CN101111573B - Method for applying corrosion protection layers comprising thioamides to metallic surfaces - Google Patents
Method for applying corrosion protection layers comprising thioamides to metallic surfaces Download PDFInfo
- Publication number
- CN101111573B CN101111573B CN2006800035470A CN200680003547A CN101111573B CN 101111573 B CN101111573 B CN 101111573B CN 2006800035470 A CN2006800035470 A CN 2006800035470A CN 200680003547 A CN200680003547 A CN 200680003547A CN 101111573 B CN101111573 B CN 101111573B
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- China
- Prior art keywords
- thioamides
- coating
- group
- carbon atom
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 150000003556 thioamides Chemical class 0.000 title claims description 94
- 238000005260 corrosion Methods 0.000 title abstract description 31
- 230000007797 corrosion Effects 0.000 title abstract description 31
- 239000000049 pigment Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 35
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- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims description 177
- 239000011248 coating agent Substances 0.000 claims description 167
- 239000000463 material Substances 0.000 claims description 136
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 31
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- 238000005275 alloying Methods 0.000 description 1
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003251 chemically resistant material Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- CSAZMTWHVNCILA-UHFFFAOYSA-N hex-2-enenitrile Chemical compound CCCC=CC#N CSAZMTWHVNCILA-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Method for applying corrosion protection layer on a metallic surface comprises treating the surface with a formulation containing at least one binding agent, a pigment and/or a filler and a corrosion protecting agent, which is at least one thioamide group containing compounds. Method for applying corrosion protection layer on a metallic surface comprises treating the surface with a formulation containing at least one binding agent, a pigment and/or a filler and a corrosion protecting agent, which is at least one thioamide group of formula -C(S)NR1>R2> containing compounds such as thioamide compound (D1) of formula R4>n-R3>-C(S)NR1>R2> or thioamide (D2) with at least two thioamide group. n : 1-5; R1>, R2>H or optionally substituted 1-20C alkyl; R3>(n+1)-valenced 1-30C hydrocarbon; and R4>functional group. Independent claims are included for: (1) a method for applying an integrated pretreating layer on metallic surface comprising treating the metallic surface with a crosslinkable preparation, containing a binding agent, a crosslinkable component, where the crosslinkable group is bounded with the binding agent and/or additionally a crosslinker is used, a pigment and/or filler, a corrosion protecting agent and optionally a solute, and crosslinking the applied layer, where the amount of the binding agent is 20-70 wt.%, filler contains 20-70 wt.% of at least one inorganic fine particulate fillers with an average particle size of less than 10 mu m, and the corrosion protecting agent contains 0.25-10 wt.% of thioamide group containing compounds, where the wt.% relate to the sum of all components except the solute; (2) a polymer comprising at least two terminally and/or laterally positioned thioamide group of formula -C(S)NR1>R2>; (3) integrated pretreating layer on a metallic surface of steel, zinc or its alloy or aluminum or its alloy obtained by the method; (4) metallic surface comprising the integrated pretreating layer.
Description
The present invention relates to that a kind of thereby a kind of compsn is handled in the metallic surface, metal coiled material (coil metal) surface coated erosion shield, the particularly method of comprehensive pretreatment coating particularly through using, said compsn contains at least a base-material (binder), a kind of linking agent, a kind of mineral filler in small, broken bits and contains at least two thioamides groups or contain the compound of a thioamides group and at least one functional group.The invention still further relates to can be through the comprehensive pretreatment coating of this method acquisition.
In order to make sheet metal workpiece for example trolley part, car body component, tool housing, building exterior finish, top ceiling or window frame (window profile), can carry out forming processes to the sheet metal that is fit to through the for example punching press of suitable method, boring, folding, die mould and/or deep draw.Bigger assembly is body of a motor car for example, if suitablely can weld together through for example that some are independent parts and it is assembled out.The starting material that for this reason use generally comprise long metal strip, and this long metal strip obtains through metal is rolled, and in order to store and to transport, and are often rolled-up and formation is called as the form of coiled material.
Generally must protect to prevent corrosion said metal assembly.Particularly automotive field is very high to etch-proof requirement.Present new automobile can guarantee the perforation that prevents to get rusty in maximum 30 years.The car body of car of new model is produced through multiple working procedure, has the multilayer different coatings.
In the past, anti-corrosive treatment is carried out to Manufactured metal works basically, and for example to the car body through welding assembly, and at present, anti-corrosive treatment is directed against metal coiled material through the coiled material coating more and more and carries out.
The continuous coating that coiled material coating is to use the coating material that is generally liquid on metal strip or metal coiled material, to carry out.With thickness be 0.2 to 2mm, the metal coiled material of the maximum 2m of width transmits through the coiled material coating machine with the speed that is up to 200m/min, in this process, it is coated with.For this reason, can use coil of strip material or aluminium and/or the duraluminum coiled material that for example passes through cold rolling mild steel band or architectural grade steel band, the galvanized thin plate of process, process galvanizing.Typical equipment comprises feed zone, coil storage device, cleaning and pretreating zone, has the second coating section, lamination section and cooling zone, coil storage device and winder that first of baking oven and cooling zone, downstream is coated with section, has baking oven.
The coiled material painting process generally includes following treatment step:
1. if desired: through the cleaning bath metal strip is cleaned,, and remove interim rust preventive oil with the pollutent of removal metal strip lay up period accumulation.
2. through dip-coating or spray method or through method of roll coating coating one deck pre-treatment thin layer (< 1 μ m).The purpose of using this coating is to increase erosion resistance, and improves the sticky limit of follow-up coating in the metallic surface.It is known that what can be used for this purpose is to contain Cr's (VI) and the pretreatment baths that do not contain chromium.
3. through method of roll coating coating one deck priming paint.The dry thickness of this layer is about 5-8 μ m usually.Wherein use coating system based on solvent.
4. be coated with one or more layers top coating through method of roll coating.Its floating coat dry thickness is about 15-25 μ m.Here also use coating system based on solvent.
Shown layer structure among Fig. 1 through the steel plate galvanized of aforesaid method coating.Wherein shown the cross section that has zinc layer (2) and be coated with the coil of strip material (1) of conventional pretreatment coating (3), priming paint (4) and top coating (5) above that.
The metal coiled material that will pass through above-mentioned coating is used for for example making the shell of large household appliance (electricrefrigerator etc.), as the face wall of buildings or be used for automobile making.
As stated, metal coiled material coating pretreatment coating (3) and priming paint (4) are required great effort very much.And, constantly increase being used for the etch-proof demand that does not contain the system of Cr (VI) on the market.Therefore attempting separate application pretreatment coating (3) and organic underlayer coating (4) are replaced with being coated with the individual layer comprehensive pretreatment coating that has above-mentioned two-layer function concurrently always.This coating structure is illustrated among Fig. 2 through the mode of instance.Such single-stage operation can make through the manufacturing of the metal coiled material of coating significantly to be simplified.
US 5,322, and 870 disclose a kind of compsn that is used to form the comprehensive pretreatment coating, wherein contain polymer-coated material, linking agent, also have alkyl or aryl SULPHOSUCCINIC ACID ESTER and/or alkyl or aryl phosphonic acid ester in addition.Said composition also can be chosen wantonly and contain pigment.
DE-A 199 23 084 discloses a kind of water-based coating material that does not contain chromium that is used for single-stage coating, and this material contains the hexafluoro negatively charged ion of Ti (IV), Si (IV) and/or Zr (IV), film forming base-material and a kind of organic phosphoric acid of water-soluble or water dispersible at least.Said composition also can be chosen wantonly and contain a kind of pigment and linking agent.
DE-A 29 43 833 discloses thiocarbamide and verivate thereof as the purposes of the additive in the water-based conversion coatings compsn, contains free sulfuric acid, hydrogen peroxide and silicon-dioxide in the said coating composition.
EP-A 878 519 discloses the preferred waterborne compositions that does not contain chromium that is used to make erosion shield, the thiocarbonyl compound comprising 0.2 to 50g/l, 0.1 to 5g/l SULPHOSUCCINIC ACID ESTER and water miscible base-material or base-material dispersion-s.Wherein can choose wantonly and have 10 to 500g/lSiO
2Thiocarbonyl compound can for example be thiocarbamide, thioamides, thioaldehydes or thiocarboxylic acid.The thioamides that does not openly contain an above thioamides group.
JP-A 2002-64856, JP-A 2002-241957, JP-A 297384 and JP-A2003-73856 disclose the multiple waterborne compositions that is used to make erosion shield, wherein contain different aqueous polymer dispersions, other components and thiocarbonyl compound for example thiocarbamide or second sulphamide.The thioamides that does not openly contain an above thioamides group.
An object of the present invention is to provide a kind of improved method that on the metallic surface, is coated with erosion shield, particularly make the method for comprehensive pretreatment coating, and improved comprehensive pretreatment coating is provided.
Correspondingly found a kind of method that on the metallic surface, is coated with erosion shield; Wherein the metallic surface is with a kind of treated that contains a kind of base-material, a kind of pigment and/or a kind of filler and a kind of anticorrosive agent at least, and wherein said anticorrosive agent is at least a thioamides group (I)-C (S) NR that contains
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4It is a functional group.
