CN1513929A - Nano-fluoro carbon aircraft paint and its preparation method - Google Patents

Nano-fluoro carbon aircraft paint and its preparation method Download PDF

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Publication number
CN1513929A
CN1513929A CNA031114881A CN03111488A CN1513929A CN 1513929 A CN1513929 A CN 1513929A CN A031114881 A CNA031114881 A CN A031114881A CN 03111488 A CN03111488 A CN 03111488A CN 1513929 A CN1513929 A CN 1513929A
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nano
fluorine carbon
synthetic resin
aeroplane dope
solvent
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CN1207357C (en
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刘福春
韩恩厚
柯伟
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In Science And Technology (suzhou) Co Ltd Nano Coating
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Institute of Metal Research of CAS
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Abstract

A nano-class fluorocarbon paint for airplane is composed of the modified synthetic resin and the solidifying agent. Said modifyed synthetic resin is prepared through adding nano slurry to synthetic resin solution, mixing with solvent and pigment, grinding and filtering. Its advantages are high storage stability and high weatherability.

Description

Nano-fluorine carbon aeroplane dope and preparation method thereof
Technical field
The present invention relates to coating technology, be specially a kind of fluorocarbon resin coating and preparation method thereof with super weather-proof function.
Background technology
The raising of aircraft speed and the variation of complex environment of living in make people have higher requirement to aeroplane dope.Phthalic resin coating, epoxypaint, acrylic resin paint, silicone resin coating, poly-propylhomoserin coating successively use on aircraft.Fluorine resin coating has obtained extensively should having in industrial aspect owing to good weathering resistance, chemical proofing, mechanical property.Fluorine resin paints can be dissolved in common solvent and be made at a lower temperature especially in recent years, but even drying and forming-film just at room temperature, and protect light and tint retention good.This fluorine resin coating have weathering resistance and pollution resistance well outside, application property is also very good, is a kind of filmogen that is fit to do aeroplane dope.United States Patent (USP) 4,347,376 have reported that the coating by the preparation of perfluor propine acetylide can be used for the protection of aircraft windscreen.United States Patent (USP) 4,595,718 have reported and are making and can use a kind of normal temperature solidifying fluorine-carbon polymer coating during the maintenance aircraft, the elastomer coating that its forms has anti-fuel functional.The disclosed two kinds of fluorocarbon resin coatings of above-mentioned United States Patent (USP) are all normal temperature solidified, made things convenient for construction.
The fast development of nanosecond science and technology is for the development of coating provides opportunity.The research that utilizes nano material to improve coating property has also obtained remarkable progress.Reported with nanometer slurry preparation nano-photo catalytic fluorocarbon resin coating method as Chinese patent (application number 02109488.8), but this coating has photo-catalysis function, the cost height only is applicable to the special occasions that needs environmental purification.Chinese patent CN1412258A discloses a kind of nano UV resistant acrylate paint, though the ultraviolet light performance of this coating improves a lot, weathering resistance also has certain gap from fluorocarbon resin coating.
In addition, U.S. Pat P6,432,486 have reported that recently the coating that aircraft surfaces plasma spraying fluoropolymer coating forms has the freezing function, and this fluoropolymer coating needs the specific equipment spraying, and construction adaptability has been subjected to considerable restraint.
Summary of the invention
The purpose of this invention is to provide a kind of nano-fluorine carbon aeroplane dope and preparation method thereof with super-weathering resistance.
Technical scheme of the present invention is: a kind of nano-fluorine carbon aeroplane dope is made of matching used synthetic resins and solidifying agent two-pack, synthetic resins is one or more of fluorocarbon resin of hydroxyl, solidifying agent is the isocyanates solidifying agent, described synthetic resins is modified synthetic resin, by weight percentage, modified synthetic resin is by the solvent composition of 1-75% nanometer slurry, 10-65% synthetic resins, 0-40% pigment, surplus; The proportioning of solidifying agent and modified synthetic resin is pressed NCO: OH=0.8-1.5: 1 mol ratio;
Described nanometer slurry refers to the Nanos type nanometer slurry with uvioresistant function of Metal Inst., Chinese Academy of Sciences's development, and nanometer slurry content in modified synthetic resin is preferably 10-55%;
