CN101111572A - Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces - Google Patents
Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces Download PDFInfo
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- CN101111572A CN101111572A CNA2006800035273A CN200680003527A CN101111572A CN 101111572 A CN101111572 A CN 101111572A CN A2006800035273 A CNA2006800035273 A CN A2006800035273A CN 200680003527 A CN200680003527 A CN 200680003527A CN 101111572 A CN101111572 A CN 101111572A
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- China
- Prior art keywords
- multipolymer
- monomer
- metallic surface
- coating
- acid
- Prior art date
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- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 92
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims description 13
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title description 6
- 238000002203 pretreatment Methods 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 238000002360 preparation method Methods 0.000 claims abstract description 63
- 125000000524 functional group Chemical group 0.000 claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 32
- 239000010959 steel Substances 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 106
- 239000011248 coating agent Substances 0.000 claims description 98
- 239000003795 chemical substances by application Substances 0.000 claims description 81
- 239000000178 monomer Substances 0.000 claims description 81
- 238000013000 roll bending Methods 0.000 claims description 57
- 239000010410 layer Substances 0.000 claims description 52
- 238000007747 plating Methods 0.000 claims description 40
- 239000000853 adhesive Substances 0.000 claims description 35
- 230000001070 adhesive effect Effects 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 35
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 25
- 238000005536 corrosion prevention Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 20
- 229920002367 Polyisobutene Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 18
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- 229920000728 polyester Polymers 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 10
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 2
- 239000008397 galvanized steel Substances 0.000 claims description 2
- -1 thioamide compound Chemical class 0.000 abstract description 46
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 25
- 239000000049 pigment Substances 0.000 abstract description 22
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- 238000009472 formulation Methods 0.000 abstract description 7
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- 239000000945 filler Substances 0.000 abstract 5
- 125000001391 thioamide group Chemical group 0.000 abstract 5
- 239000003223 protective agent Substances 0.000 abstract 4
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 description 57
- 239000002184 metal Substances 0.000 description 57
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 48
- 239000000463 material Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 229920001577 copolymer Polymers 0.000 description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 16
- 239000003513 alkali Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000012972 dimethylethanolamine Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229920003009 polyurethane dispersion Polymers 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 150000008064 anhydrides Chemical group 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 7
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000011020 pilot scale process Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
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- 150000002118 epoxides Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- CDSLHOULXDQDPN-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].C[NH+](C)CCO CDSLHOULXDQDPN-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
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- 239000000839 emulsion Substances 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
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- 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 comprise at least a tackiness agent, linking agent, inorganic filler in small, broken bits and the composition of dicarboxylic acid-olefin copolymer by use handles, in the metallic surface, especially at the roll bending metallic surface, plated thickness is the method for the comprehensive pretreatment layer of 1 to 25 μ m.Also relate to formed metal articles and be used to implement the preparation of this method with this comprehensive pretreatment layer.
Be metal works for example trolley part, car body component, instrument panel, exterior building wallboard, ceiling panel or the window frame of preparation thin-walled, make suitable sheet metal forming by for example punching press of suitable technology, brill, superimposed, die mould and/or deep draw.Large component is body of a motor car for example, if suitable the welding by a plurality of independent parts is assembled.The starting material that are used for this purpose generally comprise the long metal strip that forms by rolled metal, for ease of storing and transporting it are rolled into so-called roll bending shape.
The metal parts of mentioning must carry out corrosion prevention usually.Especially in trolley part, very high for the requirement of corrosion prevention.At present new automobile guarantee to prevent the to get rusty time limit of perforation is up to 30 years.The Hyundai Motor vehicle body is that the operation of a plurality of steps of process makes, and has the different coat film of multilayer.
Carry out on but in the past, the metal parts in completion is handled basically in corrosion prevention the body of a motor car of welding assembling---for example by---, up to modern age, the corrosion prevention processing just gradually on the roll bending metal mode by the roll bending coating carry out.
The roll bending coating is to metal strip, or the continuous coating process of roll bending, uses liquid coating material to carry out usually.The metal roll bending that thickness is 0.2 to 2mm, width is 2m to the maximum is carried with the speed that is up to 200m/min by roll bending coating production line, carries out coating in this process.What can be used for this purpose has, for example, and the rolled steel plate or the aluminum or aluminum alloy roll bending of the cold rolling roll coil of strip of soft steel or architectural grade steel, the thin plate of electrogalvanizing, galvanizing.Typical production line comprises feed station, roll bending storehouse, cleaning and pretreating zone, along the cooling zone in the first coating station of baking oven and downstream, the second coating station of band baking oven, divide stop and cooling zone and roll bending storehouse and up-coiler.
The operating process of roll bending coating generally includes following processing step:
1. as needing: the clean metal roll bending is removed interim corrosion prevention oil to remove at metal roll bending storage process accumulative dirt with by the cleaning bath.
2. by dipping or method of spray plating or by roller coat thin pretreatment layer (＜1 μ m) is carried out coating.The purpose of this coating is to improve erosion resistance, and can also play the adhering effect of the follow-up coating of enhancing in the metallic surface.What become known for this purpose has the Cr of containing (VI), contains Cr (III) and not chromate-containing pretreatment baths.
3. by rolling method coating priming paint.The thickness of drying layer is generally 58 μ m.This situation is used solvent based coating system usually.
4. by one or more layers exterior coating of rolling method coating.The thickness of inferior situation drying layer is about 15 25 μ m.Usually also use solvent based coating system herein.
By the metal roll bending of this mode coating for example the rolled steel plate of coating layer structure as shown in Figure 1.Plating is conventional pretreatment layer (2), priming paint (3) and one or both or more kinds of different exterior coating (4) on metal (1).
By this way the metal roll bending of coating be used for for example producing the shell of so-called large household appliance (refrigerator etc.), as the outside panelling of buildings or be used for automatization.
Require great effort very much with pretreatment layer (2) and priming paint (3) coated metal roll bending.In addition, on market, be used for the demand of corrosion prevention in continuous increase for no Cr (VI) system.Thereby and be no lack of such trial, replace with single, comprehensive pretreatment layer (2 ') with the pretreatment layer (2) and the organic underlayer coating (3) that will apply respectively, this comprehensive pretreatment layer can play the effect of two coatings.The structure of this layer is shown in Fig. 2 by by way of example with graphics.The result of this single stage method operation will simplify the production of coated metal roll bending greatly.
M ü 11er etc. discloses in " Corrosion Science; 2000; 42; 577-584 " and " Die Angewandte Makro mole ekulare Chemie 1994; 221,177-185 " and has used the purposes of styrene-maleic acid copolymer as the corrosion prevention agent of zinc pigment and/or aluminium pigment.
EP-A 122 229, CA 990 060, JP 60-24384 and JP-A 2004-68065 disclose toxilic acid and multiple other monomer for example the multipolymer of vinylbenzene, other alkene and/or other vinyl monomer be used for the purposes of water-based system corrosion prevention agent.
EP-A 244 584 discloses modification toxilic acid unit and vinylbenzene, sulfonated phenylethylene, alkyl vinyl ether, C
2To C
6The multipolymer of alkene and (methyl) acrylamide is as the additive of water coolant.Modification toxilic acid unit has the functional group that links by spacer, for example,
OH ,-OR ,-PO
3H
2,-OPO
3H
2,-COOH or preferred-SO
3H.
EP-A 1 288 232 and EP-A 1 288 228 disclose for example multipolymer of acrylate, vinyl ether or alkene of modification toxilic acid unit and other monomer, and modification toxilic acid unit contains the heterogeneous ring compound that links by spacer.The document discloses this polymkeric substance as for example corrosion prevention agent in the chilled(cooling) water return (CWR) of Aquo System, and as the purposes of coating composition.
JP-A 2004-204243 and JP-A 2004-204244 disclose the steel plate that improves weldability, for improving its weldability, earlier with steel plate tin, use zinc then, and then the use preparation carries out aftertreatment to it.Aqueous formulation comprises 100 to 800g/l water base acrylic resins, 50 to 600g/l water soluble resins, 10 to 100g/l corrosion prevention agent and 1 to 100g/l antioxidant.Spendable corrosion prevention agent comprises amine and styrene-maleic anhydride copolymer.The preferred polymkeric substance that uses the ammonium salt of toxilic acid monoesters as polymerized unit.Do not comprise linking agent in the preparation, do not comprise weighting agent or pigment yet.With coating 90 ℃ of dryings.The thickness of coating 0.05 to the 10 μ m that respectively does for oneself.
JP-A 2004-218050 and JP-2004-218051 disclose corresponding preparation and by the steel plate of its coating, have also comprised the dispersible SiO of water in its preparation
2
JP-A 60-219 267 discloses a kind of coating formulation of radiation-hardenable, comprises multipolymer, 5% to 30% resol and 30% to 90% the monomeric acrylate of 5% to 40% vinylbenzene and unsaturated dicarboxylic acid and/or its monoether in the preparation.Can obtain anti-rust film by this coated material, this anti-rust film available bases is removed, and its thickness is 5 to 50 μ m.