In a kind of particularly preferred embodiment of the present invention, erosion shield is the comprehensive pretreatment coating.
In second aspect of the present invention, having found can be through the comprehensive pretreatment coating on the metallic surface of aforesaid method acquisition, and preferably it has the thickness of 3 to 15 μ m.
In the third aspect of the invention, found to be used to implement the preparation of aforesaid method, said preparation contains above-mentioned thioamides.
In fourth aspect of the present invention, found the polymerization thioamides.
When erosion shield was the comprehensive pretreatment coating, its coating process may further comprise the steps at least:
(1) with a kind of crosslinkable treated metallic surface, said crosslinkable preparation contains at least:
(A) a kind of base-material,
(B) crosslinkable component, it can be the crosslinkable groups that links to each other with base-material and/or can be the linking agent of at least a other use,
(C) a kind of pigment and/or filler,
(D) a kind of anticorrosive agent, and
(E) randomly, a kind of solvent, and
(2) make the layer of coating crosslinked,
Wherein
● the amount of said base-material is 20 to 70 weight %,
● the amount of said pigment or filler is 20 to 70 weight %, and said filler is at least a mineral filler in small, broken bits, and the mean particle size of said mineral filler in small, broken bits is less than 10 μ m,
And
● said anticorrosive agent contains at least a thioamides group (I)-C (S) NR that contains of 0.25 to 10 weight %
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4Be a functional group,
Condition is said weight percent to remove the total amount of all components behind the solvent.
The present invention provides a kind of method that is coated with erosion shield in the metallic surface; Wherein the metallic surface is characterized in that with a kind of treated that contains a kind of base-material, a kind of pigment and/or a kind of filler and a kind of anticorrosive agent at least said anticorrosive agent is at least a thioamides group (I)-C (S) NR that contains
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having 1 to 30 carbon atom and possibly also contain the divalent linker of other functional groups, or (D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' independently of one another for having the straight or branched alkyl of 1 to 6 carbon atom.
The present invention also provides a kind of method that is coated with the comprehensive pretreatment coating in the metallic surface, may further comprise the steps at least:
(1) with a kind of crosslinkable treated metallic surface, said crosslinkable preparation contains at least:
(A) a kind of base-material,
(B) crosslinkable component, it can be the crosslinkable groups that links to each other with base-material and/or can be the linking agent of at least a other use,
(C) a kind of pigment and/or filler,
(D) a kind of anticorrosive agent, and
(E) randomly, a kind of solvent, and
(2) make the layer of coating crosslinked,
Wherein
● the amount of said base-material is 20 to 70 weight %,
● the amount of said pigment or filler is 20 to 70 weight %, and said filler is at least a mineral filler in small, broken bits, and the mean particle size of said mineral filler in small, broken bits is less than 10 μ m,
And
● said anticorrosive agent contains at least a thioamides group (I)-C (S) NR that contains of 0.25 to 10 weight %
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having 1 to 30 carbon atom and possibly also contain the divalent linker of other functional groups, or (D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' be straight or branched alkyl independently of one another with 1 to 6 carbon atom,
Condition is said weight percent to remove the total amount of all components behind the solvent.
In a preferred embodiment of said method, R
1And R
2Be H.
In a preferred embodiment of said method, the R of functional group
4For containing the group of O and/or N atom.
In a preferred embodiment of said method, the metallic surface was cleaned through other cleaning (0) before handling with preparation.
In a preferred embodiment of said method, the metallic surface is the surface of steel, zinc or zinc alloy, aluminum or aluminum alloy.
In a preferred embodiment of said method, the thickness of comprehensive pretreatment coating is 3 to 15 μ m.
In a preferred embodiment of said method, handle and carry out through roller coat, spraying or dip-coating method.
In a preferred embodiment of said method, the metallic surface is the metal coiled material surface.
In a preferred embodiment of said method, metal coiled material is the steel through plating or process galvanizing.
In a preferred embodiment of said method, handle and carry out through continuation method.
The present invention also provides comprehensive pretreatment coating or the erosion shield on a kind of metallic surface that is positioned at steel, zinc or zinc alloy, aluminum or aluminum alloy, and it can obtain through method of the present invention.
In a preferred embodiment of said comprehensive pretreatment coating, the thickness of coating is 3 to 15 μ m.
The present invention also provides a kind of metallic surface, comprises comprehensive pretreatment coating of the present invention.
In a preferred embodiment of said metallic surface, have on the comprehensive pretreatment coating and be coated on one or more layers coating film over each other.
The present invention also provides a kind of metal coiled material of steel, and it comprises Zn or Zn alloy layer and has surface of the present invention.
The present invention also provides a kind of preparation that is used for the coating erosion shield in the metallic surface; Wherein contain a kind of base-material, a kind of pigment and/or a kind of filler and a kind of anticorrosive agent at least, it is characterized in that said anticorrosive agent is at least a thioamides group (I)-C (S) NR that contains
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having 1 to 30 carbon atom and possibly also contain the divalent linker of other functional groups, or (D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein n is 1 to 5 natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' independently of one another for having the straight or branched alkyl of 1 to 6 carbon atom.
The present invention also provides a kind of preparation that is used for the coating comprehensive pretreatment coating in the metallic surface, wherein contains following component at least:
(A) a kind of base-material,
(B) crosslinkable component, it can be the crosslinkable groups that links to each other with base-material and/or can be the linking agent of at least a other use,
(C) a kind of pigment and/or filler,
(D) a kind of anticorrosive agent, and
(E) randomly, a kind of solvent,
Wherein
● the amount of said base-material is 20 to 70 weight %,
● the amount of said pigment or filler is 20 to 70 weight %, and said filler is at least a mineral filler in small, broken bits, and the mean particle size of said mineral filler in small, broken bits is less than 10 μ m, and
● said anticorrosive agent contains at least a thioamides group (I)-C (S) NR that contains of 0.25 to 10 weight %
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having 1 to 30 carbon atom and possibly also contain the divalent linker of other functional groups, or (D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein n is 1 to 5 natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' be straight or branched alkyl independently of one another with 1 to 6 carbon atom,
Said weight percent is to remove the total amount of all components behind the solvent.
Description of drawings
Fig. 1: the sectional view of the galvanized steel coiled material that obtains through the two-stage pre-treatment
Fig. 2: the sectional view of the galvanized steel coiled material that obtains through comprehensive pretreatment
Detailed description of the present invention is following:
Through method of the present invention, can protect any metal object in principle to prevent corrosion.
In a kind of embodiment of the present invention, metal object can be fixed metal construction for example buildings, bridge, electric pole, oil tank, pipeline, power house or chemical plant.For this embodiment, generally at the scene through brushing or spraying coating erosion shield.This erosion shield is under atmospheric environment, promptly at ambient temperature and dry in the presence of the air and under the general atmospheric moisture and solidify.According to required degree of protection, the surface is protected to prevent that corrosion also is divided into slight protection against corrosion, moderate protection against corrosion and severe protection against corrosion through erosion shield.
In another embodiment of the invention, the planar metallic structure with comprehensive pretreatment coating, for example panel, tinsel, sheet material, particularly metal coiled material can also be provided particularly advantageous.This coating preferably makes through the coiled material coating.Dry and curing is generally carried out under higher relatively temperature, for example in the baking oven that is fit to, carries out, and perhaps uses suitable source of radiation to be cured with the photochemistry mode.
With regard to the character of metal, can relate to any required metal in principle.But related metal or alloy particularly is used as the metal building material usually and needs protection to prevent the corrosive metal or alloy.
Said surface is the surface of iron, steel, Zn, Zn alloy, Al or Al alloy particularly.They can be for fully by the surface of the structure of said metal and/or alloy composition.Perhaps they can be for only being coated with these metals itself by the consitutional surface of other materials, and said other materials for example is other metals, alloy, polymkeric substance or mixture.Said surface can be in particular the surface of galvanized iron or steel.In a kind of embodiment preferred of present method, it is the surface of the steel of metal coiled material, particularly warp plating or galvanizing.Described metal coiled material can be zinc-plated or at double side zinc coating in one side.
Zn alloy or Al alloy are well known by persons skilled in the art.Those skilled in the art finally should be used for selecting alloying constituent and consumption thereof according to required.The general composition of zinc alloy is particularly including Al, Pb, Si, Mg, Sn, Cu or Cd.The general composition of duraluminum is particularly including Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.Said alloy also can be the Al/Zn alloy that Al and Zn exist with approximately equalised amount.The steel that cover with above-mentioned alloy can obtain from the market.Said steel can contain conventional alloy compositions well known by persons skilled in the art.
Term among the present invention " comprehensive pretreatment coating " refers to coating of the present invention directly is coated on the metallic surface and need not any protection against corrosion pre-treatment; Passivation or phosphatization that said protection against corrosion pre-treatment is for example carried out in advance, the processing of particularly using Cr (VI) compound to carry out.The comprehensive pretreatment coating is merged into one deck with passivation layer and organic underlayer coating.But possibility that has thin layer, particularly thin oxide layer on the metallic surface do not got rid of in term " directly coating ", formation when such layer places air with metal inevitably in conventional operation.