Described synthetic resins content is preferably 10-40%;
Described pigment content is preferably 5~35%;
Described solvent is that one or more of aliphatic hydrocarbon, aromatic hydrocarbon, ester class, ketone, terpene, replacement hydro carbons are composite.Wherein aliphatic solvents refer to sherwood oil, No. 200 solvent oils, raffinate oil, butane, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, octane, octane-iso; Aromatic hydrocarbon solvent refers to benzene,toluene,xylene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, ethylbenzene, isopropyl benzene; Ketones solvent refers to acetone, methylethylketone, mibk, pimelinketone, isophorone, diacetone alcohol, metacetone, methyl propyl ketone; Esters solvent refers to vinyl acetic monomer, n-butyl acetate, isobutyl acetate, capryl acetate, acetic acid heptyl ester, acetic acid ester in the last of the ten Heavenly stems, n-Butyl lactate, methoxyacetic acid propyl ester; Terpene type solvent refers to turps, pine tar, kautschin; Replace varsol and refer to trichloroethane, 2-nitropropane; Solvent is No. 200 solvent oils, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, toluene, dimethylbenzene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, methylethylketone, mibk, pimelinketone, isophorone, vinyl acetic monomer, n-butyl acetate, isobutyl acetate, methoxyacetic acid propyl ester, trichloroethane preferably;
Described pigment is selected from titanium white, ground barium sulfate, GL ground limestone, precipitated calcium carbonate, talcum powder, quartzy, zinc phosphate, aluminium triphosphate, yellow ultramarine, strontium yellow, baryta yellow, zinc-chrome yellow, wollastonite, kaolin, mica powder, phthalocyanine green, cadmium red, toluidine red, red iron oxide, iron oxide yellow, iron oxide black, graphite, phthalocyanine blue, ultramarine, Chinese blue, red lead, yellow lead, carbon black, zinc powder, aluminium powder, lithopone, zinc sulphide, Cadmium Sulfide, one of barium metaborate or two or more composite.
In the nano-fluorine carbon aeroplane dope of the present invention, employed synthetic resins, can be selected from the fluorocarbon resin of Japan AGC Zhu Shi commercial firm commodity Lumiflon by name, as Lumiflon LF-100, Lumiflon LF-200, Lumiflon LF-400 etc., the ザ Off ロ Application trade mark fluorocarbon resin of Japan East Asia synthetic chemistry company, the Ford of the new chemical industry of Xi'an Le Jia company limited Fluorocarbon resin, the FEVE type fluorocarbon resin of Mingzhan fluorin coating stock Co., Ltd., Dalian city; Can be selected from the Desmodur of Bayer (Bayer) company as the curing agent component of nano-fluorine carbon aeroplane dope N75, Desmodur N100, Desmodur N3390, Desmodur N3300, Desmodur VPLS 2010/1, Desmodur VPLS 2103, Desmodur Z4470; The Tolonate of France inferior (Rhodia) company in sieve ground TMHDB-75MX, Tolonate TMHDT-90; CORONATE 2604, CORONATE HX-T, CORONATE 2384, the CORONATE HK of Japan fluorocarbon resin Co., Ltd..The proportioning of curing agent component and modified synthetic resin component is NCO: OH=0.8-1.5: 1 (mol ratio).
The present invention also provides the preparation method of above-mentioned nano-fluorine carbon aeroplane dope, and its process is as follows:
1) preparation modified synthetic resin: by weight percentage, at first 1-75% nanometer slurry is added in the 10-65% synthetic resin solution, the solvent that adds 0-40% pigment, surplus again mixes, high speed dispersion also is ground to fineness less than 30 μ m, makes the modified synthetic resin component of nano-fluorine carbon aeroplane dope;
2) preparation coating: the proportioning of solidifying agent and modified synthetic resin is pressed NCO: OH=0.8-1.5: 1 mol ratio uniform mixing, promptly form the nano-fluorine carbon aeroplane dope.
Nano-fluorine carbon aeroplane dope mixing of the present invention and grinding dispersing apparatus are the common equipments in the paint manufacturing process, comprise high speed dispersor, sand mill, ball mill, ball mill and triple-roller mill.
Advantage of the present invention is as follows:
1. the present invention proposes and adopt the method for nanometer slurry to prepare the nano-fluorine carbon aeroplane dope, employed nanometer slurry is mainly to be made up of the nano powder of stable dispersion, and this method has improved nano-fluorine carbon aeroplane dope package stability.
2. finely disseminated nanoparticle can reduce the porosity of coating, improves the permeability resistance of coating, has improved the weathering resistance and the solidity to corrosion of coating.
3. coating application adaptability of the present invention is strong, and cost is low.
4. nano-fluorine carbon coating of the present invention has super-weathering resistance.
Embodiment
Unless outside specializing among the present invention, related ratio all is weight percentage.
The evaluation method of nano-fluorine carbon coat-thickness: coating dry film thickness is measured with the 6000FN1 type thickness tester of U.S. DeFelsko company.