WO 99/29790 discloses and has comprised the heterocyclic compound with at least two secondary nitrogen-atoms.This compound also can be the toxilic acid unit of modification and the multipolymer of vinylbenzene or 1-octene, and the toxilic acid unit of modification has the piperazine unit that links to each other by spacer.It is used for handling epoxy resin varnish when temperature is lower than 40 ℃.Mentioned the corrosion protective coating that is used for the architectural grade steel in the document, its thickness is 112 to 284 μ m.
US 6,090,894 disclose toxilic acid monoesters or diester and alpha-olefin-carboxylic acid and, if suitable, other monomeric multipolymer, and disclosing by making COOH group on the multipolymer and other functionallization of epoxy compounds reaction.This compound can be used for preparing the coating material.
But the method for the comprehensive corrosion protective layers of all unexposed coating offered in above-mentioned institute quoted passage, especially is not disclosed in the continuation method that applies comprehensive corrosion protective layers on the roll bending metal.
DE-A 199 23 084 discloses the non-chrome water-based coating material that is used for the single step coating, and it comprises at least Ti (IV), Si (IV) and/or the hexafluoro negatively charged ion of Zr (IV), water-soluble or dispersible binder for film formation of water and organic phosphoric acid.Composition also can be chosen wantonly and comprise pigment and linking agent.
WO 2005/078025 discloses the comprehensive pretreatment layer and has been used to apply and comprised the method for phosphorodithioate as the comprehensive pretreatment layer of corrosion prevention agent.We still inedited patent application DE 102005006233.4 disclose a kind of be used to apply contain the method for dithiophosphinic acids as the comprehensive pretreatment layer of corrosion prevention agent.Unexposed use polymkeric substance corrosion prevention agent.
One of purpose of the present invention provides a kind of being used to and generates improving one's methods of comprehensive pretreatment layer (integrated pre-treatment layer), and improved comprehensive pretreatment layer itself.
So found a kind of method at metallic surface plating comprehensive pretreatment layer, described method comprises following at least step:
(1) with a kind of crosslinkable preparation plating in the metallic surface, described preparation comprises at least
(A) adhesive composition (A) of at least a thermally cross-linkable of 20% to 70 weight % and/or photochemical crosslinking,
(B) at least a mean particle size of 20% to 70 weight % is less than the inorganic filler in small, broken bits of 10 μ m,
(C) at least a corrosion prevention agent of 0.25% to 40 weight % and
(D) randomly, a kind of solvent,
Condition desolventizes the summation meter of outer all components for weight % is based on, and
(2) make coating layer heat cross-linking and/or photochemical crosslinking,
Wherein the corrosion prevention agent is at least a by following monomer structure unit synthetic multipolymer (C):
(c1) at least a monoethenoid unsaturated hydrocarbons (c1a) of 70 to 30 moles of % and/or at least a being selected from are used the X of functional group
1The monomer (c1b) of monoethenoid unsaturated hydrocarbons of modification (c1b ') and vinyl ether (c1b "),
(c2) at least a monoethenoid unsaturated dicarboxylic acid and/or its acid anhydrides (c2a) and/or its derivative (c2b) of 30 to 70 moles of % with 4 to 8 carbon atoms,
Derivative (c2b) is that dicarboxylic acid and general formula are HO-R
1-X
2 nThe ester of alcohol (I) and/or with ammonia and/or general formula be HR
2N-R
1-X
2 nThe acid amides of amine (II) or imide, abbreviation is defined as follows:
R
1: have the alkyl of (n+1) valency of 1 to 40 carbon atom, wherein non-conterminous carbon atom also can be substituted by O and/or N;
R
2: H, C
1To C
10Alkyl or-(R
1-X
2 n)
N:1,2 or 3; With
X
2: a kind of functional group; And
(c3) other olefin type unsaturated monomer of 0 to 10 mole of %, be different from (c1) and (c2) but can with (c1) and (c2) copolymerization,
Its amount is separately based on the total amount meter of all monomeric units in the multipolymer.
In a kind of preferred embodiment of present method, the inventive method is a kind of continuation method that is used for the coated metal roll bending.
In addition, found a kind of preparation that is suitable for implementing present method.
Description of drawings
Fig. 1: the cross section that goes on foot the metal roll bending of pre-treatment coatings with prior art two.
Fig. 2: with the cross section of the metal roll bending of comprehensive pretreatment coating of the present invention.
Can provide metallic surface by method of the present invention with comprehensive pretreatment layer.The thickness of comprehensive pretreatment layer of the present invention is 1 to 25 μ m.
Surface discussed herein can be the surface of the metal products of arbitrary shape in principle.It can be the surface of the goods all be made up of metal; Perhaps, also can be just with the metal coating and itself can be by other material goods of forming of polymkeric substance or composition for example.
But particularly advantageously, described goods can be the similar tabular goods with metallic surface, and promptly thickness is significantly less than the goods that other direction is measured.Example comprises panelling, paillon foil, steel plate, especially metal roll bending and by its manufacturing---for example by cutting, reshaping and joint---the metallic surface parts, for example by its body of a motor car that makes or parts.The thickness of this metallic substance or wall thickness preferably are lower than 4mm, and for example 0.25 to 2mm.
Can be used for all types of metals of coating on the methodological principle of the present invention.But preferred basic metal or the alloy that in the structural metal material, uses and need carry out corrosion prevention usually of described metal.
Method of the present invention can be preferred for the surface-coated comprehensive pretreatment layer at iron, steel, zinc, zinc alloy, aluminum or aluminum alloy.Described surface especially can be the surface of galvanized iron or steel.In a kind of preferred embodiment of present method, described surface is the surface of roll bending metal, especially electrogalvanizing steel or electro-galvanized steel.Rolled steel plate can single face herein, and is also can the two sides zinc-plated.
Zinc alloy or aluminium alloy and to be used for the steel plate coating be known to those skilled in the art.Those skilled in the art can select the characteristic and the amount of alloying constituent according to required end-use.The composition of typical zinc alloy especially comprises Al, Pb, Si, Mg, Sn, Cu or Cd.The composition of typical aluminium alloy especially comprises Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.Term " zinc alloy " also comprises the Al/Zn that wherein A1 and Zn exist with about equally amount.With the commercially available acquisition of the steel of this alloy coating.Steel itself can comprise general alloying constituent well known by persons skilled in the art.
Being used for term of the present invention " comprehensive pretreatment layer " means coating of the present invention directly is coated on the metallic surface and need not any corrosion-inhibition pre-treatment, for example passivation, coating conversion coating or phosphatizing especially need not to use in advance Cr (VI) compound to handle.The comprehensive pretreatment layer with passivation layer and bottom organic coating and, if suitable, other coating is merged into a single layer.Term " metallic surface " is not definitely to be equivalent to naked metal herein certainly, and is meant the surface of usually using metal or forming inevitably during clean metal before applying the comprehensive pretreatment layer in atmospheric environment.Actual metal for example can have one deck moisture content film or skim oxide compound or hydrous oxide.
On the comprehensive pretreatment layer, can advantageously directly apply other paint film, and need not to apply again in advance organic priming paint.But should be understood that, can use other organic underlayer coating under specific circumstances, although preferably do not use.The characteristic of other paint film can be decided according to the purposes of metal expection.
The preparation that the present invention is used to apply the comprehensive pretreatment layer can be based on the preparation of organic solvent, moisture or main aqueous preparation or not solvent-laden preparation.Comprise adhesive composition (A), at least a inorganic filler in small, broken bits (B) and at least a corrosion prevention agent (C) of at least a heat cross-linking and/or photochemical crosslinking in the preparation.
Term " crosslinkable adhesive composition " hereinafter refers to, in a kind of known in principle mode, for those parts that form in the preparation that film works.It forms polymeric web in heat and/or photochemical solidification process.Comprise the crosslinkable composition of heat and/or photochemistry in the crosslinkable adhesive composition.The crosslinkable composition can be lower-molecular substance, oligopolymer or polymkeric substance.They have at least two crosslinkable groups usually.Crosslinkable group can be can with the radical reaction of himself kind (" with its oneself "), also can be can with the active function groups of complement activity functional group reactions.Can envision various possible combinations by known mode in principle.Adhesive composition can comprise that for example, itself is polymer binder and one or more lower-molecular substances or the oligopolymer linking agent (V) of crosslinkable not.Perhaps polymer binder itself can contain can with polymkeric substance in and/or the crosslinkable groups of other crosslinkable radical reaction in the linking agent that uses in addition.
Particularly advantageously, can use oligopolymer or the prepolymer that comprises crosslinkable groups and utilize linking agent to be cross-linked to each other.
When heating the film that applies under the temperature more than room temperature, adhesive composition thermally cross-linkable or heat cured takes place crosslinked.This coating system those skilled in the art are also referred to as " roasting varnish ".It contains at room temperature and does not react, does not perhaps react at least with tangible speed, and the crosslinkable group of reaction at high temperature only.The performance that crosslinkable adhesive composition especially is fit to the inventive method be its be higher than 60 ℃, preferably be higher than 80 ℃, more preferably be higher than 100 ℃, extremely preferably be higher than under 120 ℃ the temperature crosslinked.Advantageously, can use 100 to 250 ℃, preferably 120 to 220 ℃, more preferably at 150 to 200 ℃ of those crosslinked adhesive compositions.
