thin-film solar cells simultaneously, improve the efficiency of light absorption of solar cell.Improve the generating efficiency of solar cell.
Nano metal aluminum particulate is easy to passivation, although can change shape and size, after passivation, nanoparticle attribute change is very little.Nanoparticle has rough surface, and scattered beam can enter wide spectrum wavelength region more.This can bring larger absorption, thereby improves the whole efficiency of battery.The scattering of metallic aluminium nanoparticle has increased light and has rested on the time in film, makes the light of overall absorption reach a kind of level, and traditional solar cell can match in excellence or beauty.Through using the thin-film solar cells of film processing of the present invention to improve 3-15% than the thin-film solar cells performance without the processing of this film.Thin-film solar cells is used after this film, and metallic aluminium nanoparticle can direct light enter solar cell preferably, prevents light escape.Solve in traditional " thick film " solar cell, nanoparticle does not have any effect and all essential problems that relies on thickness solution of light absorption.
Embodiment
embodiment 1
(1) by polyacrylic acid perfluoro alkyl ethyl solution (resin solid content 10%) 0.5Kg with epoxide group, viscosity-controlling agent (METHYLPYRROLIDONE) 0.1Kg, 99.3995Kg N, dinethylformamide mixes, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by 0.005Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; (5) above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells fluorine modified epoxy ink for ink-jet printer.
By the ink of the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
embodiment 2
(1) will be mixed with solution with polyacrylic acid perfluoro alkyl ethyl solution (resin solid content 8%) 2Kg, viscosity-controlling agent (METHYLPYRROLIDONE) 0.3Kg of epoxide group, with 10Kg ethanol, 20Kg acetone, 67.6999Kg glycol ethers acetic ester containing nano imvite, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by 0.0001Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; Above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells fluorine modified epoxy ink for ink-jet printer.
By the ink of the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
embodiment 3
(1) by Hexafluorobutyl mathacrylate epoxy resin solution (resin solid content 5%) 3Kg containing nano-powder, viscosity-controlling agent (METHYLPYRROLIDONE) 0.8Kg, 25Kg methyl ethyl ketone, 31.15Kg ethylene glycol ethyl ether, 20Kg butylacetate mix, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by 0.05Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; Above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells fluorine modified epoxy ink for ink-jet printer.
By the ink of the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
embodiment 4
(1) by dihydroxyphenyl propane epoxy-Hexafluorobutyl mathacrylate resin solution (resin solid content 3%) 4Kg, viscosity-controlling agent (poly-3 methyl thiophene) 1Kg, be mixed with solution with 20Kg butyl glycol acetate, 10Kg butanols, 20Kg tetrahydrofuran (THF), 44.9 Kg ethyl propionates mix, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by 0.1Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; Above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells fluorine modified epoxy ink for ink-jet printer.
By the ink of the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
embodiment 5
(1) by dihydroxyphenyl propane epoxy-vinylformic acid perfluoro alkyl ethyl resin solution (resin solid content 1%) 5Kg, viscosity-controlling agent (poly-3 methyl thiophene) 0.6Kg, use 10KgN, dinethylformamide, 20Kg acetone, 20Kg tetrahydrofuran (THF), 44.92Kg butylacetate are mixed with solution, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by 0.08Kg acetone nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; Above emulsion with after strainer filterings more than 300 orders both flexible or thin-film solar cells fluorine modified epoxy ink for ink-jet printer.
By the ink of the present embodiment, respectively according to national QB/T2730.1-2005, QB/T2603-2007, GB/T13217.2-2009, GB/T 18724-2008/ISO 2836:2004 standard detection.To the quality inspection index of ink, as proportion, pH value, surface tension, viscosity, specific conductivity etc. detect, detected result all meets national GB.Tested ink is poured in cold-resistant packing bottle, put into (20 ± 1) DEG C cryostat and take out to 24h, return to after room temperature, detect its print performance.Detected result: its reductibility is good, never degenerates, not spoiled.
