CN101824253A - High weatherability self-cleaning fluorocarbon coating - Google Patents
High weatherability self-cleaning fluorocarbon coating Download PDFInfo
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- CN101824253A CN101824253A CN200910131225A CN200910131225A CN101824253A CN 101824253 A CN101824253 A CN 101824253A CN 200910131225 A CN200910131225 A CN 200910131225A CN 200910131225 A CN200910131225 A CN 200910131225A CN 101824253 A CN101824253 A CN 101824253A
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- tetrafluoroethylene
- coating
- cleaning
- vinyl ether
- agent
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- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000004140 cleaning Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003223 protective agent Substances 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 11
- -1 quencher Substances 0.000 claims description 10
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229960000969 phenyl salicylate Drugs 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 150000003902 salicylic acid esters Chemical class 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 240000002853 Nelumbo nucifera Species 0.000 description 4
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- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- JXQJXXUBPMVRNX-UHFFFAOYSA-N butyl carbamodithioate;nickel Chemical compound [Ni].CCCCSC(N)=S JXQJXXUBPMVRNX-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 210000001595 mastoid Anatomy 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OUGZCCJYXXBAFW-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene ethenyl acetate Chemical compound C(C)(=O)OC=C.FC(=C(Cl)F)F OUGZCCJYXXBAFW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000007932 benzotriazole esters Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention discloses a tetrafluoroethylene-vinyl ether copolymer fluorocarbon coating which can be in curing under the normal temperature and contains an anti-aging composite additive and self-cleaning additive and a preparation method thereof.
Description
Technical field
The present invention relates to a kind of can curing at normal temperatures, and contain the tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating and the preparation method of anti-aging composite assistant, automatically cleaning auxiliary agent.
Background technology
Fluorocarbon resin is with Fluorine containing olefine, carry out homopolymerization or copolymerization as tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), vinylidene fluoride (VDF), vinyl fluoride (VF) etc. for elementary cell, or carry out copolymerization with other monomer based on this, and contain the monomer autohemagglutination of fluorine carbon chemical bond or copolymerization on the side chain and contain polymkeric substance in the molecular structure that obtains than polyfluoro carbon bond (F-C).And serve as that the coating made of basis is called fluorocarbon resin coating (Fluorocarbons resin Coatings) with it.Be referred to as " fluorocarbon coating " (Fluorocarbon Coating) in western countries such as America and Europes, Japan is called fluorine resin coating, is called " fluoro-containing coating " or " fluorine coating " traditionally in China.
Fluorocarbon coating by purposes can be divided into following three kinds dissimilar:
1) be representative with U.S.'s atropic-Fei Na company, producing the PVDF resin is the exterior wall weathering resistance fluorine resin coating of main component, and such coating has superpower weathering resistance, and the concrete manifestation life-span is long, colour-fast, pollution-free and ageing-resistant etc.
2) be the Teflon stickness paint not of representative with the du pont company, be mainly used in aspects such as non-stick cooker, tableware and mould, be embodied in be not stained with, the low pollution and easy cleaning etc.
3) be the outdoor ambient cure fluorine resin coating of FEVE of representative with Japanese rising sun pin company, being mainly used in bridge, TV tower etc., to be difficult to the pylon of often construction anticorrosion etc., and it is long to be embodied in easy construction, good and anticorrosion life-span of protection effect.
Though PTFE, PVDF, PVF series product excellent performance, exist poorly soluble, need shortcomings such as high bake film forming, gloss be low, its range of application is restricted.In order to remedy these deficiencies of fluorocarbon coating, main direction of studying is that fluorocarbon resin excellent properties and good film forming properties and the adaptability of some coating resin are combined.The most successful in this regard is the fluorine resin polyvalent alcohol (FEVE) of fluoroolefin and the copolymerization of alkyl vinyl Zhi ether and the thermoset fluorocarbon resin coating that isocyanic ester cooperates.
The FEVE fluorocarbon resin is fluoroolefin and alkyl vinyl ether or fluoroolefin and the mutual multipolymer of arranging of alkyl vinyl ester.Shown in the following graph structure formula 1 of structural formula.From the chemistry and space structure, the fluoroolefin cell protection unsettled vinyl ether structural unit, make it avoid oxidative attack.Alkane alkene ether on the side chain provides resin dissolves, transparency, gloss, and carboxylic group provides pigment wettability, tack, and oh group provides crosslinked group.