Adhesive composition (A) can be the adhesive composition commonly used in roll bending coating material field.Use the coating of roll bending coating material coating to require to have enough elasticity.Thereby the adhesive composition that is used for roll bending coating material preferably contains soft segment.The tackiness agent and the adhesive composition that are fit to are known in principle to those skilled in the art.Should be understood that leaf can use different mixture of polymers, main mixing process does not produce any undesired effect.The example that is tackiness agent comprises (methyl) acrylate (being total to) polymkeric substance, polyethylene base ester, polyester, Synolac, polylactone, polycarbonate, polyethers, Resins, epoxy-amine adduct, polyureas, polymeric amide, polyimide or the urethane of partial hydrolysis.Those skilled in the art can carry out appropriate selection according to the end-use of required coated metal.
Can preferably use based on the adhesive composition of polyester, Resins, epoxy, urethane or acrylate for the system of thermofixation and to implement the present invention.
Can be based on the adhesive composition of polyester by known mode in principle, by lower-molecular substance dicarboxylic acid and glycol and, if suitable, other monomer is synthetic.Other monomer especially comprises the monomer with branching, for example tricarboxylic acid or triol.For the roll bending coating, use usually to have low-molecular-weight relatively polyester, preferably having Mn is 500 to 10000g/ moles, preferred 1000 to 5000g/ moles, the more preferably polyester of 2000 to 4000g/ moles.
Can regulate by selecting " firmly " or " soft " monomer by known mode in principle based on the consistency and elasticity of the film of polyester.The example of " firmly " dicarboxylic acid comprises aryl dicarboxylic acid or its hydrogenated derivatives, for example m-phthalic acid, terephthalic acid, phthalic acid, hexahydro-phthalic acid and derivative thereof, especially its acid anhydrides or ester.The example of " soft " dicarboxylic acid especially comprises the aliphatic series 1 with at least 4 carbon atoms, alpha, omega-dicarboxylic acid, for example hexanodioic acid, nonane diacid, sebacic acid or dodecanedioic acid.The example of " firmly " glycol comprises ethylene glycol, 1,2-propylene glycol, neopentyl glycol or 1,4-cyclohexanedimethanol.The example of " soft " glycol comprises glycol ether, triglycol, has the aliphatic series 1 of at least 4 carbon atoms, omega-diol, for example 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol or 1,12-dodecanediol.Be used to implement preferred polyester of the present invention and comprise at least one " soft " monomer.
Be used for the commercially available acquisition of polyester of coating.At for example " the Liv Ullmann industrial chemistry encyclopaedia " of electronic edition distribution, sixth version, 2000, " paint and coating-saturated polyester coating " (" Paints and Coatings-Saturated Polyester Coatings " inUllmann ' s Encyclopedia of Industrial Chemistry, 6th ed., 2000, Electronic Release) provided the details of polyester in.
Adhesive composition based on epoxide can be used for organic radical or water-base preparation.The polymkeric substance of epoxy-functional can be prepared by a kind of known in principle mode, for example by epoxy-functional monomer for example diglycidyl rthers of bisphenol-A, Bisphenol F diglycidyl ether or hexylene glycol diglycidyl ether, for example dihydroxyphenyl propane or Bisphenol F reaction make with alcohol.Particularly suitable soft segment is the rare and/or polyoxytrimethylene segment of polyoxyethylene.It can be advantageously by using ethoxylation and/or propoxylated bisphenol to add.Tackiness agent should be preferably chloride not.The commercially available acquisition of epoxy-functional polymkeric substance, for example trade name is Epon
Or Epikote
Polymkeric substance." the Liv Ullmann industrial chemistry encyclopaedia " that the details of epoxy-functional polymkeric substance is for example issued at electronic edition, sixth version, 2000, " Resins, epoxy " (" Epoxy Resins " in U11mann ' sEncyclopedia of Industrial Chemistry, 6th.ed., 2000, Electronic Release) provides in.
The epoxy-functional tackiness agent also can be further functionalized.Resins, epoxy-amine adduct for example, it can be by making described epoxy-functional polymkeric substance and amine, and especially for example diethanolamine or the reaction of N-methyl butanol amine obtain with secondary amine.
The polyacrylic ester based adhesive is particularly suitable for water-base preparation.The example of the acrylate that is fit to comprises emulsion polymer or multipolymer, especially by ordinary method by vinylformic acid and/or acrylic acid derivative and/or vi-ny l aromatic monomers for example vinylbenzene and, if it is suitable, the stable acrylate dispersoid of negatively charged ion that crosslinkable monomer obtains, the example of described acrylic acid derivative is for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate or (methyl) 2-EHA of acrylate.Those skilled in the art can be by a kind of known in principle mode, by adjusting for example vinylbenzene or methyl methacrylate and " soft " monomer ratio of butyl acrylate or 2-EHA for example of " firmly " monomer, the hardness of tackiness agent is regulated.Be particularly preferred for the acrylic acid dispersion preparation have in addition can with the monomer of the functional group of linking agent reaction.Can especially be the OH base with the functional group of linking agent reaction.The OH base can perhaps use epoxy acrylate then to be hydrolyzed and add in the polyacrylic ester by using monomer for example hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyl butylacrylic acid ester or N hydroxymethyl acrylamide.The commercially available acquisition of polyacrylate dispersion that is fit to.
Tackiness agent based on polyurethane dispersions is particularly suitable for water-base preparation.Polyurethane dispersions can obtain dispersion stable by introducing anionic segments and/or hydrophilic segment in the polyurethane chain by a kind of known in principle mode.Can preferably use amount meter as soft segment based on used glycol, the relative high-molecular weight glycol of 20 to 100 moles of %, preferred Mn is about the polyester glycol of 500 to 5000g/ moles, preferred 1000 to 3000g/ moles.Particularly advantageously can use and contain the Polyurethane dispersion enforcement the present invention of two (4-isocyanic ester cyclohexyl) methane as isocyanate prepolymer composition.The Polyurethane dispersion of the type is disclosed in for example DE-A 19,914 896.The commercially available acquisition of Polyurethane dispersion that is fit to.
The linking agent that is used for heat cross-linking that is fit to is known in principle to those skilled in the art.
Suitable example comprises the epoxide based cross-linker, wherein by linking group two or more epoxide groups is combined togather.Example comprises the low-molecular weight compound with two epoxy group(ing), hexanediol diglycidyl ether, phthalic acid diglycidylether or cyclanes compound 3 ', 4 '-epoxycyclohexyl carboxylic acid 3 for example for example, 4-epoxycyclohexyl methyl esters.
Be suitable as the highly active melamine derivative of having of linking agent in addition, for example hexamethylolmelamine or the corresponding etherate aminoresin of HMMM, six butoxymethyl trimeric cyanamides or optional modification for example.The commercially available acquisition of this class linking agent, for example Luwipal
(BASF AG).
Especially preferably use the block polyisocyanate linking agent to implement the present invention.When carrying out block reaction, isocyanic ester group and block agent generation reversible reaction.When being heated to comparatively high temps, the block agent is removed again.The example of suitable block agent is disclosed among the DE-A 199 14 896 12 and is listed as the 13rd and walks to 13 and be listed as the 2nd row.The preferred especially polymeric polyisocyanate that has the ε-Ji Neixianan block that uses.
For quickening cross-linking process, can in preparation, add suitable catalyzer by a kind of known in principle mode.
Those skilled in the art can suitably select in linking agent according to used tackiness agent and required result.Should be understood that under the condition that character of coating is not had a negative impact, also can use the mixture of different linking agents.The amount of linking agent can advantageously be 10% to 35 weight % of tackiness agent total amount.
The epoxy-functional polymkeric substance for example can use based on polyamines, such as the linking agent of Diethylenetriaminee (DETA), and for example amine adduct or polyamino acid amides.For example has advantage based on carboxylic acid anhydrides or the linking agent mentioned based on trimeric cyanamide.The preferred especially block polyisocyanate of having mentioned.
The acrylate dispersoid that is used for heat cross-linking for example can use above-mentioned linking agent based on trimeric cyanamide or blocked isocyanate.In addition, the epoxy-functional linking agent also is suitable.
The Polyurethane dispersion or the polyester that are used for heat cross-linking can use for example above-mentioned linking agent or epoxy-functional linking agent based on trimeric cyanamide, blocked isocyanate.
But with regard to the preparation of photochemical crosslinking, adhesive composition (A) but in comprise the group of photochemical crosslinking.Term " photochemical crosslinking " comprise by various energetic rays for example UV, VIS, NIR or electron rays (electron beam) carry out crosslinked.But described group can be the group of various photochemical crosslinkings in principle, but preferred alkenes type unsaturated group herein.
But the adhesive composition of photochemical crosslinking generally includes oligomeric or polymeric compounds, but contain in the described compound photochemical crosslinking group and, if suitable, also contain and be generally monomeric reactive thinner.The viscosity of reactive thinner is lower than viscosity oligomeric or the polymeric linking agent, thereby has adopted thinner composition in radiation-curing system.This adhesive composition that is used for photochemical crosslinking also comprises one or more light triggers usually.