This ink set is simple, easy to manufacture, and technique is easily grasped, and only needs Mixing Machine, ultrasonic dispersion and filter machinery to get final product suitability for industrialized production, easily reaches quality standards.
embodiment 7
Fluorine modified epoxy base resin solution, acetone, glycol ethers acetic ester, ethyl acetate, cyclohexanone and ethylene glycol ethyl ether are mixed according to described ratio 0.5:20:10:20:29.3:20, in emulsify at a high speed device, process 20 minutes with rotating speed 20000rpm, be processed into even mix emulsion fluid; After above mix emulsion fluid machines, with under same processing rotating speed environment, the nanometer aluminium powder that was 0.2 by weight percent in 20 minutes in batches trace adds continuously; Above emulsion after nanometer aluminium powder adds completely, more fully emulsified 20 minutes; The flexibility that both must need after 1000 object strainer filterings or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer and preparation method thereof for above emulsion.
embodiment 7
Fluorine modified epoxy base resin solution, acetone, glycol ethers acetic ester, butyl glycol acetate, cyclohexanone and methoxypropanol are mixed according to described ratio 0.5:20:10:20:29.4:20, in emulsify at a high speed device, process 10 minutes with rotating speed 100000 rpm, be processed into even mix emulsion fluid; After above mix emulsion fluid machines, with under same processing rotating speed environment, the nanometer aluminium powder that was 0.1 by weight percent in 10 minutes in batches trace adds continuously; Above emulsion after nanometer aluminium powder adds completely, more fully emulsified 10 minutes; The flexibility that both must need after 500 object strainer filterings or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer and preparation method thereof for above emulsion.
In the embodiment of the present invention, fluorine modified epoxy used is all purchased from Yongzhou Li great resin raw material company limited.
Claims (10)
1. a fluorine modified epoxy base ink for thin-film solar cells, is characterized in that, comprises the following component of following mass percent:
Solution (resin solid content 1-10%) 0.5-5% of fluorine modified epoxy base resin;
Nanometer aluminium powder 0.0001-0.1%;
Viscosity-controlling agent 0.1-1%;
Surplus is solvent.
2. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described fluorine modified epoxy refers to the polyacrylic acid perfluoro alkyl ethyl of epoxide group, containing one or more the mixing in the polyacrylic acid perfluoro alkyl ethyl with epoxide group of nano imvite, Hexafluorobutyl mathacrylate epoxy resin containing nano-powder, dihydroxyphenyl propane epoxy-Hexafluorobutyl mathacrylate resin, dihydroxyphenyl propane epoxy-vinylformic acid perfluoro alkyl ethyl resin.
3. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described viscosity-controlling agent is METHYLPYRROLIDONE or poly-3 methyl thiophene.
4. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described solvent is one or more in alcohol, ester, ether, amine, acid amides, ketone or hydrocarbon.
5. fluorine modified epoxy base ink for thin-film solar cells according to claim 1 is characterized in that: in described ink, contain ketone, ester and ether simultaneously.
6. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, or one or more in the fluorinated alohol of above-mentioned alcohol.
7. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, it is characterized in that: described ketone is acetone, cyclohexanone one or more in methylethylketone, first isopropyl acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N-Methyl pyrrolidone.
8. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described ester is one or more in alcohol ether-ether, methyl acetate, ethyl acetate, acetic acid 1-methoxyl group-2-propyl ester, propyl acetate, butylacetate, methyl propionate or ethyl propionate, glycol ethers acetic ester, butyl glycol acetate.
9. fluorine modified epoxy base ink for thin-film solar cells according to claim 1, is characterized in that: described ether is one or more in diethyl ether, dipropyl ether, tetrahydrofuran (THF), dioxan, ethylene glycol ethyl ether or ethylene glycol monomethyl ether.
10. fluorine modified epoxy base ink for thin-film solar cells claimed in claim 1, is characterized in that: comprise the steps:
(1) by fluorine modified epoxy solution, viscosity-controlling agent and solvent, in emulsify at a high speed device, process 10-60 minute, rotating speed 10000-100000 rpm, is processed into even mix emulsion fluid;
(2) after above mix emulsion fluid machines with under same processing rotating speed environment, in 10-20 minute by nanometer aluminium powder in batches trace add continuously;
(3) above emulsion is after nanometer aluminium powder adds completely, more fully emulsified 10-30 minute; The one flexibility that both must need after strainer filterings more than 300 orders or thin-film solar cells fluorine modified epoxy base base ink for ink-jet printer for above emulsion.
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| EP3299428A4 (en) * | 2015-05-22 | 2018-12-05 | PPG Coatings (Tianjin) Co. Ltd. | Single-component high-anticorrosion quick-drying epoxy coating composition |
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