On the comprehensive pretreatment coating, can advantageously directly be coated with other coatings, cathode electric coating layer material for example, and do not need the organic priming paint of extra in advance coating.But it is understandable that under some particular cases, the organic priming paint of extra coating is fine, although preferably do not use organic underlayer coating.
The preparation that is used for the coating erosion shield in the metallic surface among the present invention contains at least a base-material.This base-material also can be chosen wantonly and contain crosslinkable groups.The clear base-material that is used for anticorrosive coating and coating of those skilled in the art.
The preparation that the present invention is used to be coated with the comprehensive pretreatment coating contains at least a base-material (A) and crosslinkable component (B).Crosslinkable component can contain at least a linking agent, and this linking agent is the another kind of material that except that base-material, uses, and perhaps can contain the crosslinkable groups that is connected on the base-material.It is understandable that, also can make base-material contain crosslinkable groups and use linking agent in addition.
Here enumerate multiple possible combination.For example, base-material and linking agent can use respectively.In this case, base-material comprise can with the reactive functional groups of complementary interaction property functional group reactions in the linking agent.Perhaps base-material also can be the self-crosslinking base-material, wherein contain can with the functional group of similar with it (" with himself ") or and same polymer in complementary interaction property functional group participate in the reactive functional groups of crosslinking reaction jointly.Can also react mutually for linking agent purely.
Base-material (A) can be the conventional base-material in the coiled material coating material field.The instance of the base-material that is fit to comprises polyvinyl ester, polyester, Synolac, polylactone, polycarbonate, polyethers, epoxy resin-amine adduct, polyureas, polymeric amide, polyimide or the polyurethane(s) of (methyl) propenoate (being total to) polymers, partly hydrolysed.Also can advantageously use the mixture of various polymerization thing, condition is that this mixture can not produce any undesirable action.
Preferred polyester or the epoxy resin-amine adduct of using.(weldable) coating material that polyester is specially adapted to weld, epoxy resin-amine adduct are preferred for the coating material that do not carry out welding.
The polyester that is fit to is particularly including the condenses of low-molecular-weight dicarboxylicacid and divalent alcohol.The instance of the dicarboxylicacid that is fit to comprises aliphatic dicarboxylic acid for example hexanodioic acid, nonane diacid, sebacic acid and dodecanedioic acid; The aliphatic ester naphthenic acid is the lipid acid dimer for example; Be the product that unsaturated fatty acids reacts each other, alicyclic ring dicarboxylicacid for example 1,4-or 1; 3-cyclohexane dicarboxylic acid and tristane dicarboxylicacid, and aromatic dicarboxylic acid for example m-phthalic acid, terephthalic acid or phthalic acid.It is understandable that, also can use the verivate of dicarboxylicacid.Particularly suitable verivate is for example Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride or four dehydrogenation Tetra hydro Phthalic anhydrides (tetradehydrophthalic anhydride) of acid anhydride.
The instance of the divalent alcohol that is fit to comprises fatty alcohol for example terepthaloyl moietie, glycol ether, triglycol, Ucar 35,1; 3-butyleneglycol, 1; Ammediol, 1,4-butyleneglycol, NSC 6366,1-methyl-prop-1,3-glycol, 2-butyl-2-ethyl glycol, pentanediol, pinakon, ethohexadiol, dodecanediol, new penta diester of hydroxypivalic acid; Alicyclic ring alcohol for example 1; 4-or 1,3-cyclohexanedimethanol, pure and mild two (4-hydroxy-cyclohexyl) methane of TCD and/or two (4-hydroxy-cyclohexyl) propane, and dimer diols (hydrogenant dimer fatty acid).It is understandable that, can use for example ester of pure verivate in a known manner, especially corresponding methyl esters or ethyl ester.
Except the straight chain base-material, can also use the side chain base-material.The monomer that being used to of being fit to generates side chain comprises tricarboxylic acid or its acid anhydrides, for example trimellitic acid 1,2-anhydride or benzenetricarboxylic acid, and trivalent alcohol for example tri methylol alkane, for example trimethylolethane or TriMethylolPropane(TMP).
Preferably, can be through completely or partially polyester being converted into the terminal polyester of isocyanic ester that is with the polymeric polyisocyanate reaction.
OH value in the used polyester is generally about 10 to about 200mgKOH/g, is preferably 15 to 120mgKOH/g, and more preferably 20 to 80mgKOH/g, for example is about 50mgKOH/g.Molecular weight is generally 400 to 10000g/mol, is preferably 500 to 5000g/mol, and more preferably 1000 to 4000g/mol.
Can have epoxy functionalized monomer for example bisphenol A diglycidyl ether, Bisphenol F diglycidylether or hexanediol diglycidyl ether through making, with phenol for example ethoxylation or propenoxylated bisphenol-a reaction and prepare epoxide functional polymers of dihydroxyphenyl propane, Bisphenol F and/or alcohol for example.Epoxide functional polymers also can be buied, and for example trade mark is the epoxide functional polymers of
or
.
Can through make said epoxy functionalized component and phenol and/or with aliphatic dicarboxylic acid or alicyclic ring dicarboxylicacid, acid polyester or alcohol, mercaptan and amine prepared in reaction epoxy resin-amine adduct, said amine is in particular secondary amine, for example diethylolamine or N-methyl butanol amine.
Can also use latex polymer.These polymkeric substance are specially adapted to water-base preparation.The latex polymer that is fit to or the instance of multipolymer comprise acrylate dispersoid, and it can be through usual manner by vinylformic acid and/or acrylic acid derivative and/or vinylbenzene acquisition, and acrylic acid derivative is for example propenoate.The dispersion-s of polyurethane(s) also is fit to, and they are by aromatics and/or aliphatic vulcabond and polyester or the preparation of aliphatic soft segment.
Formulations employed contains the base-material of 20 to 70 weight % usually.Said amount in the preparation except solvent or solvent mixture the total amount of all components.Preferred this amount is 30 to 60 weight %, more preferably 40 to 50 weight %.
Linked (B) can have heat cross-linking group or photochemical crosslinking group.
The thermal cross-linking agent that is fit to is for example based on the linking agent of epoxide, and wherein two or more epoxide groups are connected to each other through linking group.Instance comprises the low-molecular weight compound with two epoxide groups, hexanediol diglycidyl ether, phthalic acid diglycidylether or alicyclic compound 3 ', 4 '-epoxy cyclohexane formic acid 3 for example for example, 4-epoxycyclohexyl methyl esters.Other instances of the linking agent that is fit to comprise the linking agent based on melamine.
Especially preferably use the blocked polyisocyanate linking agent.In the end-blocking process, isocyanate groups and end-capping reagent generation reversible reaction.When being heated to comparatively high temps, can remove end-capping reagent again.The instance of the end-capping reagent that is fit to walks in the 13rd hurdle the 2nd row on DE-A 19914896 the 12nd hurdle the 13rd and is disclosed.Especially preferably use by the end capped polymeric polyisocyanate of ε-Ji Neixianan.
The linking agent that is fit to photochemical crosslinking is in particular the compound that contains two or more ethylenically unsaturated groups, especially two senses or polyfunctional propenoate, for example diacrylate fourth diester, the own diester of diacrylate or Viscoat 295.
If linking agent uses separately, then its consumption is generally 0.5 to 10 weight %, is preferably 1 to 8 weight %, more preferably 2 to 6 weight %.It is understandable that, also can use the mixture of different linking agents, condition is can the character of coating not to be had a negative impact.
The method formulations employed of coating erosion shield of the present invention also contains at least a pigment and/or a kind of filler.The mean particle size of preferred said filler/pigment is no more than 10 μ m.Said material can be in particular at least a anticorrosive pigment.The anticorrosive pigment that is fit to is well known by persons skilled in the art and describes to some extent below.
Formulations employed also contains at least a mineral filler in small, broken bits or a kind of pigment (C) in the preferred method of coating comprehensive pretreatment coating of the present invention.Said filler or pigment also can contain other a kind of organic coating to be used for for example hydrophobization or hydrophilization.The filler mean particle size should not surpass 10 μ m.Preferred average particle size is between 10nm to 9 μ m, more preferably between 100nm to 5 μ m.For the particle of circle or sub-circular, this numerical value refers to diameter; For erose particle needle-shaped particles for example, this numerical value refers to major axis.Particle size refers to initially (primary) particle size.Those skilled in the art recognize that certainly the common agglomeration of solid in small, broken bits is a larger particles, must thoroughly disperse during use.Particle size can be selected according to required coating performance by those skilled in the art.It also receives the influence of for example required coat-thickness.In general, those skilled in the art can select than small-particle for obtaining lower coat-thickness.
The filler that is fit to comprises conducting pigment and filler on the one hand.This additive can improve weldability and improve the follow-up coating of using the electropaining material.The conductive filler material that is fit to and the instance of pigment comprise phosphide, vanadium carbide, titanium nitride, moly-sulfide, graphite, carbon black or adulterated permanent white.The preferred phosphide that uses the metal phosphide, particularly iron of Zn, Al, Si, Mn, Cr, Fe or Ni.The instance of preferred metal phosphide comprises CrP, MnP, Fe
3P, Fe
2P, Ni
2P, NiP
2Or NiP
3
Can also use nonconducting pigment or filler, amorphous silicon for example in small, broken bits, aluminium or titanium oxide, other elements wherein also can mix.As an example, can use the soft silica of process calcium ion modification.