Structural formula 1:FEVE structure
The outstanding properties of FEVE fluorocarbon resin is its super-weathering resistance.The characteristic of fluoropolymer is closely related with the characteristic of fluorine atom.Because the F-C key has the high bond energy of 485KJ/mol, has very high chemical stability, therefore with the fluoropolymer of spline structure, fluorine content is high more, and stability is good more.Fluorochemical monomer and comonomer are alternately arranged, and because C-C chain conformation in the shape of a spiral makes that the C-F of high bond energy also is a major reason of FEVE excellent performance to the C-C key of low bond energy and the shielding protection effect of C-C1.
The extraordinary weathering resistance of FEVE fluorocarbon resin can form alternating copolymer based on fluorine monomer and comonomer, and alternately degree is high more, and the defective of molecular chain is few more, and fluorine monomer just can provide enough protections to comonomer.
To thermoset FEVE fluorocarbon resin, having the fluoroolefin unit of excellent stability and being subjected to the alkane alkene ether unit alternating structure of erosion medium resistance is the important structure factor of bearing the outstanding performance of fluorocarbon resin, is confirmed by many experimental studies, and is subjected to the approval of coating circle.
But FEVE fluorocarbon coating in the market also has following subject matter:
(1) adopt benzene kind solvent usually, its VOC content causes certain injury than higher to human body and environment;
(2) general on the market is the fluorocarbon coating of polymkeric substance with trifluorochloroethylene vinyl acetate or trifluorochloroethylene alkane alkene ether, though its performance is better than the antiseptic property of acroleic acid polyurethane coating, but because the fluorine content of coating is lower, its performance is compared with high-end tetrafluoroethylene alkane alkene ether fluorocarbon coating and is still had very big gap;
(3) for the mistaken ideas on the polluting proofing property aspect existence understanding of FEVE coating:, should have good print resistance because the hydrophilic contact angle of coating surface is bigger.Contact angle with water more is easy to generate pollution generally at 85 °～95 ° but FEVE films.
The method that improves the coating polluting proofing property is divided into two groups: the one, improve coatingsurface and water contact angle, and form the super hydrophobic surface of similar lotus leaf effect; The one, form the hydrophilization coating at coating surface, make dirt washed away easily.The ultimate principle of lotus leaf effect is: the super-hydrophobicity feature of lotus leaf is by there being certain roughness, and the existence of the mastoid process of micrometer structure and surperficial cured shape thing causes jointly on the uneven surface.Also exist nanostructure on the mastoid process of the micrometer structure of lotus leaf surface, the hierarchical structure that this micrometer structure combines with nanostructure is the basic reason that causes surface super hydrophobic.Anti-pickup mechanism based on water-wetted surface: pollutent is divided into two kinds of wetting ability and lipophilicities.Wetting ability pollutents such as sand have the tendency that washes away along with rainwater, lipophilicity substance is subjected to rain drop erosion owing to not firm in the hydrophilization surface attachment, also can be easy to wash away, studies show that:, increase its polluting proofing property of its hydrophobicity and but descend being hydrophobic coating originally.Therefore, to the stronger solvent based coating of the lower hydrophobicity of script water-intake rate, become wetting ability as far as possible and film by reducing its hydrophobicity, make to film.Form the hydrophilization surface by the special auxiliary agent that in FEVE coating, adds " rainproof muscle ", thereby obtain self-clean type fluorine coating.
Summary of the invention
For overcoming above-mentioned deficiency, the present invention intends the analysis and research to existing dissimilar FEVE fluorocarbon resin product structures and performance, find out the dependence of performance and structure, realize that by means such as anti-aging composite assistants, surface hydrophilic processing tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating has good processing characteristics, workability, thereby prepare high weather-proof, self-cleaning FEVE fluorocarbon coating.