But the example of the adhesive composition of photochemical crosslinking comprises for example polyfunctional group (methyl) acrylate, urethane (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbonic ether (methyl) acrylate, polyethers (methyl) acrylate, if suitable for example (methyl) methyl acrylate, butylene glycol diacrylate, hexanediyl ester or Viscoat 295 mix with reactive thinner.The page 3 the 10th that is described in more detail among the WO 2005/080484 of relevant radiation-solidified tackiness agent walks to the 16th page of the 35th row and provides.The light trigger that is fit to provides at 19 page of the 10th row of the 18th page of eighth row to the of this specification sheets.
Implement to should be understood that when of the present invention that also can use can be by light and heat chemofacies bonded mode solidified adhesive composition (these systems are also referred to as dual-curing system).
The adhesive composition (A) that contains 20% to 70 weight % in the formulations employed of the present invention.This quantity based on desolventize or solvent mixture outside the summation meter of preparation all the components.This measures preferred 30% to 60 weight %, more preferably 40% to 50 weight %.
The preparation that is used for the inventive method also comprises at least a inorganic filler in small, broken bits (B).Also can comprise in the weighting agent for example as hydrophobic or hydrophilic other organic coating.The mean particle size of weighting agent is less than 10 μ m.Mean particle size is preferably 10nm to 9 μ m, more preferably 100nm to5 μ m.For the particle of sphere or almost spherical, these data refer to diameter; For example for the elongated piece, it refers to major axis for erose particle.Granularity refers to main particulate size.What those skilled in the art obviously knew is that solid particulate in small, broken bits agglomeration takes place and form bigger particle through regular meeting, and it must be well-dispersed in the preparation in use.Granularity can capable field technique personnel be selected according to the character of required coating.Can also select according to for example thickness of required coating.Generally speaking, can select smaller particles for thin coat-thickness those skilled in the art.
On the other hand, the weighting agent of Shi Heing comprises electric conductivity pigment and weighting agent.This class weighting agent plays the effect that improves welding property and improve follow-up coating by the electropaining material.Suitable electric conductivity weighting agent and pigment comprise phosphide, vanadium carbide, titanium nitride, moly-sulfide, graphite, carbon black or adulterated barium sulfate.The preferred phosphide that uses phosphide, the especially iron of Zn, Al, Si, Mn, Cr, Fe or Ni.The example of preferred metal phosphide comprises CrP, MnP, Fe
3P, Fe
2P, Ni
2P, NiP
2Or NiP
3
Also can use non-conducting pigment or weighting agent, amorphous silica for example in small, broken bits, alumina or titanium oxide, other element also can mix in the above-mentioned substance.Can use the unformed silica of calcium ion calcium as an example.
Other example of pigment comprises anticorrosive pigment for example zinc phosphate, zinc metaborate or a water barium metaborate.
Should be understood that the mixture that also can use different pigment.The usage quantity of pigment is 20% to 70 weight %.Accurate amount is decided according to required coating characteristic by those skilled in the art.Amount when employed amount is generally greater than the non-conducting weighting agent of use when using conductivity pigment.Preferably measuring when using conductivity pigment and weighting agent is 40% to 70 weight %; Preferably measuring when using non-conducting pigment is 20% to 50 weight %.
Multipolymer (C)
According to the present invention, also comprise at least a multipolymer (C) in the composition as the corrosion prevention agent.Multipolymer by monomer (c1) and (c2) and optional (c3) synthetic, certainly if possible, use two or more different monomers (c1), (c2) and/or optional (c3) separately.Except (c1), (c2) and if desired (c3), there is not other monomer.
Monomer (cl)
Used monomer (c1) is that at least a monoethenoid unsaturated hydrocarbons (c1a) and/or at least a being selected from of 70 to 30 moles of % used the X of functional group
1The monomer (c1b) of the monoethenoid unsaturated hydrocarbons c1b ' of modification and monoethenoid unsaturated ethers (c1b ").This quantity gives the total amount meter of used monomeric unit in the multipolymer.
(cla)
Monomer (c1a) can be the used hydrocarbon that contains the monoethenoid unsaturated group in principle.It can make the aliphatic hydrocrbon (alkene) and/or the alicyclic hydrocarbon (cycloolefin) of straight or branched.It also can be hydrocarbon, the especially vinyl aromatic compounds that also contains aryl except that the olefin type unsaturated group.Double bond position is in the α position in the preferred alkenes type unsaturated hydrocarbons.Generally speaking, at least 80% two keys that should have a α position in the employed monomer (c1a).
Term " hydrocarbon " also comprises the oligopolymer of propylene or has the C of the unbranched or preferred side chain of olefin type unsaturated group
4To C
10The oligopolymer of alkene.The number-average molecular weight M of employed oligopolymer
nUsually be not higher than 2300g/mol, preferred M
nBe 300 to 1300g/mol, more preferably 400 to 1200g/mol.The oligopolymer of preferred iso-butylene can be chosen wantonly in this oligopolymer and also comprises other C
3To C
10Alkene is as comonomer.Thisly be called " polyisobutene " based on continuing to use common name below the oligopolymer of iso-butylene.Used polyisobutene should preferably have α-double bond content of at least 70%, more preferably has at least 80%.It is known and commercially available acquisition to those skilled in the art that this polyisobutene---is also referred to as active polyisobutene---.
Except that described oligopolymer, be used to implement suitable monomer of the present invention (c1a) and comprise, especially, have the monoethenoid unsaturated hydrocarbons of 6 to 30 carbon atoms.The example of this hydrocarbon comprises hexene, heptene, octene, nonene, decene, undecylene, dodecylene, tetradecene, cetene, vaccenic acid, petrosilane, n-docosane, Diisobutylene, tri-isobutylene or vinylbenzene.
The preferred use has 9 to 27, more preferably has for example monoethenoid unsaturated hydrocarbons of 18 to 24 carbon atoms of 12 to 24 carbon atoms.Should be understood that the mixture that also can use different hydrocarbon.This mixture also can be the special mixture of different hydrocarbon, for example special C
20-24Mixture.
(c1a) especially preferably uses alkene as monomer, preferably has the 1-alkene of above-mentioned carbonatoms.Alkene is preferably linear or is at least substantially linear.The side chain that " substantially linear " is used in reference to any existence only is methyl or ethyl, and preferred is methyl only.
Described oligopolymer also is particularly suitable, preferred polyisobutene.Surprisingly can improve the handling property of Aquo System in this way especially.But oligopolymer does not preferably use as single monomer, but uses with the mixture with other monomer (c1a).Found that the content of oligopolymer for the total amount of all monomers (c1) is advisable to be no more than 60 moles of %.If exist, the amount of oligopolymer is generally 1 to 60 mole of %, and is preferred 10 to 55, more preferably 20 to 50 moles of %, for example about 20 moles of %.What be particularly suitable for that polyisobutene mixes mutually is the alkene with 12 to 24 carbon atoms.
(c1b’)
Use the X of functional group
1The monoethenoid unsaturated hydrocarbons of modification (c1b ') can be to have H atom on olefin type unsaturated group and wherein one or more hydrocarbon by the X of functional group in principle
1All hydrocarbon that replace.
It can be alkene, cycloolefin or the alkene that contains aryl.Preferred wherein double bond position is in the olefin type unsaturated hydrocarbons of α position.Monomer (c1b ') has 3 to 30 carbon atoms usually, preferred 6 to 24 carbon atoms, and more preferably 8 to 18 carbon atoms.It preferably contains an X of functional group
1Monomer (c1b ') be preferably have 3 to 30 carbon atoms, preferred 6 to 24 carbon atoms and more preferably linearity or the substantially linear α-undersaturated-omega-functionalized olefin and/or the 4-substituted phenylethylene of 8 to 18 carbon atoms.
By the X of functional group
1Can advantageously influence solubleness and the adhering in metallic surface and/or binder matrix of multipolymer (C) in preparation.According to the characteristic of adhesive composition and metallic surface, those skilled in the art can make appropriate selection to functional group.Described functional group is preferably at least a being selected from-Si (OR
3)
3(R wherein
3Be C
1To C
6Alkyl) ,-OR
4,-SR
4,-NR
4 2,-NH (C=O) R
4, COOR
4The R of ,-(C=O)
4,-COCH
2COOR
4,-(C=NR
4) R
4,-(C=N-NR
4 2) R
4,-(C=N-NR
4-(C=O)-NR
4 2) R
4,-(C=N-OR
4) R
4,-O-(C=O) NR
4,-NR
4(C=O) NR
4 2,-NR
4(C=NR4) NR
4,-CSNR
4 2,-CN ,-PO
2R
4 2,-PO
3R
4 2,-OPO
3R
4 2, (R wherein
4Be H, C independently of one another
1To C
6The salt of alkyl, aryl, alkali (soil) metal or-SO
3H) group.