Other instances of pigment comprise anticorrosive pigment for example zn phosphate, zinc metaborate or a hydration barium metaborate.
It is understandable that, also can use the mixture of different pigment.The consumption of pigment is generally 20 to 70 weight %.Can confirm accurate amount according to required coating performance by those skilled in the art.When using conducting pigment, its consumption is the consumption when using non-conductive filler usually.Preferred consumption is 40 to 70 weight % when using conducting pigment and filler; Preferred consumption is 20 to 50 weight % when using non-conductive pigment.
The preparation that be used for being coated with erosion shield among the present invention, is preferred for being coated with the comprehensive pretreatment coating also contains at least a thioamides group (I)-C (S) NR that contains
1R
2Compound.
R in the formula
1And R
2Represent the optional substituted alkyl group of H or straight or branched independently of one another, said alkyl group has 1 to 20 carbon atom, preferably has 1 to 10 carbon atom, more preferably has 1 to 6 carbon atom.Other substituting groups can be in particular the substituting group that contains aerobic or nitrogen: for example OH group or NH
2Group.In addition, in having the group of at least 3 carbon atoms, non-conterminous non-terminal carbon can be replaced by O and/or N atom.Preferred radicals R
1And R
2Instance comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl and n-hexyl respectively.Preferred group R
1And R
2In at least one be H, more preferably the two is H.
The thioamides that uses among the present invention is general formula (II) R
4 n-R
3-C (S) NR
1R
2Compound (D1), wherein contain a thioamides group and one or more functional group, perhaps be compound (D2), wherein contain at least two thioamides groups.
In compound (D1), the thioamides group is through the alkyl R of (n+1) valency
3With n the R of functional group
4Connect, n is 1 to 5 natural number.Preferred n is 1 to 3, more preferably 1 or 2.
R
3Be preferably aliphatic hydrocarbyl, alicyclic hydrocarbon radical, aromatic hydrocarbyl or the fragrant aliphatic hydrocarbyl of (n+1) valency, it has 1 to 30 carbon atom, preferably has 1 to 20 carbon atom, more preferably has 1 to 10 carbon atom.To those skilled in the art, clearly the possible numerical value of n receives the influence of carbon atom number in theory.In general, at alkyl R
3Each carbon atom on average have and be no more than a functional group.Be connected radicals R
3On one side the thioamides group is arranged, also have n the R of functional group on the other hand
4These functional groups can be similar functional group or inhomogeneous functional group.
The R of functional group
4For example can be-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' be alkyl group independently of one another, be preferably straight or branched alkyl with 1 to 6 carbon atom, more preferably-CH
3
In a kind of embodiment preferred of the present invention, the R of functional group
4For only containing N and/or O atom as heteroatomic group.Such examples of groups comprises-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5With-NHCONHR
5
Preferred especially functional group is-OH and/or-NH
2
In a kind of embodiment preferred of the present invention, radicals R
3Be bivalent hydrocarbon radical; Promptly in this case, n is 1.In this case, can mention general formula especially is-(CH
2)
k-straight chain 1, ω-alkylidene group, k is 1 to 30 natural number, is preferably 1 to 20, more preferably 1 to 10.Also can comprise divalent aromatic radical, for example 1, the 4-phenylene perhaps can be general formula and is-(CH
2)
K '-(C
6H
4)-or-(CH
2)
K '-(C
6H
4)-(CH
2)
K "-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, be preferably 1 to 3.
The instance of preferred especially thioamides (D1) comprises that general formula is HO-(CH
2)
k-C (S) NR
1R
2The 'omega '-hydroxy carboxylic acid thioamides, the definition of group and subscript is as above.K in these compounds is preferably 3 to 8.Such examples for compounds comprises 2-hydroxyl thioacetamide, 3-hydroxyl thiopropionamide, 4-hydroxyl sulfo-yulocrotine, 5-hydroxyl sulfo-valeramide, 7-hydroxyl sulfo-heptamide or 8-hydroxyl sulfo-decoylamide, 9-hydroxyl sulfo-pelargonamide or 10-hydroxyl sulfo-decyl amide.
The simplest form of compound (D2) that contains at least two thioamides groups can be rubeanic acid R
1R
2N (S) C-C (S) NR
1R
2
In addition, said compound can be general formula R
6(C (S) NR
1R
2)
mCompound, wherein m thioamides group is through linking group R
6Be connected to each other, m is at least 2 natural number.This compound can be low-molecular weight compound, oligomeric compound or polymkeric substance.Linking group R
6The aliphatic hydrocarbyl, alicyclic hydrocarbon radical, aromatic hydrocarbyl and/or the fragrant aliphatic hydrocarbyl that comprise straight or branched, wherein non-conterminous carbon atom also can be replaced by heteroatoms, particularly O and/or N atom or functional group, and wherein can also contain other functional groups.Other functional groups can be in particular the radicals R of above-mentioned definition
4
In a kind of embodiment preferred of the present invention, D2 comprises low-molecular weight compound.R in this case
6Have 1 to 30 carbon atom, preferred 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, m numerical value in these compounds is 2 to 6, is preferably 2 to 4, more preferably 2.
In a kind of particularly preferred embodiment, (D2) be general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides.R in this compound
7For having the divalent linker of 1 to 30 carbon atom.
R
7Particularly including general formula be-(CH
2)
k-straight chain 1, ω-alkylidene group, k is 1 to 30 natural number, is preferably 2 to 20, more preferably 2 to 8.Wherein also can comprise divalent aromatic radical, for example 1, the 4-phenylene perhaps can be general formula and is-(CH
2)
k'-(C
6H
4)-or-(CH
2)
k'-(C
6H
4)-(CH
2)
k"-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, be preferably 1 to 3.
The instance of such Compound D 2 comprises malonyl-dithio acid amides, own dithio acid amides, 1, the 4-diphenyl disulfide for acid amides (1,4-benzodithioamide) or 1, the 2-diphenyl disulfide for acid amides (1,2-benzodithioamide).
R
7Also can preferably include general formula is-(CH
2)
K '-R
8-(CH
2)
K "-group, R
8Be divalence functional group, particularly contain the functional group of P.Such examples of groups comprises-OP (O) (OR
9) O-,-P (O) (OR
9)-,-P (S) (OR
9)-,-P (S) (SR
9), R wherein
9Be H, monovalent metallic ion or alkyl group, be preferably straight or branched alkyl with 1 to 6 carbon atom.
The preparation that contains the compound of thioamides group is known for a person skilled in the art.They can be for example by corresponding nitrile through with H
2S reacts and prepares.
In another kind of embodiment preferred of the present invention, (D2) be the polymkeric substance that comprises at least two ends and/or side group thioamides group.Term " polymer " " comprise oligopolymer and comprise by one or more monomers having a high-molecular weight compound through what polymerization obtained by routine.Said polymkeric substance can be straight-chain polymer basically or be branched chain polymer.The average molar mass M that contains the polymkeric substance of thioamides group
nBe generally 300 to 10000000g/mol, be preferably 500 to 1000000g/mol, more preferably 1000 to 100000g/mol.
Thioamides group on the polymkeric substance can be end group or is side group.Thioamides group as side group can directly be connected on the main polymer chain, perhaps is connected on the main polymer chain through spacer (spacer).
Can contain the polymkeric substance of itrile group through preparation at first, and after polymerization, make itrile group and H2S reaction with generation thioamides group, thereby prepare said polymkeric substance through the known method of principle.For the polymkeric substance that contains an acrylonitrile unit, the said process diagram is (scheme (I)) as follows.
In principle, the raw material of reaction can use the homopolymer or the multipolymer of all nitrile group-containings.When the unique restriction during selection is H2S and polymer reaction, the ill effect that the side reaction do not expected of not having causes.The suitable monomeric instance that is used for the polymkeric substance of synthetic nitrile group-containing comprises α, ω-thiazolinyl nitrile, and for example vinyl cyanide, allyl nitrile, crotononitrile, pentenenitrile or hexene nitrile, general formula is H
2C=C (CH
3) CONH-R
10(methyl) acrylic amide of-CN or general formula are H
2C=C (CH
3) COO-R
10(methyl) propenoate of-CN, wherein R
10Under various situation, represent bivalent hydrocarbon radical.Preferred vinyl cyanide.
The instance of the comonomer that is fit to comprises alkene; The preferred alkenyl aromatic compound is vinylbenzene, alpha-methyl styrene or substituted vinylbenzene for example, and (methyl) vinylformic acid or (methyl) propenoate for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi or 2-EHA.The raw material that is used for embodiment of the present invention is preferably the for example multipolymer of vinylbenzene and vinyl cyanide.
