CN101659803A - Preparation method of heavy metal-free anticorrosive paint, finish paint and corresponding primer - Google Patents
Preparation method of heavy metal-free anticorrosive paint, finish paint and corresponding primer Download PDFInfo
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- CN101659803A CN101659803A CN200910074106A CN200910074106A CN101659803A CN 101659803 A CN101659803 A CN 101659803A CN 200910074106 A CN200910074106 A CN 200910074106A CN 200910074106 A CN200910074106 A CN 200910074106A CN 101659803 A CN101659803 A CN 101659803A
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- paint
- corrosion
- polyaniline
- finish
- priming paint
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- 239000003973 paint Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 35
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 230000037452 priming Effects 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- -1 Synolac Polymers 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 238000010073 coating (rubber) Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229940067573 brown iron oxide Drugs 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229920000767 polyaniline Polymers 0.000 abstract description 44
- 239000000654 additive Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 22
- 230000000996 additive effect Effects 0.000 abstract description 20
- 231100000252 nontoxic Toxicity 0.000 abstract description 8
- 230000003000 nontoxic effect Effects 0.000 abstract description 8
- 239000010960 cold rolled steel Substances 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 238000005341 cation exchange Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 230000002401 inhibitory effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000001815 facial effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
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Abstract
The invention provides an anti-corrosion paint without heavy metal. The primer and the finish of the anti-corrosion paint both contain anti-corrosion additives. The anti-corrosion additive contained in the primer is polyaniline, and the anti-corrosion additive contained in the finish paint is a non-toxic additive with cation exchange capacity. The invention provides a method for preparing a polyaniline-containing anti-corrosion primer. The primer is coated on cold-rolled steel plates, and has excellent adhesion, impact resistance and flexibility. The invention also provides a preparation method of the finishing paint using the cation exchanger as the additive. Salt spray experiments show that the finish paint has excellent corrosion resistance when used together with the primer containing polyaniline. The preparation method of the primer and the finish paint provided by the invention has the advantages of no environmental pollution, simple and easy process and low cost.
Description
One, technical field
The present invention relates to the corrosion of metal protection.Furtherly, the present invention relates to use organic coating protection metal, make it avoid corruption and touch.Specifically, the present invention relates to a kind of protection against corrosion priming paint of heavy metal and method for making of the finish paint that matches of priming paint therewith of not containing.
Two, technical background
Corruption takes place and touches in metal products such as aircraft, vehicle, boats and ships and various hardware in environment, cause extremely enormous economic loss.The application organic coating slows down corruption and touches speed, the protection metal, and existing permanent history is the preventing metal corrosion method of generally using.
For reaching etch-proof purpose, must contain anticorrosive additive in the organic coating.The most effective anticorrosive additive is heavy metal compounds such as chromium lead now, their serious environment pollutions.Though developed many nontoxic anticorrosive additives, as aluminium triphosphate and various phosphoric acid salt corrosion-inhibiting pigments etc., their Corrosion Protection is also less than the anticorrosive additive that contains heavy metals such as chromium lead.
No matter nontoxic anticorrosive additive still contains the anticorrosive additive of heavy metals such as chromium lead, all is to make an addition among the priming paint.The present invention adds nontoxic anticorrosive additive in priming paint and finish paint.The non-toxic anticorrosion erosion additive that adds priming paint is a polyaniline.The non-toxic anticorrosion erosion additive that adds finish paint is the nontoxic additive of tool cation exchange capacity (CEC).
Last century, the eighties found that conducting polymer (polyaniline) has the effect of preventing metal corrosion.Polyaniline might be more effective than compounds such as chromium lead as anticorrosive additive, is expected to replace the widely used now anticorrosive additive that contains heavy metals such as chromium lead.Two develop industrial polyaniline anticorrosion paint during the last ten years, are subjected to extensive attention always.
Polyaniline cooperates with other component as anticorrosive additive, makes protection against corrosion priming paint.Chinese patent CN 1243852A, CN 1358812A, CN 1401718A, CN 12157644A, CN 1182213C, CN1903956A, CN 1803951A, CN 101314697A etc. match polyaniline with Resins, epoxy etc.
CN 1752160 has adopted two kinds of diverse ways to prepare the polyaniline anticorrosion lacquer: first method is first synthesized polyaniline, then polyaniline is mixed with aluminium triphosphate, various phosphoric acid salt corrosion-inhibiting pigment and polyvinyl butyral solution, be mixed with the A component, phosphorous sour water of B component and alcohol, A before the brushing, B two components are mixed in proportion.Second method is to mix with aluminium triphosphate, various phosphoric acid salt corrosion-inhibiting pigment and polyvinyl butyral solution without polymeric aniline, to be mixed with the A component, and the B component also contains chromic acid class oxygenant except that phosphoric acid, water and alcohol.A before the brushing, B two components are mixed in proportion.After the mixing, under the effect of chromic acid class oxygenant, the aniline in the A component becomes polyaniline on institute matel coated surface in the B component.