Particularly preferred radicals X
1Be Si (OR
3)
3(R wherein
3=C
1To C
6Alkyl) ,-OR
4,-NR
4 2,-NH (C=O) R
4, COOR
4,-CSNR
4 2,-CN ,-PO
2R
4 2,-PO
3R
4 2,-OPO
3R
4 2, (R wherein
4Be H, C independently of one another
1To C
6The salt of alkyl, aryl, alkali (soil) metal or-SO
3H).Extremely especially preferably-COOH.
The example of suitable monomer (c1b ') comprises C
4To C
20(α, ω)-thiazolinyl carboxylic acid, for example vinylacetic acid or undecylene carboxylic acid; C
2To C
20(α, ω)-alkenyl phosphonic acid, for example monoesters of vinyl phosphonate, vinyl phosphonate or diester or salt; C
3To C
20The thiazolinyl nitrile is vinyl cyanide, allyl cyanide, 1-butylene nitrile, 2-methyl-3-crotononitrile, 2-methyl-2-butene nitrile, 1-, 2-, 3-or allyl acetonitrile or 1-hexene nitrile for example; Perhaps 4-substituted phenylethylene, for example 4-hydroxy styrenes or 4-carboxyl styrene.Should be understood that the mixture that also can use two or more monomers (c1b ').Preferably (c1b ') be 10-undecylene carboxylic acid.
(c1b”）
Vinyl ether (c1b "), in a kind of known in principle mode, for general formula is H
2C=CH-O-R
6Ether, R in the described ether
6Be the alkyl that has 1 to 30 carbon atom, preferably has 2 to 20 carbon atoms and more preferably have straight chain, side chain or the cyclic preferred aliphatic series of 6 to 18 carbon atoms.Described vinyl ether also can be a radicals R
6On one or more H atoms by the X of functional group
1The modified vinylic-ether that replaces, wherein X
1Definition as above.R
6Be preferably the group of linearity or substantially linear, wherein functional group preferably is present in and is preferably placed at terminal.Should be understood that and also can use two or more different vinyl ether (c1b ").
The example of suitable monomer (c1b ") comprises 1,4-hydroxymethyl-cyclohexane mono vinyl ether, glycol monomethyl vinyl ether, diglycol monotertiary vinyl ether, hydroxy butyl vinyl ether, methylvinylether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether or tert-Butyl vinyl ether.
Be the used multipolymer (C) of preparation the present invention, can only use monomer (c1a) or only use monomer (c1b) or use monomer (c1a) and mixture (c1b).Preferably only use monomer (c1a) or mixture (c1a) and (c1b).For the situation of using (c1a) and mixture (c1b), the mixture of preferred use (c1a) and (c1b ').For the situation of using mixture, the amount of monomer (c1b) is generally 0.1 to 60 mole of % for the total amount of all monomers (c1), preferred 1 to 50 mole of %, more preferably 5 to 30 moles of %.
Monomer (c2)
According to the present invention, use at least a of 30 to 70 moles of % to have 4 to 8 carbon atom monoethenoid unsaturated dicarboxylic acids and/or its acid anhydrides (c2a) and/or its derivative (c2b) as monomer (c2).Described quantity is with reference to the total amount meter of all monomeric units in the multipolymer (C).
(c2a)
The example of monoethenoid unsaturated dicarboxylic acid (c2a) comprises toxilic acid, fumaric acid, citraconic acid (citraconic acid), methylfumaric acid, methylene-succinic acid, methylene radical propanedioic acid or 4-cyclohexyl-1,2-dicarboxylic acid.Monomer also can be diacid acid salt and---in possible situation---its cyclic acid anhydride.Preferred monomers (c1a) is toxilic acid and/or maleic anhydride.
(c2b)
The derivative of monoethenoid unsaturated dicarboxylic acid (c2b) is that dicarboxylic acid and general formula are HO-R
1-X
2 nThe ester of alcohol (I) and/or with ammonia and/or general formula be HR
2N-R
1-X
2 nThe acid amides of amine (II) or imide.Each situation is preferred respectively 1, omega-functionalized alcohol and amine.
X in these formula
2Be any functional group.By the X of functional group
2Can advantageously influence solubleness and the adhering in metallic surface and/or binder matrix of multipolymer (C) in preparation.According to the characteristic of adhesive composition and metallic surface, those skilled in the art can make appropriate selection to functional group.Described functional group for example can be acidic groups or by acidic groups deutero-group.Described functional group especially can be a kind of being selected from-Si (OR
3)
3(R wherein
3Be C
1To C
6Alkyl) ,-OR
4,-SR
4,-NR
4 2,-NH (C=O) R
4, COOR
4The R of ,-(C=O)
4,-COCH
2COOR
4,-(C=NR
4) R
4,-(C=N-NR
4 2) R
4,-(C=N-NR
4-(C=O)-NR
4 2) R
4,-(C=N-OR
4) R
4,-O-(C=O) NR
4,-NR
4(C=O) NR
4 2,-NR
4(C=NR
4) NR
4,-CSNR
4 2,-CN ,-PO
2R
4 2,-PO
3R
4 2,-OPO
3R
4 2, (R wherein
4Be H, C independently of one another
1To C
6The salt of alkyl, aryl, alkali (soil) metal or-SO
3H) group.Be preferably-SH ,-CSNH
2,-CN ,-PO
3H
2Or-Si (OR
3)
3And/or its salt, and extremely preferred CN or-CSNH
2
The X of functional group at (I) or (II)
2Number n are generally 1,2 or 3, and preferred 1 or 2, and more preferably 1.
R in formula (I) or (II)
1For having (n+1)-valency alkyl of 1 to 40 carbon atom, described alkyl is with OH base and/or NHR
2With functional group or a plurality of X of functional group
2Be connected.In described group, non-conterminous carbon atom can be replaced with O and/or N.Group described herein is preferably 1, ω-functional group.
For divalent linker R
1Situation, described group is preferably the linearity 1 that has 1 to 20, preferably has 2 to 6 carbon atoms, ω-thiazolinyl.Preferred especially 1,2-vinyl, 1,3-propenyl, 1,4-butenyl, 1,5-pentenyl or 1,6-hexenyl.Further preferred described group can be the group with O atom, for example CH
2-CH
2-O-CH
2-CH
2-or general formula be
CH
2-CHR
7-[O-CH
2-CHR
7-]
m-many alkoxyl groups, wherein m is 2 to 13 natural number and R
7Position H or methyl.Has the basic R of this connection
1Examples for compounds comprise HO-CH
2-CH
2-CSNH
2, HO-CH
2-CH
2-SH, H
2N-CH
2-CH
2-CH
2-Si (OCH
3)
3, H
2N-(CH
2-)
6-CN, H
2N-CH
2-CH
2-OH or H
2N-CH
2-CH
2-O-CH
2-CH
2-OH.
If described group is intended for use to connect two or more functional groups, two or more functional groups are connected on the terminal C atom.But this situation R
1Preferably have one or more side chains.Straight chain can comprise C atom or preferred N atom.Examples for compounds with this group is (propyloic) amino dimethylene phosphonic acids (III) or (amino-ethyl) amino dimethylene phosphonic acids (IIIa).
Above-mentioned formula (I) and (II) in, R
2Be H, C
1To C
10Alkyl (preferred C
1To C
6Alkyl) or group-R
1-X
2 n, R wherein
1And X
2 nDefinition as above.Preferred R
2Be H or methyl and preferred especially H.
The derivative of dicarboxylic acid (c2b) can make two COOH groups of dicarboxylic acid all distinguish combined thing (I) and/or (II) esterification or amidation separately.But preferably has only an esterified or amidation in two COOH groups separately.The nature imide can only be formed by two COOH groups usually.It preferably has two adjacent COOH groups; Certainly it also can have non-conterminous COOH group.
Monomer (c3)
Multipolymer used in the present invention (C) also can comprise 0 to 10 mole of %, preferred 0 to 5 mole of %, more preferably other olefin type unsaturated monomer of 0 to 3 mole of % is as structural unit, described other olefin type unsaturated monomer is different from (c1) and (c2), but can with (c1) and (c2) copolymerization.This monomer can be used for---to be adjusted the character of multipolymer if desired---.Extremely especially preferably do not comprise monomer (c3).
The example of monomer (c3) comprises, especially, and (methyl) acrylic compound, for example (methyl) vinylformic acid or (methyl) acrylate; The hydrocarbon that perhaps has conjugated double bond, for example divinyl or isoprene.Described (methyl) acrylate also can contain other functional group, for example OH or COOH group.In addition, described monomer also can be the monomer with crosslinked action, wherein has two or more isolated olefin type unsaturated double-bonds.But the crosslinking copolymers degree should be too not big.If there is cross-linking monomer, its amount should not surpass 5 moles of %, preferred 3 moles of % and more preferably 2 moles of %, all monomeric total amount meters relatively usually.
Used monomer (c1), (c2) and the amount (c3) of the present invention provides.(c1) amount is preferably 35 to 65 moles of % and amount (c2) is preferably 65 to 35 moles of %; (c1) amount is preferably 40 to 60 moles of % especially and (c2) is 60 to 40 moles of %; And amount (c1) is preferably 45 to 55 moles of % extremely especially and (c2) is that exemplarily (c1) and amount (c2) can reach about 50 moles of % to 55 to 45 moles of %. separately.