Itrile group and H
2The reaction of S can advantageously be carried out in the presence of alkali.Applying pressure device and use methyl alcohol for example wherein as solvent.Can be for example through using
13C-NMR spectrum, through relatively CN and CSNH
2The intensity of signal is measured transforming degree, and transforming degree generally should be 20% to 100%, is preferably 40% to 100%.
Another kind possibly be to use the monomer that contains reactive group in addition to carry out polymerization, and said reactive group can react with the compound that contains the sulfo-amide group that is fit to.Can be used as instance should be mentioned that contain the toxilic anhydride group and can with the polymkeric substance of for example ω-hydroxyl thioamides or omega-amino-thioamides reaction, saidly be reflected at exemplarily demonstration in following scheme (II) and the scheme (III).
Be proved to be suitable polymers and for example comprise the multipolymer that is formed by toxilic anhydride and comonomer as the raw material of modification, said comonomer is for example (methyl) vinylformic acid, (methyl) propenoate, alkene ether and/or alkene.Said multipolymer for example is vinylbenzene-maleic anhydride copolymers.
Erosion shield, particularly comprehensive pretreatment coating can prepare through using single thioamides or two or more different thioamides D1 and/or D2.Those skilled in the art can specifically select available thioamides in principle according to the character of required comprehensive pretreatment coating.It is apparent that not to be the thioamides D1 of all kinds and/or binder systems for use, solvent system or the surface that D2 is applicable to all kinds comparably to those skilled in the art.Through functional group or the linking group of selecting to confirm, can make thioamides be suitable for concrete system most.For example, can prepare comparatively hydrophilic or comparatively hydrophobic Compound D 1 and/or D2 specifically to be used for aqueous coating system respectively or to be used for the organic coating system.
Certainly with the thioamides D1 that uses among the present invention and/or D2 with other thioamides, other thiocarbonyl compounds or more broadly say with other anticorrosive agents and mix use; Condition is can not produce undesirable property, the thioamides that said other thioamides are promptly different with above-mentioned definition.In general, the amount of the thioamides part of the present invention of use should be at least 50 weight %, is preferably at least 75 weight %, and said amount is in the total amount of used whole organic anti-corrosive erosion agent.Especially preferably only use thioamides D1 and/or D2.
The amount of used thioamides is generally 0.25 to 10 weight % among the present invention, is preferably 0.5 to 8 weight %, more preferably 1 to 6 weight %.
Generally include suitable solvent in the preparation of the present invention as component (E), each component is dissolved therein or is disperseed, so that carry out the homogeneous coating from the teeth outwards.Do not contain solvent in the preparation or do not contain solvent basically but can also make in principle, but as powder coated material.The preferred solvent that uses.
The solvent that is fit to for can dissolve, the solvent of dispersion, suspension or emulsification The compounds of this invention.They can be organic solvent or water.It is understandable that, also can use the mixture of different organic solvents or the mixture of organic solvent and water.Those skilled in the art can suitably select available solvent in principle according to required end-use and used concrete The compounds of this invention.
The instance of organic solvent comprises hydrocarbon for example toluene, YLENE or mixture, the mixture that for example in crude oil refining, obtains, the for example definite hydrocarbon-fraction of boiling range; Ether, for example THF or polyethers polyoxyethylene glycol for example; Ether alcohol is ethylene glycol monobutyl ether for example; The ether ethyl glycol acetate is ethylene glycol ethyl ethers acid esters monobutyl ether for example; Ketone is acetone for example; And alcohol for example methyl alcohol, ethanol or propyl alcohol.
In addition, can also use the preparation that contains water or be mainly the solvent mixture of water-based.This means and contain at least 50 weight %, preferred at least 65 weight %, the more preferably water of at least 80 weight % in these mixtures.Other components be can be miscible with water solvent.The example comprises monohydroxy-alcohol for example methyl alcohol, ethanol or propyl alcohol, and higher alcohols are for example ethylene glycol monobutyl ether or methoxypropanol of terepthaloyl moietie or polyether polyol and ether alcohol for example.
The amount of solvent can be selected according to required preparation nature and required coating process by those skilled in the art.In general, desire does not form restriction to the present invention, and the weight ratio of coating ingredients and solvent preferably was about 2: 1 between 10: 1 to 1: 10.Certainly make dope earlier and only in use it is diluted to desired concn.
Through thoroughly being mixed with solvent, the component of preparation prepares preparation.The mixing equipment or the dispersing apparatus that are fit to are well known by persons skilled in the art.
Except component (A) to (D) and optional (E), preparation also can comprise one or more auxiliary agents and/or additive (F).The purpose that adds this auxiliary agent and/or additive is that the character of coating is finely tuned.Their consumption is no more than the 20 weight % that remove all components total amount behind the solvent usually, preferably is no more than 10%.
The instance of the additive that is fit to is dyestuff and/or effect pigment, be used for thermofixation or actinic radiation solidified reactive diluent, auxiliary rheological agents, UV absorption agent, photostabilizer, free-radical scavengers, radical add polygalacturonase inhibitor, heat cross-linking catalyzer, photoinitiator and photosensitive coinitiator (photocoinitiator), slip additive, polymerization retarder, skimmer, emulsifying agent, inhibition volatilizer (devolatilizer), wetting agent, dispersion agent, adhesion promotor, levelling agent, film coalescence aid, rheology control additive (thickening material), fire retardant, siccative, anti, other corrosion inhibitors, wax and matting agent; For example can be from textbook " Lackadditive " [Additives for coatings]; Johan Bieleman; Wiley-VCH; Weinheim; New York walks to the content of learning the 15th hurdle the 54th row in 1998 or from the 13rd hurdle the 56th of German patent application DE 19914896A1.
Preferred additives is the dibutyl tin dilaurate as the heat cross-linking catalyzer.
Be the method for embodiment of the present invention, with said treated metallic surface.
In slight protection against corrosion, moderate protection against corrosion or severe protection against corrosion, method of the present invention can or be brushed through for example spraying, then coating solidified method in atmospheric environment carried out.Certainly also can be coated with the coating that has identical or different composition more than two-layer or two-layer continuously.The total thickness of this erosion shield can be decided according to the character of required erosion shield by those skilled in the art.It generally is at least 15 μ m, is preferably at least 25 μ m.Be limited to 2mm on total coating thickness---is the total thickness of all erosion shields of being coated with---, preferably less than 1.5mm, be more preferably less than 1mm, extremely preferably less than 800 μ m, particularly less than 500 μ m.
Usually the mode through the coiled material coating is coated with the comprehensive anticorrosive erosion resisting coating.For the comprehensive anticorrosive erosion, the surface can be chosen wantonly before handling and clean.When processing of the present invention metal finishing and then---for example the plating of coil of strip material or galvanizing---and when carrying out, can coiled material contacted and not clean in advance with treatment soln of the present invention usually.But when the metal coiled material of handling is carrying out before the coating of the present invention through storing and/or during transportation, then it has rust preventive oil usually or become contaminated to a certain degree at least, thereby need clean before the coating of the present invention carrying out.Cleaning can known by one of skill in the art method use conventional sanitising agent to carry out.
In the method for coating comprehensive pretreatment coating of the present invention, through the mode of for example spraying, dip-coating or roller coat the metallic surface is handled with preparation.After the dip-coating operation, excessive treatment soln is removed through the mode of drip-dry; For metal sheet, tinsel or analogue, can select to remove excessive treatment soln through for example pushing or scraping.In treating processes, other components in the metallic surface, surface and component between are produced firm combine thereby make by chemisorption at least a portion in the used polymkeric substance and the preparation.Usually at room temperature handle, but do not intend the possibility that eliminating is handled in principle under comparatively high temps with said preparation.
Processing can be so-called no flushing operation, wherein, and treatment soln convection drying and not washing in loft drier at once after coating.But also can be with cleaning fluid flushing surface after handling.
For the coating of especially preferably metal coiled material being carried out, coating can be carried out also can carrying out on the two sides on a face.Preferred especially coating is carried out with continuation method.
The coiled material coating can for example move the coiled material coating machine continuously through use and carry out; This coating machine is like
Lexikon Lacke und Druckfarben; Georg Thieme Verlag; Stuttgart; New York is described in 1998, the 55 pages " Coil coating " or the German patent application DE 19632426A1.It is understandable that, also can use the machine of other structures.
The speed of metal coiled material can be selected according to the coating character and the curing properties of used preparation by those skilled in the art.General 10 to 200m/min speed is proved to be to suit, and preferred 12 to 120m/min, and more preferably 14 to 100m/min, and extremely preferred 16 to 80m/min, and particularly 20 to 70m/min.
Coating material of the present invention can be coated with through any method, for example through spraying, flow coat or roller coat.In these coating processes, therefore the roller coat particularly advantageous preferably uses in the present invention.
Each application step in the roller coat process can be used two or more rollers.Two to four rollers of preferred use, particularly two.
In the roller coat process, rotation is got in the storage tank that material roller immerses coating material of the present invention, thereby takes coating material to be coated out of.This material directly or through at least one angle stripper is transferred on the rotary coating roller from getting on the material roller.When coiled material moved with equidirectional or opposite direction, coating material was peeled off and is transferred on the coiled material from this coating roll.