The present invention realizes by following embodiment:
A kind of high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating is characterized in that, described fluorocarbon coating is made up of by following weight ratio two kinds of components of A, B,
A component: tetrafluoroethylene-vinyl ether copoly type fluorocarbon resin 40%～70%; Pigment 5%～40%; Filler 0%～10%; Wetting dispersing agent 0.3%～4%; Defoamer 0.1%～0.5%; Leveling auxiliary agent 0.2～0.8%; Protective agent 0.5%～2%; Automatically cleaning auxiliary agent 1%～3%; Solvent 5%～15%;
B component: solidifying agent 65%～85%; Solvent 15%～35%.
The ratio of the weight of A, B component is 5～10: 1～4, preferred 6～10: 1～2, more preferably 8～10: 1, and most preferably 10: 1.
The present invention also comprises following embodiment, a kind of preparation method of above-mentioned high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating, and it comprises the steps:
The preparation of A component: in proportion wetting dispersing agent, defoamer, pigment and filler are joined in the fluorocarbon resin of sufficient quantity and the organic solvent and stir, grind to form monochromatic slurry behind the thorough mixing; Carry out paint according to the color needs then, each monochromatic slurry is joined in resin and the solvent in proportion, add leveling auxiliary agent, protective agent and automatically cleaning auxiliary agent, stir;
The preparation of B component: in proportion solidifying agent is dissolved in the high boiling organic solvent, stirs.
During use,, promptly get tetrafluoroethylene of the present invention-vinyl ether copoly type fluorocarbon coating with two kinds of component thorough mixing of A, B and stirring.
In preferred embodiments, the particle diameter of pigment and filler is below the 30 μ m; Preferably at 1～30 μ m; More preferably at 5～30 μ m; 15～25 μ m most preferably.
The gross weight of pigment and filler coating based is preferably 5～50% weight, more preferably 10～45% weight, most preferably 15～40% weight.
Wherein said protective agent is formed by UV light absorber, quencher and radical scavenger are compound.
Described UV light absorber (UVA) is preferably selected from the salicylate class, as salol, and BAD, TBS, OPS etc.; Benzophenone, as UV-9, UV-531 etc., or benzotriazole compound, as UV-P, UV-327, UV-326 etc.; Triazines is as UV light absorber triazine-5 etc.; Group-substituted acrylonitrile is as UV-Ab-sorber 317 etc.
Quencher claims passivator again, is by the transfer of the energy energy that dissipates, and when being in unsettled " excited state " after polymer molecule absorbs ultraviolet ray, quencher can be accepted its energy, the stable low-energy state that polymer molecule is returned.Radical scavenger can be caught the free radical that the polymkeric substance disassociation produces, and makes it become stable compound, the terminating chain reaction.
Described quencher is preferably selected from metal complexs such as ferrous iron, cobalt, copper, nickel, and organic moiety is substituted phenol or thiobisphenol etc., dithiocar-bamate, phosphonate monoester nickel type, thiobisphenol type etc., more preferably second, n-butyl dithiocarbamate nickel.
Preferred described radical scavenger is selected from hindered amine light stabilizer (HALS) compound, mainly is that piperazine system, piperidines are that derivative and imidazolidone are derivative etc., and two (1,2,2,6, the 6-pentamethyl--4-piperidyl) sebates of choosing are more arranged.
Described automatically cleaning auxiliary agent is can be to the hydrophilization auxiliary agent of film coated surface migration and hydrolysis, preferred fluorine modified siloxane.
Shine upon in the luminous energy on ground 5% ultraviolet ray is arranged approximately, ultraviolet wavelength is 290nm～400nm, energy is 314kJ/mol～419kJ/mol, the activation energy of most of polymkeric substance autoxidation reaction is 42kJ/mol～167kJ/mol, ionic dissociation energy is 167kJ/mol～418kJ/mol, remove the high bond energy that the F-C key has 485KJ/mol, can resist outside the ultraviolet attack, the chemical bond of most of polymkeric substance all can be destroyed by ultraviolet ray.Ultraviolet ray degrades polymkeric substance by photochemical reaction: polymer molecule of a ultraviolet photon activation, the molecular energy that is activated reaches is enough to make chemical bond generation homolysis, generate two free radicals, free radical and other molecules such as airborne oxygen molecule further react, produce the more freedom base, reaction chain is handed on, be consumed until free radical and finish or be hunted down, reaction just can stop.
UV light absorber can absorb ultraviolet ray consumingly, and is converted into harmless heat energy form and discharges.