The evaluation method of nano-fluorine carbon coating adhesion: GB9286-88 tests by GB.
The nano-fluorine carbon coating is pressed GB/T 1865-1997 3500 hours artificial weathering of continuous illumination experiment on the Ci3000 ageing device of U.S. Atlas Electric Devices company, and weathering resistance is carried out the Comprehensive Assessment grade according to GB1766-1995 and estimated.
The used nanometer slurry of preparation nano-fluorine carbon aeroplane dope is starched for the Nanos type nanometer of Metal Inst., Chinese Academy of Sciences's development, its preparation method is as follows: take by weighing methylethylketone 80g, trichloroethane 10g in the 500ml beaker, add 10g macromolecule dispersing agent Dispers610 (Di Gao chemical company), add nano-titanium oxide 30g, nano zircite 30g and nano zine oxide 40g again, with ball mill grinding 11 hours, make nano material content and be 50% Nanos type nanometer slurry.
Embodiment 1
In the beaker of 300ml, claim 25g Lumiflon LF-400 fluorocarbon resin, add Nanos type nanometer slurry 32g, add titanium white 6g, kaolin 5g, zinc phosphate 5g then, add 25g dimethylbenzene, 1g methylethylketone, 1g vinyl acetic monomer again, more than mixed paint vehicle 1600rpm high speed dispersion 50 minutes, and be ground to fineness less than 30 μ m, be prepared into the modified synthetic resin component; Curing agent component is Desmudur N75; Solidifying agent and modified synthetic resin component two components are pressed NCO: OH=0.9: 1 (mol ratio) proportioning, stirring the back uses spreader to be coated with this nano-fluorine carbon aeroplane dope on through oil removing, except that the LY12 aluminium alloy plate of the 150mm * 75mm * 2mm after the water treatment, behind the sample Air drying of coating composition, making build is the coating sample of 23 ± 2 μ m.
Embodiment 2
In the beaker of 300ml, claim 25g Lumiflon LF-400 fluorocarbon resin, add Nanos type nanometer slurry 8g, add titanium white 6g, kaolin 5g, zinc phosphate 5g then, add 49g dimethylbenzene, 1g methylethylketone, 1g vinyl acetic monomer again, more than mixed paint vehicle 2000rpm high speed dispersion 40 minutes, and be ground to fineness less than 30 μ m, be prepared into the modified synthetic resin component; Curing agent component is Tolonate TMHDT-90; Solidifying agent and modified synthetic resin component two components are pressed NCO: OH=0.9: 1 (mol ratio) proportioning, stirring the back uses spreader to be coated with this nano-fluorine carbon aeroplane dope on through oil removing, except that the LY12 aluminium alloy plate of the 150mm * 75mm * 2mm after the water treatment, behind the sample Air drying of coating composition, making build is the coating sample of 23 ± 2 μ m.
Embodiment 3
In the beaker of 300ml, claim 25g Lumiflon LF-400 fluorocarbon resin, add Nanos type nanometer slurry 52g, add titanium white 6g, kaolin 5g, zinc phosphate 5g then, add 5g dimethylbenzene, 1g methylethylketone, 1g vinyl acetic monomer again, more than mixed paint vehicle 2400rpm high speed dispersion 30 minutes, and be ground to fineness less than 30 μ m, be prepared into the modified synthetic resin component; Curing agent component is CORONATE HX-T; Solidifying agent and modified synthetic resin component two components are pressed NCO: OH=0.9: 1 (mol ratio) proportioning, the stirring back uses line rod spreader to be coated with this nano-fluorine carbon aeroplane dope on through oil removing, except that the LY12 aluminium alloy plate of the 150mm * 75mm * 2mm after the water treatment, behind the sample Air drying of coating composition, making build is the coating sample of 23 ± 2 μ m.
Comparative example 1
In the beaker of 300ml, claim 25g Lumiflon LF-400 fluorocarbon resin, add titanium white 6g, kaolin 5g, zinc phosphate 5g, add 57g dimethylbenzene, 1g methylethylketone, 1g vinyl acetic monomer again, more than mixed paint vehicle 2000rpm high speed dispersion 40 minutes, and be ground to fineness less than 30 μ m, be prepared into the modified synthetic resin component; Curing agent component is Desmudur N75; Solidifying agent and synthetic resins component are pressed NCO: OH=0.9: 1 (mol ratio) proportioning, stirring the back uses spreader to be coated with this fluorocarbon resin coating on through oil removing, except that the LY12 aluminium alloy plate of the 150mm * 75mm * 2mm after the water treatment, behind the sample Air drying of coating composition, making build is the contrast coating sample of 23 ± 2 μ m.
Table 1
Nanometer slurry (%) in the modified synthetic resin Sticking power (level) Weathering resistance (level)
Embodiment 1 ????32 ????0 ????0
Embodiment 2 ????8 ????0 ????1
Embodiment 3 ????52 ????0 ????1
Comparative example 1 ????0 ????0 ????4
Table 1 is the super weather resistance fluorocarbon resin coating of nanometer of different N anos type nanometer slurry content.As shown in Table 1, the Nanos type nanometer of embodiment 1~3 slurry content is in the 10-55% scope, and durability of coating and coating adhesion are very good.