As a kind of possibility, also can coating material of the present invention directly be pumped in the gap or roll gap between two rollers, those skilled in the art is called the roll gap charging with this.
According to the present invention, shifting through reverse stripping or inverse roller coating method is favourable and therefore preferred the use.
In the roller coat process, the SFM of getting material roller and coating roll can have very big-difference between a painting process and another painting process.The SFM of coating roll is preferably 110 to 125% of web speed, and the SFM of getting material roller is 20 to 40% of a web speed.
After being coated with preparation based on the present invention, remove any solvent that exists in the coating and also make coating crosslinked.This can carry out in two steps of separating, and also can carry out simultaneously.For removing solvent, preferably use suitable device that coating is heated.Drying also can be carried out through contacting with air-flow.Two kinds of methods can be used in combination.
Curing receives the linking agent The properties, in general carries out through by the use of thermal means.But also can be cured by actinic radiation or by heat cure and combining of actinic radiation curing.Those skilled in the art also are called dual cure with this with heat and the curing of actinic radiation bonded.Here and actinic radiation implication hereinafter described be electromagnetic radiation, for example near infrared, visible light, UV radiation or X ray, especially UV radiation, or granular radiation electron beam for example.
Solidify required temperature and receive the influence of used linking agent especially.The linking agent of high reaction activity is compared and can under lower temperature, be cured with the relatively low linking agent of reactive behavior.The temperature of coating curing is generally between 120 to 250 ℃.
For thermofixation, preferably coating film of the present invention is heated, and/or for coiled material based on iron through convective heat transfer, near infrared or far-infrared radiation, heat through electro-induction.
Instant heating solidified time length heat-up time changes with employed coating material of the present invention.This time is preferably 10 seconds to 2 minutes.When basic use convection heat transfer, under preferred web speed, the length of plenum baking oven should be 30 to 50m, and particularly 35 to 45m.Force ventilated temperature should be higher than the temperature of coating certainly, reaches as high as 350 ℃.
Also can be through being exposed in the actinic radiation to assist the thermofixation of coating film of the present invention.
Also can only carry out but solidify, for example described in the German patent application DE 19835206A1 through actinic radiation.
Method of the present invention makes it possible on metallic surface, particularly iron, steel, zinc or zinc alloy, aluminum or aluminum alloy surface, obtain the comprehensive pretreatment coating.The definite structure of comprehensive pretreatment coating still is unknown with forming.Wherein except that the reaction product that contains polymkeric substance and linking agent, also contain filler, thioamides and other optional components.In addition, wherein also can exist from the metallic surface to extract and sedimentary again component, if the for example conventional aluminium or the amorphous oxide of zinc are and the suitable amorphous oxide that also has other metals.The composition of passivation layer looks like uneven, but demonstrates concentration gradient.
The thickness of comprehensive pretreatment coating can be confirmed according to required coating performance by those skilled in the art.The general thickness of 3 to 15 μ m of finding suits, but under some particular cases, thickness also can be outside this scope.Preferred thickness is 4 to 10 μ m, particularly 5 to 8 μ m.Thickness depends on the amount of the compsn that is coated with under the various situation.
Top other coatings that is coated with metallic surface of comprehensive pretreatment coating.
The coating of other coatings can be carried out in identical coiled material coating machine, and in this coiled material coating machine, the curing section series connection that comprises under two or more coating sections and the suitable situation is provided with.Perhaps, after the coating of comprehensive pretreatment coating and solidifying, will pass through the coiled material of coating and roll again and other coatings of coating in other equipment.After producing coiled material, can coiled material to be coated be rolled then and further handle in another place through coating; Perhaps, it directly it is further handled when exporting from the coiled material coating machine.For example, can carry out lamination or apply removable protection film with plastics it.
But the size that also can further not be coated with and at first will have a coiled material of comprehensive pretreatment coating reduces, and the parts of moulding are further handled.Also can difform component-assembled be got up through welding.The instance of the forming method that is fit to comprises extruding and deep draw.
The element with profiled outline of gained or profiled part scratch resistance, corrosion-resistant, weather resistance and chemically-resistant material, and be easy to be coated with polytype coating material.
If will not contain the coating that the coating material of conducting pigment is used for the about 10-15 μ of thickness m, can be with its substitute as the cathodic electricity coating.
Similarly, can use other coatings to be coated with once more through brushing the erosion shield that obtains.
Below intend and the present invention is described with embodiment.
Basic recipe (base formula) based on (organic) coiled material coating material of epoxy base material
The preparation that is used for making the comprehensive pretreatment coating has used following component:
Component is stirred by said order in the stirred vessel that is fit to, and use dissolver carry out ten minutes pre-dispersed.The gained mixture transferred in the ball mill that has cooling jacket and and mix with the SAZ granulated glass sphere of 1.8-2.2mm size.Abrasive (millbase) was ground 1 hour 30 minutes.Then abrasive is separated with granulated glass sphere.
With abrasive by a kind of commercially available routine of a kind of end-blocking hexamethylene diisocyanate (from
VP LS 2253 of Bayer AG) of said order and 5.9 weight parts and 0.4 weight part not stanniferous crosslinking catalyst (from
VP 0245 of Borchers GmbH) mix.
Basic recipe PU: based on the coiled material coating material (water-based) of polyurethane eater base stocks:
Used base-material is that (solids content is 44 weight % to the aqueous polyurethane dispersion-s, and acid number is 25, N
nBe about 8000g/mol, M
wBe about 21000g/mol), this is dispersion-based in the polyester glycol (M as soft segment
nBe about 2000g/mol), 4,4 '-two (isocyanato-cyclohexyl) methane and the monomer and the chainextender that contain acidic-group.
In the stirred vessel that is fit to; In order the dispersing additive of the polyurethane ester dispersion of 18.8 weight parts, 4.5 weight parts, 1.5 weight parts a kind of had the flowing regulator of froth breaking effect, a kind of melamine resin linking agent of 5.5 weight parts (
072; BASF AG), a kind of hydrophilic pyrogenic silica (from
200V of Degussa) of 0.2 weight part, the Finntalc M5 talcum of 3.5 weight parts, teshirogitlite 2310 white pigments of 12.9 weight parts, the polyurethane ester dispersion of 8.0 weight parts, the silicon-dioxide with calcium ion modification (from
of Grace Division) of 3.5 weight parts, the zn phosphate (from
ZP-BS-M of Waardals Kjemiske Fabriken) of 4.9 weight parts, the black pigment (from
Black of BASF AG) of 1.2 weight parts mix, with mixture with dissolver carry out ten minutes pre-dispersed.The gained mixture transferred in the ball mill that has cooling jacket and and mix with the SAZ granulated glass sphere of 1.8-2.2mm size.Abrasive was ground 45 minutes.Then abrasive is separated with granulated glass sphere.
Abrasive is mixed with the polyurethane ester dispersion of 27 weight parts, a kind of skimmer of 1.0 weight parts, a kind of an acidic catalyst (end-blocking tosic acid,
2500) of 3.2%, a kind of skimmer of 1.5 weight parts and a kind of flow aids of 1.0 weight parts in order.
The embodiment of the invention 1 to 5, the comparative example 1 to 3
Each mixes with the thioamides that contains two thioamides groups or the polymerization thioamides of a kind of the present invention's use of 3 weight parts at least again with the basic recipe material.Employed thioamides is listed in the table 1.
Synthesized following polymerization thioamides in addition:
Polymerization thioamides A
Be used for the synthetic raw material and be the multipolymer (
358N, BASF AG) that the vinyl cyanide of a kind of commercially available vinylbenzene and 25 weight % by 75 weight % forms.
In 2 liters of test whisking appliances that have paddle stirrer and a built-in temperature meter, under 50 ℃ with the 150g material dissolution in 160g THF and 150g methyl alcohol.The acquisition solids content is 34.8% transparent polymer solution.
Under the room temperature said polymers soln of 102.5g and 12.5g are dissolved in the diethylamine adding pressurized vessel in the 60ml THF.Inject 6g hydrogen sulfide then.Reaction mixture is heated to 60 ℃ and stirred 4 hours.After container pressure discharges, under 50 ℃ of pressure with about 650-500mbar with the resulting polymers solution concentration to 118.2g.And then add the 106g THF and under 50 ℃ of pressure with about 650-500mbar, be concentrated into 112.2g once more.The acquisition solids content is 32.5% transparent brown polymers soln.Through using quantitatively
13C NMR spectrum records CN to CSNH
2Degree of conversion be 45%.
Polymerization thioamides B
Being used for the synthetic raw material is toxilic anhydride, positive 12-1-alkene and different C
20-24The non-modified copolymer of the mixture of alkene (usage ratio 1/0.6/0.4), synthesize according to following explanation:
Have 1500 of paddle stirrer, temperature monitor and nitrogen inlet at one and boost in the power reactor drum, under 60 ℃, pump into 36.96kg C
20-24Alkene, and suck the positive 12-1-alkene of 31.48kg.Initial admixture is heated to 150 ℃.Then with being metered into incoming flow of forming by 1.03kg two-tert-butyl peroxide 1 and the incoming flow of forming by 30.57kg fused toxilic anhydride 2 in 6 hours.Add after the incoming flow 1 and 2, under 150 ℃, this batch material was stirred 2 hours.Remove the acetone and the trimethyl carbinol through distillation under 150-200mbar then.