According to selected tetrafluoroethylene-vinyl ether copoly type fluorocarbon resin molecular structure, preferred protective agent middle-ultraviolet lamp absorption agent: quencher: the radical scavenger molar ratio is 0.8～1.5: 0.4～1.2: 0.4～1.3, more preferably 0.9～1.4: 0.5～1.1: 0.5～1.2, most preferably 1.0～1.3: 0.6～0.9: 0.6～0.9.Protective agent: the fluorocarbon resin part by weight is preferably 1.5～4.0, and more preferably 1.8～3.7, most preferably 2.0～3.6.
The automatically cleaning auxiliary agent is can be to the compound of surface transport and hydrolysis, in the curing of coating process, can more promptly move to film coated surface, through hydrolysis after a while, particularly through after the rainy season, form a hydrophilic film coated surface, make oil-dirt be difficult for adhering to, through rain drop erosion, oil-dirt and inorganic hydrophilic spot all can be removed, and reach the automatically cleaning effect.
The gross weight of automatically cleaning auxiliary agent coating based is preferably 1～3% weight, more preferably 1.2～2.8% weight, most preferably 1.5～2.5% weight.
In preferred embodiments, wetting dispersing agent in the A component is the auxiliary agent of this area routine, as contain polyamine block copolymer solution, contain the polyamine amide solution of the interpolymer solution of acidic-group, unsaturated polyprotonic acid etc., the block copolymer solution of preferred polyamine, contain the interpolymer solution of acidic-group, more preferably contain the interpolymer solution of acidic-group.Leveling auxiliary agent also is the auxiliary agent of this area routine, as modified polyorganosiloxane type flow agent, the restricted long-chain resin type of consistency flow agent, as Voncoat R 3310 and multipolymer; With the high boiling solvent is the flow agent of main component, preferred modified polyorganosiloxane type flow agent, polyimide, polycarbonate, polyacrylic acid, more preferably modified polyorganosiloxane type flow agent.Solvent is preferably high boiling organic solvent, ester class and ketone, without toluene, dimethylbenzene.More preferably ester class and ketone, also most preferably 1-Methoxy-2-propyl acetate and N-BUTYL ACETATE.
The solidifying agent preferred aliphat isocyanic ester of B component, the more preferably biuret and the tripolymer of hexamethylene diisocyanate (HDI).HDI tripolymer most preferably.
The preferred high boiling organic solvent of B component solvent, as high boiling point aromatic hydrocarbons, ester class and ketone, but without toluene and dimethylbenzene, more preferably ester class, most preferably N-BUTYL ACETATE.
The present invention is by selecting and composite (modification) suitable resin-based materials, in conjunction with the curing system that has excellent weather resistance, curing cross-linked is respond well, the color stuffing system that screening, surface modification and optimization uvioresistant are good, add and examine the auxiliary agent combined system of coupling, it is suitable to the effective solvent system of environmental improvement to select, develop and a kind ofly have high weather resisteant, long-effective corrosion, self-cleaning function, environmental friendliness, and have anticorrosion fluorocarbon coating finish paint of good long lifetime of decorative effect.
Its concrete characteristics are as follows:
A) curative systems that adopts tetrafluoroethylene-vinyl ether copoly type fluorocarbon resin and be fit to require is developed the FEVE fluorocarbon coating of high fluorine content (solvend fluorine content 〉=24%).
B) select for use suitable anti-aging ultraviolet radiation absorption auxiliary agent to reduce the destruction of UV ultraviolet ray in the coating, improve the weathering resistance of paint coatings paint coatings.
C) select well behaved and eco-friendly special solvent system substituted benzene solvent.This special medium hybrid technology makes in the coating addition of material that environment and human body are damaged be reduced, and compared with traditional solvent-borne type product obvious improvement has been arranged for the protection of environment and human body.
D) since FEVE and water contact angle between 80 °～90 °, though surface tension is than common coating, little as vinylformic acid, acroleic acid polyurethane, but surface tension does not have little of not only hydrophobic, but also the degree of oleophobic, therefore still can keep good surface appearance in a short time, time has been grown and rainprint will occur, has a strong impact on decorative effect.This research intends adopting the novel silica ester cpds hydrophilic agent by adding the Balloon base to form the hydrophilization surface, dirt is washed away by rainwater easily, thereby keep clean paint film appearance, and then realize the automatic cleaning action of coating.