Check paint film Corrosion Protection method in common is a salt-fog test.For priming paint, the sticking power between it and metallic surface, the impact resistance of paint film and snappiness all are the important techniques indexs.An industrialized painting, essential through sticking power, impact strength, snappiness, and test such as salt-fog test.CN1752160A is applied to polyaniline priming paint on the tinplate sheet, is coated with one deck alkyd resin enamel again after doing, and has measured sticking power with drawing the circle method.Do not see that as yet other Chinese patent has the polyaniline of mensuration priming paint sticking power, impact resistance, reaches flexible report.CN 1639278A, CN101368055A have measured polyaniline paint Corrosion Protection with salt-fog test.
Three, summary of the invention
The invention provides a kind of method for making of protection against corrosion paint.The priming paint and the finish paint of this protection against corrosion paint all contain anticorrosive additive.The contained anticorrosive additive of priming paint is a polyaniline, and the contained anticorrosive additive of finish paint is the nontoxic additive with cation exchange capacity (CEC).
The invention provides a kind of method for making that contains polyaniline anticorrosion priming paint.This priming paint is applied on the cold-rolled steel sheet, and good cohesive force is arranged, impact resistance and snappiness.The summary that contains polyaniline anticorrosion priming paint method for making is: make aniline by base material, filler, and the material formed such as solvent in polymerization.Base materials employed is polyvinyl butyral, Resins, epoxy etc.Used filler is talcum powder, titanium dioxide, ground barium sulfate etc.Solvent for use is single alcoholic solvent (ethanol, Virahol, butanols) or their mixture.
The present invention provides the method for making a kind of and finish paint that polyaniline priming paint matches simultaneously.Salt-fog test shows that this finish paint and the above-mentioned polyaniline priming paint that contains are used, and antiseptic property is good.The summary of the finish paint method for making that matches with polyaniline priming paint is: with cationic exchange pigment (as the silica gel of calcium ion-exchanged) or Zeo-karb, with other macromolecule resin, filler, and solvent etc. mix, be made into finish paint.Used other macromolecule resin comprises Resins, epoxy, aminoresin, urethane resin, Synolac, acrylic resin, vibrin, fluorine resin and synthetic rubber coating etc.Whether use selecting for use of solvent and agent solvent, get main determining in adopting which kind of resin.
Four, description of drawings
Fig. 1, the photo after polyaniline paint film adhesion (the draw circle method) test: draw circle method test photo through polyaniline priming paint (no finish paint), the sample first half is irised wipe trace and is not had around it and peel off for drawing.Reach 1 grade.
Fig. 2, the photo after the polyaniline paint film impact resistance test: polyaniline priming paint (no finish paint) impulse withstand test, there is an impact dent in sample first half central authorities, paint film flawless, wrinkle and peel off around the pit.(pit of Fig. 1 photo bottom also is the print after the impact resistance test).
Fig. 3, the photo of demonstration polyaniline paint film flexibility: the sample middle part is behind flexibility test, and its bending paint film has no reticulate pattern, crackle and peels off.
Fig. 4, the 3%NaCl solution soaking is tested and finish paint contrast (photo): the left side print has no corrosion for polyaniline priming paint adds after finish paint 3%NaCl solution soaking is tested, and the right side is common rust-inhibiting paint obviously corrosion foaming after the test of 3%NaCl solution soaking of no polyaniline priming paint.
Fig. 5, the photo of 500 hours salt-fog test test back coatings: the polyaniline lacquer is coated with facial mask diagonal lines cut, and there is corrosion at the score line place behind salt mist experiment, but corrosion is not coated with the diffusion of facial mask place to next door polyaniline lacquer.
Fig. 6, the photo of 500 hours salt-fog test test back coatings: the polyaniline lacquer is coated with facial mask, common rust-inhibiting paint edge sealing, the polyaniline paint film is not seen corrosion after salt-fog test, but the corrosion of common rust-inhibiting paint edge sealing.
Five, embodiment
Example 1. preparation priming paint
With following material mixing
Talcum powder 0-25 part
Titanium dioxide 0-25 part
Ground barium sulfate 0-25 part
Polyvinyl butyral, Resins, epoxy 10-15 part
Alcoholic solvent is an amount of
Phosphoric acid (85%) 1-3 part
Aniline (technical grade) 0.3-1.5 part
Add the ammonium persulfate aqueous solution behind the above-mentioned material mixing, the material color turns promptly becomes priming paint after green.
Example 2. preparation finish paints
Finish paint partly is made up of A, B two.
Finish paint A preparation partly is exemplified below:
Talcum powder 5-50 part
Titanium dioxide 5-50 part
Ground barium sulfate 5-50 part
Mica powder 5-50 part
Calcium ion-exchanged silica gel 5-50 part
Resins, epoxy 20-30 part
Epoxy resin diluent is an amount of
Above-mentioned material mix grinding is evenly promptly made A
Finish paint B partly is a polyamide resin.During use A, B be mixed in proportion and add an amount of T-31 siccative and can be used as finish paint and use.