Make the reaction of this raw material and hydroxy-propionic acid thioamides.
Test feeding 120.7g toxilic anhydride/C in the whisking appliance to a 2L who has paddle stirrer and built-in temperature meter
12Alkene/C
20-24Alkene (1/0.6/0.4) and 40.0g hydroxy-propionic acid thioamides, and introduce nitrogen, this batch material was stirred 1 hour down at 100 ℃.Add the 17.8g diox then and continue and stirred 4 hours.With the 142.9g methyl ethyl ketone this batch material is diluted to 50% then.The acquisition solids content is 49.1% transparent brown polymers soln.Through IR optical spectrum monitor reaction process.In this process, observe two keys (1835 and 1735cm of acid anhydride
-1) reduce, and the increase of two keys, said two keys belong to the ester group (1708cm of reaction product
-1) and the hydroxy-acid group (1777cm that forms
-1).When reaction finishes, no longer can detect two keys of acid anhydride.
For comparing, in a kind of basic recipe, do not add any material, in addition, a kind of compound dithiocarbamate that contains the thioamides group but do not contain functional group is tested.
Table 1: the thioamides that is used for this experiment
Note:
E: based on the coating material of epoxy base material
P: based on the coating material of polyurethane eater base stocks
The coating of comprehensive pretreatment coating of the present invention
With compsn with bar-shaped scraper be coated on Z-shape steel plate (from the OEHDG 2 of Chemetall) go up with aluminium sheet AlMgSi (from the AA6016 of Chemetall) on, make that wet-film thickness is being 6 μ m through using continuous oven under the condition of the base material temperature of 185 ℃ plenum temperature and 171 ℃, to be cured back obtainable dry coating thickness.
The check of coating
The check of steel plate:
Under alternation condition, carry out 10 all stdn check (VDA [German automakers association] alternation condition checks (alternating-conditions test) with steel plate; VDA check sheet material 621-415 Feb82).
After corrosion exposes end, visually rank sheet material.To the formation of the corrosion product of unspoiled coating area and estimate with cut place lower floor corrosion tendency on the edge of.
In this assessment, use following grade scale:
0=corrosion damage situation is identical with blank sample
+=corrosion damage situation is less than blank sample
++=corrosion damage situation is significantly less than blank sample
The check of aluminium plate:
On aluminium plate, carried out acetate spraying check ASS (DIN 50021 June 88).After corrosion exposes end, visually rank sheet material.This circular layer of having assessed whole dispensing area is from situation (circular delamination).
In this assessment, use following grade scale:
0=corrosion damage situation is identical with blank sample
+=corrosion damage situation is less than blank sample
++=corrosion damage situation is significantly less than blank sample
Assay is listed in the table 2:
Table 2: the results list of protection against corrosion check
The embodiment of the invention and comparative example demonstrate thioamides D1 used in the present invention and/or D2 is better with the comprehensive pretreatment coating that other thiocarbonyl compounds obtain than other thioamides.
Claims (22)
1. method at metallic surface coating erosion shield; Wherein the metallic surface is characterized in that with a kind of treated that contains a kind of base-material, a kind of pigment and/or a kind of filler and a kind of anticorrosive agent at least said anticorrosive agent is at least a thioamides group (I)-C (S) NR that contains
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having the divalent linker of 1 to 30 carbon atom, or
(D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' independently of one another for having the straight or branched alkyl of 1 to 6 carbon atom.
2. the process of claim 1 wherein R
7Containing general formula is-(CH
2)
k-straight chain 1, ω-alkylidene group, k are 1 to 30 natural number, perhaps
Contain divalent aromatic radical, or general formula is-(CH
2)
K '-(C
6H
4)-or-(CH
2)
K '-(C
6H
4)-(CH
2)
K "-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, perhaps
Containing general formula is-(CH
2)
K '-R
8-(CH
2)
K "-group, R
8For-OP (O) (OR
9) O-,-P (O) (OR
9)-,-P (S) (OR
9)-or-P (S) (SR
9), R wherein
9For H, monovalent metallic ion or have the straight or branched alkyl of 1 to 6 carbon atom.
3. method in metallic surface coating comprehensive pretreatment coating may further comprise the steps at least:
(1) with a kind of crosslinkable treated metallic surface, said crosslinkable preparation contains at least:
(A) a kind of base-material,
(B) crosslinkable component, it is the crosslinkable groups that links to each other with base-material and/or be the linking agent of at least a other use,
(C) a kind of pigment and/or filler,
(D) a kind of anticorrosive agent, and
(E) randomly, a kind of solvent, and
(2) make the layer of coating crosslinked,
Wherein
● the amount of said base-material is 20 to 70 weight %,
● the amount of said pigment or filler is 20 to 70 weight %, and said filler is at least a mineral filler in small, broken bits, and the mean particle size of said mineral filler in small, broken bits is less than 10 μ m,
And
● said anticorrosive agent contains at least a thioamides group (I)-C (S) NR that contains of 0.25 to 10 weight %
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having the divalent linker of 1 to 30 carbon atom, or
(D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein, n is one 1 to 5 a natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' be straight or branched alkyl independently of one another with 1 to 6 carbon atom,
Condition is said weight percent to remove the total amount of all components behind the solvent.
4. the method for claim 3, wherein R
7Containing general formula is-(CH
2)
k-straight chain 1, ω-alkylidene group, k are 1 to 30 natural number, perhaps
Contain divalent aromatic radical, or general formula is-(CH
2)
K '-(C
6H
4)-or-(CH
2)
K '-(C
6H
4)-(CH
2)
K "-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, perhaps
Containing general formula is-(CH
2)
K '-R
8-(CH
2)
K "-group, R
8For-OP (O) (OR
9) O-,-P (O) (OR
9)-,-P (S) (OR
9)-or-P (S) (SR
9), R wherein
9For H, monovalent metallic ion or have the straight or branched alkyl of 1 to 6 carbon atom.
5. the method for one of claim 1 to 4, wherein R
1And R
2Be H.
6. the method for one of claim 1 to 4, the wherein R of functional group
4For containing the group of O and/or N atom.
7. the method for one of claim 1 to 4, wherein the metallic surface was cleaned through other cleaning (0) before handling with preparation.
8. the method for one of claim 1 to 4, wherein the metallic surface is the surface of steel, zinc or zinc alloy, aluminum or aluminum alloy.
9. claim 3 or 4 method, wherein the thickness of comprehensive pretreatment coating is 3 to 15 μ m.
10. the method for one of claim 1 to 4 is wherein handled through roller coat, spraying or dip-coating method and is carried out.
11. the method for one of claim 1 to 4, wherein the metallic surface is the metal coiled material surface.
12. the method for claim 11, wherein metal coiled material is the steel through plating or process galvanizing.
13. the method for claim 11 is wherein handled through continuation method and is carried out.
14. comprehensive pretreatment coating or erosion shield on the metallic surface that is positioned at steel, zinc or zinc alloy, aluminum or aluminum alloy, its method through one of claim 1 to 4 obtains.
15. the comprehensive pretreatment coating of claim 14, the thickness of its floating coat are 3 to 15 μ m.
16. a metallic surface comprises the comprehensive pretreatment coating of a claim 14 or 15.
17. the metallic surface of claim 16 wherein has on the comprehensive pretreatment coating and is coated on one or more layers coating film over each other.
18. the metal coiled material of a steel, the surface that it comprises Zn or Zn alloy layer and has claim 16 or 17.
19. preparation that is used for coating erosion shield in the metallic surface; Wherein contain a kind of base-material, a kind of pigment and/or a kind of filler and a kind of anticorrosive agent at least, it is characterized in that said anticorrosive agent is at least a thioamides group (I)-C (S) NR that contains
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having the divalent linker of 1 to 30 carbon atom, or
(D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein n is 1 to 5 natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' independently of one another for having the straight or branched alkyl of 1 to 6 carbon atom.
20. the preparation of claim 19, wherein R
7Containing general formula is-(CH
2)
k-straight chain 1, ω-alkylidene group, k are 1 to 30 natural number, perhaps
Contain divalent aromatic radical, or general formula is-(CH
2)
K '-(C
6H
4)-or-(CH
2)
K '-(C
6H
4)-(CH
2)
K "-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, perhaps
Containing general formula is-(CH
2)
K '-R
8-(CH
2)
K "-group, R
8For-OP (O) (OR
9) O-,-P (O) (OR
9)-,-P (S) (OR
9)-or-P (S) (SR
9), R wherein
9For H, monovalent metallic ion or have the straight or branched alkyl of 1 to 6 carbon atom.