The fluorocarbon coating of final development reaches the requirement of table 1 technical indicator
Table 1
According to a preferred embodiment of the invention,, preferably base material is carried out surface preparation, to guarantee two bonding forces between the coating according to the surface property of base material.Surface preparation is the prerequisite and basis of preparation compound coating.Coating prime lacquer, intermediate coat, finish paint after the surface treatment, the preparation compound coating.
The surface pre-treating process that the present invention selects for use as follows with the application basic procedure:
Steel substrate: sandblast, dedusting, prime, be coated with intermediate coat, overpainting.
Iron rust and oxide skin are removed in sandblast.Sandblast power is no oily anhydrous pressurized air, and air pressure and nozzle do not have particular requirement.Sand adopts steel sand, corundum or quartz sand, particle diameter 0.8mm～1.7mm.Derusting grade requires to reach the Sa of GB8923-88
Level.
Blow off floating dust with the anhydrous pressurized air that does not have oil after the sandblast, or use the suction cleaner dedusting.
Surface after the sandblast dedusting should be coated with priming in 8h.Priming paint can adopt inorganic or organic zinc-rich primer, zinc phosphate priming paint, iron oxide red rust-proofing primer, preferred zinc rich primer.Adopt construction technologies such as brushing, spraying, build 50～60 μ m.
Intermediate coat is selected the coating that contains the scale color stuffing for use, as epoxy micaceous iron intermediate coat, epoxy glass flake coating etc., and preferred epoxy micaceous iron intermediate coat.Adopt roller coating, spraying application, build 120～180 μ m.
Finish paint adopts tetrafluoroethylene of the present invention-vinyl ether copoly type fluorocarbon coating, and construction technology can adopt brushing, roller coating, spraying, build 60～80 μ m.
Embodiment
The present invention is described in detail by the following examples, and described embodiment is convenient to understand the present invention, but not limitation of the present invention, those skilled in the art, on the basis of reading specification sheets of the present invention, any modification or the change made can not deviate from the spirit and scope of the present invention.
The prepared model salt spray resistance life-span of following embodiment can reach 10000h, behind the 5000h of anti-the artificial accelerated aging, and 1 grade of loss of gloss, 1 grade of variable color.
Embodiment 1
A component preparation: with 3 gram protective agents (UV light absorber salol wherein: quencher second, n-butyl dithiocarbamate nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.0: 0.6: 0.6), 2.5 gram automatically cleaning auxiliary agent fluorine modified siloxane, 2 gram modified polyorganosiloxane type flow agents, 1.5 gram wetting dispersing agent, join 60 gram fluorocarbon resins, 10 grams by 1-Methoxy-2-propyl acetate and N-BUTYL ACETATE by stirring in the mixed solvent that is made at 1: 2 more than 0.5 hour, make both thorough mixing even, with 30 gram titanium dioxides, 3 restrain 1000 order micas and join in the above-mentioned solution, stir more than 0.5 hour, to even.The slurries that mix are ground to below the fineness 25 μ m, obtain stock white.Adding 40 gram resins, 5 gram mixed solvents are modulated into white paint A component in above-mentioned stock white.
The preparation of B component: 65 gram HDI tripolymers are dissolved in to stir thorough mixing in 35 the N-BUTYL ACETATE even.
Before the coating, two kinds of components of A, B are mixed, after stirring, obtain white tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating.
Embodiment 2
A component preparation: with 3 gram protective agents (UV light absorber benzophenone wherein: quencher thiobisphenol nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.0: 0.9: 0.8), 2.5 gram automatically cleaning auxiliary agent, 2 gram modified polyorganosiloxane type flow agents, 1.5 gram wetting dispersing agent, join 60 gram fluorocarbon resins, 10 grams by 1-Methoxy-2-propyl acetate and N-BUTYL ACETATE by stirring in the mixed solvent that is made at 1: 2 more than 0.5 hour, make both thorough mixing even, with 28 gram medium chrome yellow medium yellows, 3 gram talcum powder join in the above-mentioned resin solution, stir more than 0.5 hour, to even.The slurries that mix are ground to below the fineness 25 μ m, obtain the medium chrome yellow medium yellow mill base.Adding 40 gram resins, 5 gram mixed solvents are modulated into medium chrome yellow medium yellow colored paint A component in above-mentioned mill base.