Claims (8)

1, a kind of nano-fluorine carbon aeroplane dope, constitute by matching used synthetic resins and solidifying agent two-pack, synthetic resins is the fluorocarbon resin of hydroxyl, solidifying agent is the isocyanates solidifying agent, it is characterized in that: described synthetic resins is modified synthetic resin, by weight percentage, modified synthetic resin is by the solvent composition of 1-75% nanometer slurry, 10-65% synthetic resins, 0-40% pigment, surplus; The proportioning of solidifying agent and modified synthetic resin is pressed NCO: OH=0.8-1.5: 1 mol ratio.
2, according to the described nano-fluorine carbon aeroplane dope of claim 1, it is characterized in that: described nanometer slurry content is 10-55%.
3, according to the described nano-fluorine carbon aeroplane dope of claim 1, it is characterized in that: described synthetic resins content is 10-40%.
4, according to the described nano-fluorine carbon aeroplane dope of claim 1, it is characterized in that: described pigment content is 5~35%.
5, according to the described nano-fluorine carbon aeroplane dope of claim 1, it is characterized in that: described solvent is that one or more of aliphatic hydrocarbon, aromatic hydrocarbon, ester class, ketone, terpene, replacement hydro carbons are composite.
6, according to the described nano-fluorine carbon aeroplane dope of claim 5, it is characterized in that: described solvent is a sherwood oil, No. 200 solvent oils, raffinate oil, butane, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, octane, octane-iso, benzene, toluene, dimethylbenzene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, ethylbenzene, isopropyl benzene, acetone, methylethylketone, mibk, pimelinketone, isophorone, diacetone alcohol, metacetone, methyl propyl ketone, vinyl acetic monomer, n-butyl acetate, isobutyl acetate, capryl acetate, the acetic acid heptyl ester, acetic acid ester in the last of the ten Heavenly stems, n-Butyl lactate, the methoxyacetic acid propyl ester, turps, pine tar, kautschin, trichloroethane, one of 2-nitropropane or two or more composite.
7, according to the described nano-fluorine carbon aeroplane dope of claim 1, it is characterized in that: described pigment is titanium white, ground barium sulfate, GL ground limestone, precipitated calcium carbonate, talcum powder, quartzy, zinc phosphate, aluminium triphosphate, yellow ultramarine, strontium yellow, baryta yellow, zinc-chrome yellow, wollastonite, kaolin, mica powder, phthalocyanine green, cadmium red, toluidine red, red iron oxide, iron oxide yellow, iron oxide black, graphite, phthalocyanine blue, ultramarine, Chinese blue, red lead, yellow lead, carbon black, zinc powder, aluminium powder, lithopone, zinc sulphide, Cadmium Sulfide, one of barium metaborate or two or more composite.
8, a kind of preparation method according to the described nano-fluorine carbon aeroplane dope of one of claim 1-7 is characterized in that process is as follows:
1) preparation modified synthetic resin: by weight percentage, at first 1-75% nanometer slurry is added in the 10-65% synthetic resin solution, the solvent that adds 0-40% pigment, surplus again mixes, high speed dispersion also is ground to fineness less than 30 μ m, makes the modified synthetic resin component of nano-fluorine carbon aeroplane dope;
2) preparation coating: the proportioning of solidifying agent and modified synthetic resin is pressed NCO: OH=0.8-1.5: 1 mol ratio uniform mixing, promptly form the nano-fluorine carbon aeroplane dope.
CN 03111488 2003-04-18 2003-04-18 Nano-fluoro carbon aircraft paint and its preparation method Expired - Fee Related CN1207357C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702876A (en) * 2012-03-20 2012-10-03 广东电网公司电力科学研究院 Nanometer composite fluoro-carbon heavy anticorrosive coating for electric power rod tower and preparation method of coating
CN102732107A (en) * 2012-07-13 2012-10-17 上海电缆研究所 Coating and method for improving weathering resistance of resin matrix composite mandril
CN103131273A (en) * 2012-11-07 2013-06-05 惠州圣帕新材料有限公司 High weather resistance fluorocarbon material prescription and manufacturing process
CN108641574A (en) * 2018-05-09 2018-10-12 欧利生东邦涂料(东莞)有限公司 A kind of recoverability acrylic acid high-gloss paint
CN110396331A (en) * 2019-08-28 2019-11-01 中铁二院工程集团有限责任公司 One kind can recoat flexible fluorocarbon coating