The preparation of multipolymer (C)
The preparation of the multipolymer (C) that the present invention is used is preferably undertaken by radical polymerization.The enforcement of radical polymerization process comprises required equipment, is known in principle to those skilled in the art.Polymerization process preferably uses the pyrolysis polymerization starter to carry out.Preferably can use superoxide as thermal initiator.Certainly polymerization also can be undertaken by photochemistry.
The preferred cyclic acid anhydride of---under the possible situation of chemistry---dicarboxylic acid that uses is as monomer (c2a).Especially preferably use maleic anhydride.
Spendable solvent comprises that preferably, aprotic solvent is toluene, dimethylbenzene, aliphatic cpd, alkane, volatile oil or ketone for example.But use and to have relative high boiling point, especially during the high long-chain monoethenoid unsaturated hydrocarbon monomer with 150 ℃ of boiling point, also can solvent-freely operate.In this case, unsaturated hydrocarbons itself is as solvent.
Use thermal initiator radical polymerization can 60-250 ℃, preferred 80-200 ℃, more preferably 100-180 ℃, and carry out particularly preferably in 130-170 ℃ temperature range.The monomeric relatively amount of the amount of initiator is 0.1% to 10 weight %, preferred 0.2% to 5 weight % and preferred especially 0.5% to 2 weight %.Generally speaking, the amount of about 1 weight % is used in suggestion.Polymerization time is generally 1-12h, preferred 2-10h, and more preferably 4-8h.Multipolymer can separate in solvent or directly obtains with solvent-free form by method known to those skilled in the art.
When multipolymer no longer further reacts generation derivative (c2b), make the anhydride group hydrolysis of existence form corresponding dicarboxylic acid units usually.In this case, can use described process channeling conduct by the expection of multipolymer advisably.
Be present in the situation of aqueous binder system for multipolymer to be used, suggestion is hydrolyzed in water.For reaching this purpose, the multipolymer that can contain anhydride group is introduced in the water, and advisably by mild heat and add a kind of alkali and make its hydrolysis.Found that the temperature up to 100 ℃ is suitable.Suitable alkali comprises that especially, tertiary amine is dimethylethanolamine for example.The amount of alkali is generally 0.1-2 equivalent (based on dicarboxylic anhydride unit meter in the polymkeric substance), preferred 0.5-1.5 equivalent, and more preferably 0.7-1.2 equivalent.Typically, the amount of used alkali is about each anhydride group 1 equivalent.Aqueous copolymers solution that generates or dispersion can be directly used in the crosslinkable preparation of preparation present method.Certainly, multipolymer also can separate by the known in principle method of those skilled in the art.
If multipolymer will be used for the adhesive composition based on organic solvent, it can be dissolved or dispersed in organic solvent for example in THF, dioxane or the toluene, and add entry, and also can add alkali with the required amount of stoichiometry.Hydrolysis can be undertaken by mild heat as mentioned above.Perhaps also can then carry out exchange of solvent in water after the hydrolysis.
The multipolymer that contains monoethenoid unsaturated dicarboxylic acid (c2b) in principle can be by two kinds of different synthesis mode preparations.Can use derivative (c2b) as actual polymeric monomer on the one hand.These monomers can be in advance by independent with become step by functionalized alcohol (I) and/or functionalized amine (II) and dicarboxylic acid or preferably its acid anhydrides make.
In the preferred embodiment of the present invention, as mentioned above, prepare initial multipolymer by monomer (c1) and non-deutero-olefin type unsaturated dicarboxylic acid (c1a).The dicarboxylic acid that is preferred for this purpose is so that---under the possible situation---form of its intramolecular anhydride is used, and especially preferably uses maleic anhydride.After multipolymer forms, can make the dicarboxylic acid units of copolymerization, preferred corresponding dicarboxylic anhydride unit and more preferably maleic anhydride unit by this synthetic schemes, with a kind of similar polymeric reaction and functionalized pure HO-R
1-X
2 n(I) and/or ammonia and/or functionalized amine HR
2N-R
1-X
2 n(II) reaction.
Reaction can in body, carry out (solvent-free) or, preferably, in suitable aprotic solvent, carry out.The example of suitable aprotic solvent comprises, especially, polar aprotic solvent for example acetone, methylethylketone (MEK), dioxane or THF and, if suitable, non-polar hydrocarbon is toluene or aliphatic hydrocrbon for example.
Non-modified copolymer for example can be introduced when reacting in the solvent in the reactor, and be added required functionalized pure HO-R with aequum subsequently
1-X
2 n(I), ammonia or required functionalized amine HR
2N-R
1-X
2 n(II).The functionalized reagent can advantageously be dissolved in the suitable solvent in advance.Derivatization is preferably undertaken by heating.Found that the reaction times suits in 2 to 25h scopes.When using primary amine or ammonia, preferably obtain corresponding amide in temperature, and when continuing to be increased to higher temperature, also form imide up to 100 ℃.When 130 to 140 ℃ temperature, imido formation has accounted for leading.Preferably should avoid forming imide structure.
Carrying out the amount of functionalized used reagent determines according to required functionalized degree.Found that suitable amount is every dicarboxylic acid units 0.5 to 1.5 equivalent, preferred 0.6 to 1.2, more preferably 0.8 to 1.1 and extremely preferred about 1 equivalent.If institute's consumption is lower than 1 equivalent, then residual anhydride group can step secondarily in hydrolysis open.
Certainly also can use one or more functionalized pure HO-R respectively
1-X
2 n(I) and/or ammonia or functionalized amine HR
2N-R
1-X
2 n(II) mixture.Reaction sequence also can be: at first use a kind of alcohol/ammonia/amine that reaction is carried out, then re-use another kind of alcohol/ammonia/amine and react.
The organic solution of the modified copolymer that is obtained can be directly used in the crosslinkable organic formulations of preparation.But should be understood that, also can polymkeric substance be separated from these solution by method known to those skilled in the art.
For incorporating aqueous formulation into, can suitably in solution, add entry, and can organic solvent be separated by method known to those skilled in the art.
Also some or all acidic-groups in the polymkeric substance can be neutralized.The pH of copolymer solution should be at least 6 usually, preferably be at least 7, to guarantee having enough solubleness or dispersiveness in water.With regard to non-functionalized copolymers, these data roughly are equivalent to every dicarboxylic acid units 1 normal alkali.With regard to functionalized copolymers, certain X of functional group
1Or X
2The solvability of multipolymer will be influenced.The example that is used for the suitable alkali of neutral comprises ammonia, the oxyhydroxide of basic metal and alkaline-earth metal, zinc oxide, straight chain, ring and/or side chain C
1-C
8Single-, two-and trialkylamine, the C of straight or branched
1-C
8Single-, two-and trialkanolamine, especially single-, two-and trialkanolamine, straight or branched C
1-C
8Single-, two-and the straight or branched C of trialkanolamine
1-C
8Alkyl ester, few amine and polyamines be diethylidene amine for example.Alkali can use after hydrolytic process, or advantageously, just uses in the hydrolytic process of acid anhydrides.
The molecular weight M of multipolymer
wCan capable field technique personnel select according to required end-use.Found that 1000 to 100000g/mol Mw suits, preferred 1500 to 50000g/mol, and more preferably 2000 to 20000g/mol, and extremely preferred 3000 to 15000g/mol, and for example 8000 to 14000g/mol.
For preparation comprehensive pretreatment layer, can use single multipolymer (C) or two or more different multipolymers (C).In described multipolymer (C), can make concrete selection according to the performance of required comprehensive pretreatment layer by those skilled in the art in principle.It will be apparent for a person skilled in the art that not to be adhesive composition, solvent or the metallic surface that the multipolymer (C) of all kinds all is fit to used kind comparably.
The used multipolymer (C) of the present invention generally with 0.25% to 40 weight %, preferred 0.5% to 30 weight %, more preferably the amount of 0.7% to 20 weight % and extremely preferred 1.0% to 10 weight % is used, based on the amount meter that desolventizes outer all components in the preparation.
Usually contain The suitable solvent in the preparation as component (D), wherein component is present in solution and/or the dispersion, so that the even plating of preparation is on the surface.Solvent is removed before coating curing usually.But also can prepare solvent-free or solvent-free substantially preparation in principle.The described preparation of this kind situation is for example powder coating material or photochemical solidification preparation.
The suitable solvent for can dissolve, the solvent of dispersion, suspension or emulsification The compounds of this invention.It can be organic solvent or water.Should be understood that, also can use the mixture of different organic solvents or the mixture of organic solvent and water.In principle can by those skilled in the art according to required end-use and according to the present invention the characteristics of compound used therefor in described solvent, suitably select.
The example of organic solvent comprises hydrocarbon, for example toluene, dimethylbenzene or the mixture that is obtained such as the crude refining process such as the hydrocarbon-fraction of certain boiling range (defined-boiling-range); Ether, for example THF or polyethers, for example polyoxyethylene glycol; Ether alcohol, for example butyl glycol; Ether ethylene glycol ethyl ethers acid esters, for example butyl glycol acetate; Ketone, for example acetone; And alcohol, for example methyl alcohol, ethanol or propyl alcohol.