The preparation of B component: 65 gram HDI tripolymers are dissolved in to stir thorough mixing in 35 the N-BUTYL ACETATE even.
Before the coating, two kinds of components of A, B are mixed, after stirring, obtain medium chrome yellow medium yellow look tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating.
Embodiment 3
A component preparation: with 3 gram protective agents (UV light absorber benzotriazole ester wherein: quencher phosphonate monoester nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.5: 0.8: 0.6), 2.5 gram automatically cleaning auxiliary agent, 2 gram modified polyorganosiloxane type flow agents, 1.5 gram wetting dispersing agent, join 60 gram fluorocarbon resins, 10 grams by 1-Methoxy-2-propyl acetate and N-BUTYL ACETATE by stirring in the mixed solvent that is made at 1: 2 more than 0.5 hour, make both thorough mixing even, with 28 gram medium chrome yellow medium yellows, 3 gram talcum powder join in the above-mentioned resin solution, stir more than 0.5 hour, to even.The slurries that mix are ground to below the fineness 25 μ m, obtain the medium chrome yellow medium yellow mill base.Adding 40 gram resins, 5 gram mixed solvents are modulated into medium chrome yellow medium yellow colored paint A component in above-mentioned mill base.
The preparation of B component: 65 gram HDI tripolymers are dissolved in to stir thorough mixing in 35 the N-BUTYL ACETATE even.
Before the coating, two kinds of components of A, B are mixed, after stirring, obtain medium chrome yellow medium yellow look tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating.
Claims (7)
1. high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating is characterized in that, described fluorocarbon coating is made up of by following weight ratio two kinds of components of A, B,
A component: tetrafluoroethylene-vinyl ether copoly type fluorocarbon resin 40%～70%; Pigment 5%～40%; Filler 0%～10%; Wetting dispersing agent 0.3%～4%; Defoamer 0.1%～0.5%; Leveling auxiliary agent 0.2～0.8%; Protective agent 0.5%～2%; Automatically cleaning auxiliary agent 1%～3%; Solvent 5%～15%;
B component: solidifying agent 65%～85%; Solvent 15%～35%.
The ratio of the weight of A, B component is 5～10: 1～2.
2. high weatherability self-cleaning tetrafluoroethylene according to claim 1-vinyl ether copoly type fluorocarbon coating, described protective agent by UV light absorber, quencher, radical scavenger is compound forms.
3. high weatherability self-cleaning tetrafluoroethylene according to claim 2-vinyl ether copoly type fluorocarbon coating, wherein said UV light absorber is selected from the salicylate class, as salol, benzophenone or benzotriazole compound, described quencher is selected from metal complexs such as ferrous iron, cobalt, copper, nickel, preferred dithiocar-bamate, phosphonate monoester nickel type, thiobisphenol type; Described radical scavenger is selected from hindered amine compound, as two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate.
4. according to each described high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating of claim 1-3, wherein said automatically cleaning auxiliary agent is can be to the hydrophilization auxiliary agent of film coated surface migration and hydrolysis.
5. according to each described high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating of claim 1-4, wherein said solvent is high boiling point aromatic hydrocarbons, ester class and ketone, but does not comprise toluene and dimethylbenzene.
6. the preparation method of each described high weatherability self-cleaning tetrafluoroethylene-vinyl ether copoly type fluorocarbon coating of claim 1-5, it comprises the steps:
The preparation of A component: in proportion wetting dispersing agent, defoamer, pigment and filler are joined in the resin of sufficient quantity and the organic solvent and stir, grind to form monochromatic slurry behind the thorough mixing; Carry out paint according to the color needs then, each monochromatic slurry is joined in fluorocarbon resin and the solvent in proportion, add leveling auxiliary agent, protective agent and automatically cleaning auxiliary agent, stir;
The preparation of B component: in proportion solidifying agent is dissolved in the organic solvent, stirs.
7. method according to claim 6, wherein said organic solvent are high boiling organic solvent, as high boiling point aromatic hydrocarbons, ester class and ketone, but do not comprise toluene and dimethylbenzene.
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