21. a preparation that is used for the coating comprehensive pretreatment coating in the metallic surface wherein contains following component at least:
(A) a kind of base-material,
(B) crosslinkable component, it is the crosslinkable groups that links to each other with base-material and/or be the linking agent of at least a other use,
(C) a kind of pigment and/or filler,
(D) a kind of anticorrosive agent, and
(E) randomly, a kind of solvent,
Wherein
● the amount of said base-material is 20 to 70 weight %,
● the amount of said pigment or filler is 20 to 70 weight %, and said filler is at least a mineral filler in small, broken bits, and the mean particle size of said mineral filler in small, broken bits is less than 10 μ m, and
● said anticorrosive agent contains at least a thioamides group (I)-C (S) NR that contains of 0.25 to 10 weight %
1R
2And be selected from the compound of following classification:
(D1) general formula (II) R
4 n-R
3-C (S) NR
1R
2Thioamides, and
(D2) contain the thioamides of at least 2 thioamides groups,
Wherein (D2) is general formula (III) R
1R
2N (S) C-R
7-C (S) NR
1R
2Thioamides, R
7For having the divalent linker of 1 to 30 carbon atom, or
(D2) for containing at least two ends and/or side group thioamides base-C (S) NR
1R
2Polymkeric substance,
Wherein n is 1 to 5 natural number, radicals R
1, R
2, R
3And R
4Define as follows:
-R
1And R
2Be the optional substituted alkyl with 1 to 20 carbon atom of H or straight or branched independently of one another,
-R
3Be a alkyl with (n+1) valency of 1 to 30 carbon atom, and
-R
4For-OH ,-NH
2,-NHR
5,-NR
5R
5' ,-COOH ,-COOR
5,-CONH
2,-CONHR
5,-CONR
5R
5' ,-NHCOR
5,-NR
5' COR
5,-NHCONHR
5,-SH ,-CN, R
5And R
5' be straight or branched alkyl independently of one another with 1 to 6 carbon atom,
Said weight percent is to remove the total amount of all components behind the solvent.
22. the preparation of claim 21, wherein R
7Containing general formula is-(CH
2)
k-straight chain 1, ω-alkylidene group, k are 1 to 30 natural number, perhaps
Contain divalent aromatic radical, or general formula is-(CH
2)
K '-(C
6H
4)-or-(CH
2)
K '-(C
6H
4)-(CH
2)
K "-substituted aromatic group, k ' and k " be 1 to 10 natural number independently of one another, perhaps
Containing general formula is-(CH
2)
K '-R
8-(CH
2)
K "-group, R
8For-OP (O) (OR
9) O-,-P (O) (OR
9)-,-P (S) (OR
9)-or-P (S) (SR
9), R wherein
9For H, monovalent metallic ion or have the straight or branched alkyl of 1 to 6 carbon atom.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005004292.9 | 2005-01-28 | ||
| DE200510004292 DE102005004292A1 (en) | 2005-01-28 | 2005-01-28 | Method for applying corrosion protection layer on metallic surfaces comprises treating the surface with a formulation having binding agent, pigment and/or filler and corrosion protecting agent, which is a thioamide group containing compound |
| DE200510061319 DE102005061319A1 (en) | 2005-12-20 | 2005-12-20 | Use of coating substances comprising a compound that comprises thioamide group in atmospheric corrosion protection of e.g. building, bridges, current masts, tank, container, pipelines, power stations, chemical plants, ships and cranes |
| DE102005061319.5 | 2005-12-20 | ||
| PCT/EP2006/050414 WO2006079627A1 (en) | 2005-01-28 | 2006-01-24 | Method for applying corrosion protection layers comprising thioamides to metallic surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101111573A CN101111573A (en) | 2008-01-23 |
| CN101111573B true CN101111573B (en) | 2012-03-28 |
Family
ID=36686449
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800035470A Expired - Fee Related CN101111573B (en) | 2005-01-28 | 2006-01-24 | Method for applying corrosion protection layers comprising thioamides to metallic surfaces |
| CNA2006800034444A Pending CN101155882A (en) | 2005-01-28 | 2006-01-24 | Copolymer comprising monoethylenically unsaturated dicarboxylic acid derivatives |
| CNA2006800035273A Pending CN101111572A (en) | 2005-01-28 | 2006-01-24 | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| CN2006800035593A Expired - Fee Related CN101111574B (en) | 2005-01-28 | 2006-01-24 | Preparation and method for applying corrosion protection layers |
| CN200680003468XA Expired - Fee Related CN101111571B (en) | 2005-01-28 | 2006-01-26 | Anti-corrosion coatings containing thioamide groups |
Family Applications After (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800034444A Pending CN101155882A (en) | 2005-01-28 | 2006-01-24 | Copolymer comprising monoethylenically unsaturated dicarboxylic acid derivatives |
| CNA2006800035273A Pending CN101111572A (en) | 2005-01-28 | 2006-01-24 | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| CN2006800035593A Expired - Fee Related CN101111574B (en) | 2005-01-28 | 2006-01-24 | Preparation and method for applying corrosion protection layers |
| CN200680003468XA Expired - Fee Related CN101111571B (en) | 2005-01-28 | 2006-01-26 | Anti-corrosion coatings containing thioamide groups |
Country Status (2)
| Country | Link |
|---|---|
| CN (5) | CN101111573B (en) |
| DE (1) | DE102005004292A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392251A (en) * | 2011-11-17 | 2012-03-28 | 成都盛尔嘉科技有限公司 | Rust inhibitor |
| CN104937043B (en) * | 2012-09-19 | 2018-06-29 | 阿克佐诺贝尔国际涂料股份有限公司 | The water-based paint compositions of reaction product comprising maleic anhydride and unsaturated compound and amine |
| CN103059234A (en) * | 2013-01-07 | 2013-04-24 | 辽宁工业大学 | Preparation method of black metal preservative |
| CN103725054A (en) * | 2013-11-25 | 2014-04-16 | 铜陵天河特种电磁线有限公司 | Amino resin wire enamel and preparation method thereof |
| CN103695931B (en) * | 2013-11-29 | 2016-08-24 | 明光市留香泵业有限公司 | A kind of Water-soluble metal short-term antirust liquid and preparation method thereof |
| CN105400262A (en) * | 2015-12-03 | 2016-03-16 | 巢湖诺信建材机械装备有限公司 | Isolation coating on temporary placing box made of alloy material |
| CN105440814A (en) * | 2015-12-23 | 2016-03-30 | 巢湖诺信建材机械装备有限公司 | Bottom layer protective coating on air cannon nozzle |
| CN105623606A (en) * | 2015-12-30 | 2016-06-01 | 安徽工业大学 | Oil and rust removing paste of copper and alloy material of copper |
| CN106047113A (en) * | 2016-07-27 | 2016-10-26 | 苏州明轩地坪涂料有限公司 | Efficient corrosion-resistant coating |
| CN110066358B (en) * | 2018-01-23 | 2022-09-27 | 中国石油化工股份有限公司 | Phosphorus-free polymer corrosion inhibitor and preparation method and application thereof |
| CN113122031A (en) * | 2019-12-31 | 2021-07-16 | 江苏苏博特新材料股份有限公司 | In-situ polymerization type metal corrosion inhibitor and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280578A (en) * | 1938-09-15 | 1942-04-21 | Du Pont | Amides of aliphatic polycarbothionic acids and their preparation |
| US3687908A (en) * | 1971-02-02 | 1972-08-29 | Us Air Force | Polymers containing nitrile and thioamide groups and their preparation |
| US5470908A (en) * | 1993-10-28 | 1995-11-28 | The Dow Chemical Company | Water-based acrylic coating compositions |
| CN1201056A (en) * | 1997-05-14 | 1998-12-09 | 日本涂料株式会社 | Anticorrosive paint composition and anticorrosion treatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB996489A (en) * | 1961-06-01 | 1965-06-30 | Ethyl Corp | Novel hydroxy thio benzamides |
-
2005
- 2005-01-28 DE DE200510004292 patent/DE102005004292A1/en not_active Withdrawn
-
2006
- 2006-01-24 CN CN2006800035470A patent/CN101111573B/en not_active Expired - Fee Related
- 2006-01-24 CN CNA2006800034444A patent/CN101155882A/en active Pending
- 2006-01-24 CN CNA2006800035273A patent/CN101111572A/en active Pending
- 2006-01-24 CN CN2006800035593A patent/CN101111574B/en not_active Expired - Fee Related
- 2006-01-26 CN CN200680003468XA patent/CN101111571B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280578A (en) * | 1938-09-15 | 1942-04-21 | Du Pont | Amides of aliphatic polycarbothionic acids and their preparation |
| US3687908A (en) * | 1971-02-02 | 1972-08-29 | Us Air Force | Polymers containing nitrile and thioamide groups and their preparation |
| US5470908A (en) * | 1993-10-28 | 1995-11-28 | The Dow Chemical Company | Water-based acrylic coating compositions |
| CN1201056A (en) * | 1997-05-14 | 1998-12-09 | 日本涂料株式会社 | Anticorrosive paint composition and anticorrosion treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101111573A (en) | 2008-01-23 |
| CN101111574B (en) | 2010-06-16 |
| CN101111571B (en) | 2011-07-06 |
| CN101111574A (en) | 2008-01-23 |
| CN101111572A (en) | 2008-01-23 |
| DE102005004292A1 (en) | 2006-08-03 |
| CN101111571A (en) | 2008-01-23 |
| CN101155882A (en) | 2008-04-02 |
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