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702876A (en) * 2012-03-20 2012-10-03 广东电网公司电力科学研究院 Nanometer composite fluoro-carbon heavy anticorrosive coating for electric power rod tower and preparation method of coating
CN102732107A (en) * 2012-07-13 2012-10-17 上海电缆研究所 Coating and method for improving weathering resistance of resin matrix composite mandril
CN102732107B (en) * 2012-07-13 2014-08-13 上海电缆研究所 Coating and method for improving weathering resistance of resin matrix composite mandril
CN103131273A (en) * 2012-11-07 2013-06-05 惠州圣帕新材料有限公司 High weather resistance fluorocarbon material prescription and manufacturing process
CN103131273B (en) * 2012-11-07 2015-12-02 惠州圣帕新材料有限公司 High weather resistance fluorocarbon material prescription and manufacturing process
CN108641574A (en) * 2018-05-09 2018-10-12 欧利生东邦涂料(东莞)有限公司 A kind of recoverability acrylic acid high-gloss paint
CN108641574B (en) * 2018-05-09 2020-08-21 欧利生东邦涂料(东莞)有限公司 Repairable acrylic acid highlight coating
CN110396331A (en) * 2019-08-28 2019-11-01 中铁二院工程集团有限责任公司 One kind can recoat flexible fluorocarbon coating

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