In addition, also can use moisture or main aqueous solvent mixture.Main aqueous solvent mixture means and contains at least 50 weight %, preferred at least 65 weight %, and the more preferably solvent mixture of at least 80 weight % water.Other component is the solvent that water dissolves each other.Example comprises single alcohol for example methyl alcohol, ethanol or propyl alcohol, and higher alcohol is ethylene glycol or polyether polyol for example, and ether alcohol for example butyl glycol or methoxypropanol.
The amount of solvent can be selected according to required preparation characteristic and according to required solution and coating method by those skilled in the art.Usually the weight percent of coating ingredients and solvent is 10: 1 to 1: 10, preferred about 2: 1, but there is no any plan that limit the invention to this.Certainly, also can be prepared into enriched material earlier and only just its dilution is desired concn in use.
Preparation is by the thorough mixing of solvent prepares with formulation component and---when using solvent---.Suitable mixing or diverting device are known to those skilled in the art.Multipolymer preferably uses with solution or emulsion form that anhydride group and/or its derivative hydrolysis are obtained, and if suitable, also can carry out exchange of solvent.Used solvent should be chosen as at least and used adhesive composition compatibility in these synthesis steps; The same solvent of preferred especially use.
Except that component (A) with (C) and optional (D), also can comprise one or more auxiliary agents and/or additive (E) in the preparation.The purpose of this auxiliary agent and/or additive is to adjust the performance of coating.Its amount is no more than 20 weight % usually for the summation that desolventizes outer all components, and preferably is no more than 10%.
The example of suitable additive is colour and/or effect pigment, the rheology auxiliary agent, the UV absorption agent, photostabilizer, free-radical scavengers, free radical addition polymerization initiator, the heat cross-linking catalyzer, light trigger and light are assisted initiator, slip additive, polymerization retarder, defoamer, emulsifying agent, the devolatilization agent, wetting agent, dispersion agent, adhesion promoter, flowing regulator, film coalescence aid, rheology modifier (thickening material), fire retardant, siccative, anti, other corrosion inhibitor, wax and matting agent, as by Johan Bieleman, Wiley-VCH, " Lackadditive " that Weinheim showed [Additives for coatings], NewYork, 1998, or it is known to walk to 15 row, 54 row by German patent application DE 199 14 896 A1 the 13rd row 56.
With the preparation plating in the metallic surface to implement method of the present invention.
Can choose wantonly before processing the surface is cleaned.When processing of the present invention to metal finishing---as rolled steel plate is carried out electrogalvanizing or galvanizing---after when carrying out immediately, then can make roll bending contact and need not to clean in advance usually with treatment solution of the present invention.If but the metal roll bending before carrying out plating according to the present invention through storing and/or transportation, have the corrosion prevention oil or the preservative oil that is corroded on the roll bending usually and besmirch, then must clean before carrying out plating according to of the present invention.Cleaning can use conventional sanitising agent to carry out by mode well known by persons skilled in the art.
Preparation can pass through for example spraying plating, dipping, cast or roller coat plating.After the dip operation, workpiece can carry out drip-dry to remove unnecessary preparation; For situations such as metal sheet, tinsels, also can remove unnecessary preparation by squeezing out or grinding to roll with squeegee.Use preparation to carry out plating and at room temperature carry out usually, although do not plan to get rid of the possibility of carrying out at comparatively high temps in principle.
Preparation of the present invention is preferred for the metal lining roll bending.In this roll bending plating operation, but the plating single face carries out also can two-sidedly carrying out.Also can use different preparation plating upper surface and lower surface.
Preferred extremely especially roll bending plating is undertaken by continuation method.The plating production line is known in principle continuously.It generally includes at least one coating station, drying or roasting station and/or UV station, and if suitable other pre-treatment or aftertreatment station, for example cleaning or back cleaning station.The example of roll bending coating production line can be at R mpp Lexikon Lacke und Druckfarben, GeorgThieme Verlag, Stuttgart, New York, 1998,55 pages, find in " Coilcoating " or among German patent application DE 196 32 426 A1.Should be understood that the production line with different structure also is operable.
The speed of metal roll bending is selected according to the plating and the curing properties of used preparation by those skilled in the art.Found that the speed that is fit to is generally 10 to 200m/min, preferred 12 to 120m/min, and more preferably 14 to 100m/min, extremely preferred 16 to 80, and especially 20 to 70m/min.
The used crosslinkable preparation of the present invention can or preferably carry out plating by roller coat by spraying plating, cast during the metal lining roll bending.With regard to preferred roller coat situation,, the pickup roll of rotation dipped in the preparation for the treatment of plating thereby immersing the storage tank of the used preparation of the present invention.Preparation is direct or at least one angle stripper of process from pickup roll, transfers to the plating roller of rotation.Thereby the coating material is peeled off when roll bending moves with identical or opposite direction from this plating roller and is transferred on the roll bending.According to the present invention, oppositely peel off or oppositely rolling method be favourable, thereby preferred the use.The circumferential speed of plating roller is preferably 110% to 125% of roll bending speed, and the circumferential speed of pickup roll is 20% to 40% of a roll bending speed.Perhaps, formulations employed of the present invention also can directly be pressed into the slit between the two-layer roll bending, and this area is referred to as to compress charging (nip feed).
After the plating formulations employed of the present invention, remove any be present in the solvent in the coating and coating taken place crosslinked.This can carry out or carry out simultaneously in two independent steps.To remove and desolvate, preferably coating be heated by suitable equipment.Also can carry out drying by contacting with air-flow.Two kinds of methods can be used in combination.
The solidified method can be decided according to the characteristic of adhesive therefor system.Curing can be undertaken by heat and/or photochemical method.
With regard to the situation of heat cross-linking, be that the coating with plating heats.This can preferably pass through transmission of heat by convection, near infrared or far-infrared radiation and/or, when using the roll bending of iron-based, realize by electro-induction.
Solidifying required temperature especially decides according to used crosslinkable adhesive composition.The more SA adhesive composition of highly active adhesive composition can solidify under lower temperature.Usually cross-linking process carries out under at least 60 ℃ temperature, and preferably at least 80 ℃, more preferably at least 100 ℃, and extremely preferably at least 120 ℃.Crosslinked especially can 100 to 250 ℃, preferred 120 to 220 ℃, more preferably carry out at 150 to 200 ℃.The temperature of each situation indication be peak metal temperature (peak metal temperature) (PMT), its method that can be familiar with by those skilled in the art (for example, contactless Infrared survey or use the temperature measuring that adheres to calibration tape) records.
Heat-up time, promptly thermal curing time becomes according to the used coated substance of the present invention.The described time is preferably 10s to 2min.When employed when substantially be transmission of heat by convection, when preferred roll bending speed, need make forced air draft oven have 30 to 50m length, especially have 35 to 45m length.Force ventilated temperature be higher than certainly coating temperature and can be up to 350 ℃.
Photochemical solidification is undertaken by actinic radiation.Actinic radiation means electromagnetic radiation herein, for example near infrared, visible light, UV ray or X-light, perhaps bombardment, for example electron beam.For photochemical solidification, preferably use the UV/VIS radiation.If radiation also can---suitablely---be carried out under the situation of anaerobic, for example carry out in atmosphere of inert gases.Photochemical solidification can carry out under the standard temperature condition, promptly coating is not heated, and perhaps photochemical crosslinking also can at high temperature carry out, and for example 40 to 150 ℃, preferred 40 to 130 ℃, and especially carry out at 40 to 100 ℃.
A result of the inventive method is can be in the metallic surface, and especially the surface of iron, steel, zinc or zinc alloy, aluminum or aluminum alloy obtains the comprehensive pretreatment layer.The precision architecture of comprehensive pretreatment layer and composition are not still known us.Except that crosslinked adhesive composition (A), the comprehensive pretreatment layer also comprises weighting agent, multipolymer (C) and other optional component.Also can have the component of having removed from the metallic surface and being deposited on again on the metallic surface in addition, for example aluminium or zinc and, if suitable, the typical amorphous oxide of other metal.
The thickness of comprehensive pretreatment layer is 1 to 25 μ m, and can be decided according to the end-use of required coating quality and coating by those skilled in the art.The thickness of having found 3 to 15 μ m is normally suitable for the comprehensive pretreatment layer.The thickness of preferred 4 to 10 μ m, and the thickness of preferred especially 5 to 8 μ m.Thickness depends on the amount of the composition of institute's plating under every kind of situation.
With regard to the plating of trolley part, after the plating comprehensive pretreatment layer of the present invention, in fact may not then carry out the negative electrode dip-coating in some cases.If the comprehensive pretreatment layer also plans to replace negative electrode to electroplate, thicker a little coating is used in suggestion, and for example thickness is 10 to 25 μ m, preferred 12 to 25 μ m.
But also other coat film of plating on metallic surface with comprehensive pretreatment layer.The performance of required coat film and quantity are decided according to the purposes of required coated metal or forming metal parts by those skilled in the art.Comprehensive pretreatment layer of the present invention can make and itself be covered well, and has good tack with the subsequent coated film.Other coat film can comprise, for example colored film that applies, is coated with (clearcoating) or functionalization coating material clearly.An example of functionalization coating material is the soft coating material with high relatively weighting agent content.This coating material can advantageously carry out plating before colour coating and/or outer coating material, resist the physical disturbance that is for example caused by sheets of stone or scraping with protection metal and comprehensive pretreatment layer.