The mensuration of example 3. polyaniline paint film adhesions (drawing the circle method)
The priming paint of example 1 preparation is brushed equably on cold-rolled steel sheet, measures sticking power with drawing the circle method after the drying at room temperature.Sticking power divides 7 grades, and 1 grade best, and 7 grades the poorest.Fig. 1 is the photo after polyaniline paint film adhesion (the drawing the circle method) test, and through the test of coating quality supervision and inspection center, ocean, test result shows that priming paint sticking power of the present invention is 1 grade.
The mensuration of example 4. polyaniline paint film impact resistances
The priming paint of example 1 preparation is brushed equably on cold-rolled steel sheet, measures with shock-resistant method after the drying at room temperature.Fig. 2 is the paint film photo of polyaniline paint film after the test of (50cm) impact strength, and this photo shows priming paint of the present invention paint film flawless, wrinkle and peeling phenomenon after shock test.
The mensuration of example 5. polyaniline paint film flexibilities
The priming paint of example 1 preparation is brushed equably on cold-rolled steel sheet, measures paint film flexibility with pliable and tough method after the drying at room temperature.Fig. 3 is the photo of polyaniline paint film after (1mm) anti-snappiness test, and this photo shows that the snappiness of priming paint of the present invention is fine.Its paint film has no reticulate pattern, crackle and peels off behind the flexibility test.
Example 6. anti-3%NaCl solution soaking test and finish paint contrasts
The priming paint of example 1 preparation is brushed equably on cold-rolled steel sheet, after the drying at room temperature, coats different finish paints.Then being coated with steel plate was soaked 7 days in 3%NaCl solution soaking solution, to contrast the effect of various finish paints.Fig. 4 soaks the simultaneous test photo for the white colour finish paint, and left photo is that polyaniline priming paint+finish paint has no corrosion after the test of 3%NaCl solution soaking, and the right side is common rust-inhibiting paint obviously corrosion foaming after the test of 3%NaCl solution soaking of no polyaniline priming paint.As seen finish paint of the present invention is best.The corrosion of having bubbled after test of common rust-inhibiting paint.
The Corrosion Protection of example 7. salt-fog tests test polyaniline paint
The priming paint of example 1 preparation is brushed equably on cold-rolled steel sheet, then, coat by example 2 preparations finish paint.After the drying at room temperature, mark " X " shape cut that penetrates paint film, carry out 500 hours salt-fog tests then.Fig. 5 is that score line place, 500 hours salt-fog test test backs has corrosion, but does not spread to the next door.Fig. 6 photo is that the polyaniline lacquer is coated with facial mask, common rust-inhibiting paint edge sealing, and the polyaniline paint film is not seen corrosion after the salt-fog test, but the corrosion of common rust-inhibiting paint edge sealing.As seen the present invention obviously is better than common lacquer after salt-fog test test in 500 hours.
Claims (5)
- By a kind of priming paint and therewith the finish paint that matches of the priming paint preventing metal corrosion of forming elements such as a kind of not leaded, chromium, zinc jointly paint.
- 2. the mentioned priming paint preparation method of claim 1 is, aniline is in-situ polymerization in the slip of nonconducting macromolecule filming material, filler and solvent composition, forms priming paint.
- 3. the mentioned finish paint of claim 1 is made up of nonconducting macromolecule filming material, inorganic or organic powder, solvent etc.
- 4. the mentioned inorganic or organic powder of claim 3 mixture that is one or more following powders: the silica-gel powder of talcum powder, titanium dioxide, ground barium sulfate, mica powder, Paris white, brown iron oxide, calcium ion-exchanged and Zeo-karb powder.
- 5. other mentioned macromolecule resin of claim 3 comprises Resins, epoxy, aminoresin, urethane resin, Synolac, acrylic resin, vibrin, fluorine resin and synthetic rubber coating etc.
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CN200910074106A CN101659803A (en) | 2009-04-09 | 2009-04-09 | Preparation method of heavy metal-free anticorrosive paint, finish paint and corresponding primer |
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CN200910074106A CN101659803A (en) | 2009-04-09 | 2009-04-09 | Preparation method of heavy metal-free anticorrosive paint, finish paint and corresponding primer |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102260423A (en) * | 2011-07-18 | 2011-11-30 | 苏州吉人漆业有限公司 | Alcohol-soluble phosphate high temperature resistant long-acting anti-corrosive paint and preparation method thereof |
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2009
- 2009-04-09 CN CN200910074106A patent/CN101659803A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102260423A (en) * | 2011-07-18 | 2011-11-30 | 苏州吉人漆业有限公司 | Alcohol-soluble phosphate high temperature resistant long-acting anti-corrosive paint and preparation method thereof |
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