The plating of other coat film can carry out on described roll bending coating production line.In such cases, arrange the curing station that two or more plating station is arranged and choose wantonly successively.Perhaps, in corrosion protective layers plating and after solidifying, the roll bending of coating can be rolled and afterwards, on other production line other coating of plating.Other processing of the metal roll bending of coating can be carried out on the spot, maybe it can be transported to a different location and carry out other processing.Can make it have for example removable protective layer for reaching this purpose.
Also can handle the roll bending that has the comprehensive pretreatment layer earlier---for example by cutting, moulding and seam---to be formed into the shaped metal parts.Seam also can realize by the mode of welding.Afterwards, the molded article that is obtained can have other coat film as mentioned above.
Thereby the present invention also provides to have and applied the moulded products of metallic surface that thickness is the comprehensive pretreatment layer of 1 to 25 μ m, and moulded products also has other coat film.Term " moulded products " refers to comprise metal sheet, tinsel or the metal roll bending of coating herein, and by the metal parts of its acquisition.
This base part refers to that especially those can be used for the parts of panelling, panel or liner plate.Example comprises body of a motor car or its parts, the for example motorcycle of two-wheeled or the car body of bike, the parts of frame or these class vehicles are shell or panel for example, household electrical appliance are washing machine for example, dishwasher, dry cleaning machine, gas furnace and electric furnace, microwave oven, the shell of refrigerator or refrigerator, be used for technical equipment or install for example machine, power distribution cabinet, the panelling of counter body etc., structural element in the buildings is wall part for example, facing spare, the ceiling parts, window frame, doorframe or parts, the furniture that is made by metallic substance is the metal kitchen for example, metal frame, furniture parts, perhaps other accessory.Described parts also can be the goods that are used for storing liquid or other material of hollow, for example jar, kettle, bucket.
Following examples will be set forth the present invention in more detail.
Synthesizing of part A---used multipolymer
Part I---contain multipolymer synthetic of anhydride group
Copolymer A
MAn/C
12Alkene (mol ratio 1: 1) multipolymer
In the stirring tank of one 21 pilot scale, add 176.4g (1.05mol) n-12-1-alkene, charge into nitrogen and be heated to 150 ℃.In the process of 6h, drip 147.1g fusion maleic anhydride (MAn; 80 ℃, 1.50mol) charging 1 and 4.1g ditertiary butyl peroxide (based on monomer meter, the 1%) charging 2 that is dissolved in 75.6g (0.45mol) n-12-1-alkene.Reaction mixture is at 150 ℃ of restir 2h.Generate lurid solid resin.
Multipolymer B
MAn/C
12Alkene/vinylbenzene (mol ratio 1/0.9/0.1) multipolymer
Repeat the process of the embodiment of the invention 1, but use be 1.35mol n-12-1-alkene and the cinnamic mixture of 0.15mol but not only use n-12-1-alkene.
Multipolymer C
MAn/C
12Alkene/C
20-24Alkene (mol ratio 1/0.6/0.4) multipolymer
In one 15001 pressure reactor with anchor stirrer, temperature regulator and nitrogen inlet, at 60 ℃ with being pumped into 36.96kg C
20-24Alkene also sucks 31.48kg n-12-1-alkene.Initial material is heated to 150 ℃.Then in the process of 6h, be metered into charging of forming by the 1.03kg ditertiary butyl peroxide 1 and the charging of forming by 30.57kg fusion maleic anhydride 2.After charging 1 and 2 adds end, reactor is stirred 2h at 150 ℃.Then remove the acetone and the trimethyl carbinol in the 150-200mbar distillation.
Multipolymer D
MAn/C
12Alkene/polyisobutene 550 (mol ratio 1/0.8/0.2) multipolymer
In the stirring tank that has anchor stirrer and built-in thermometer of one 21 pilot scale, stirring and introducing under the condition of nitrogen, 363g (0.66mol) M
nHigh-activity polyisobutene (alpha-olefin content＞80%) (Glissopal for 550g/mol
550, BASF) and 323.4g (2.11mol) C
12Alkene is heated to 150 ℃.Then in the process of 6h, be metered into by the 323.4g maleic anhydride (80 ℃, the 3.3mol) charging 1 of Zu Chenging and by 13.56g ditertiary butyl peroxide (based on monomer meter, 1%) and 88.8g (0.53mol) C
12The charging 2 that alkene is formed.After charging 1 and 2 add to finish, with reactor at 150 ℃ of restir 2h.Obtain solid-state yellow polymer.
Multipolymer E
MAn/C
12Alkene/polyisobutene 1000 (mol ratio 1/0.8/0.2) multipolymer
In the stirring tank that has anchor stirrer and built-in thermometer of one 21 pilot scale, stirring and introducing under the condition of nitrogen, 600.0g (0.6mol) M
nHigh-activity polyisobutene (alpha-olefin content＞80%) (Glissopal for 1000g/mol
550, BASF) and 322.5g (1.92mol) C
12Alkene is heated to 150 ℃.Then in the process of 6h, be metered into by the 294.0g maleic anhydride (80 ℃, the 3.0mol) charging 1 of Zu Chenging and by 13.0g ditertiary butyl peroxide (based on monomer meter, 1%) and 80.6g (0.48mol) C
12The charging 2 that alkene is formed.After charging 1 and 2 add to finish, with reactor at 150 ℃ of restir 2h.Obtain solid-state yellow polymer.
Multipolymer F
MAn/C
12Alkene/10-undecylenic acid (mol ratio 1/0.9/0.1) multipolymer
In one 21 pilot scale stirring tank, add 554.4g (3.3mol) n-12-1-alkene and 8.293g (0.45mol) 10-undecylenic acid, charge into nitrogen and be heated to 150 ℃.In the process of 6h, and dropping 441g fusion maleic anhydride (80 ℃, 4.5mol) charging 1 and 12g ditertiary butyl peroxide (based on monomer meter, the 1%) charging 2 that is dissolved in 126g (0.75mol) n-12-1-alkene.Reaction mixture is at 150 ℃ of restir 2h.Generate lurid solid resin.
Multipolymer G
MAn/C
8Alkene (mol ratio 1/1) multipolymer
Repeat the process of the embodiment of the invention 1, but use be n-suffering-1-alkene but not use n-12-1-alkene.
Hydrolysis/the exchange of solvent of part II---resin
Overall test explanation II-1
The copolymer resin A to G that used various of 400g are contained anhydride group pulverize and are suspended in the 1000g water in the 21 pilot scale stirring tanks, and suspension is heated to 100 ℃.In the process of 1h, drip normal alkali (based on the maleic anhydride group meter in the resin) and with mixture in 100 ℃ of restir 6h, up to obtaining solution or stable emulsion.
Exchange of solvent II-2
The aqueous solution with 350g explanation 1 in a reactor mixes with the 400g butyl glycol.Then under 50 to 60 ℃ of temperature, remove and anhydrate by underpressure distillation.
Other situation of used specific compound, alkali and the polymkeric substance that obtains is listed in the table 1.
Part III---multipolymer functionalized
Overall test explanation III-1
In the stirring tank that has anchor stirrer and built-in thermometer of one 21 pilot scale, add and be present in maleic anhydride-olefin copolymer A to G of the special needs in the organic solvent, and charge into nitrogen.Then y ℃, in x hour process, drip the compound (I) of 1 normal various required hydroxyls-functionalized or amino-functional or (II).
Exchange of solvent:
After derivatization, can carry out the exchange of organic solvent to water.For reaching this purpose, product is mixed with water and alkali up to reaching required pH value.Then under reduced pressure the organic solvent distillation is removed.
Overall test explanation III-2
In the stirring tank that has anchor stirrer and built-in thermometer of one 21 pilot scale, add the compound (I) of the maleic anhydride-olefin copolymer A to G that needs especially and 1 normal various required hydroxyls-functionalized or amino-functional or (II), charge into nitrogen, and stirred x hour at y ℃.Then product is dissolved in the appropriate organic solvent.
After derivatization, as mentioned above, can carry out the exchange of organic solvent to water.
The compound (I) of used all cpds, used hydroxyl-functionalized or amino-functional or (II) and other situation of the character of derivative copolymer list in the table 2.
Table 1: multipolymer and water-based emulsion according to the unmodified dicarboxylic acid units of leader II-1 hydrolysis
| The multipolymer numbering | Used parent material | Describe | Mol ratio | Alkali | Solvent | The K value | Solid content [weight %] | pH |
| Copolymer 1 | A | MAn/C 12Alkene | 1/1 | Dimethylethanolamine | Water | - | 28.7 | 8.3 |
| Copolymer 1 a | A | MAn/C 12Alkene | 1/1 | Dimethylethanolamine | Butyl glycol * | 14.4 | 22 | - |
| Multipolymer 2 | B | MAn/C 12Alkene/vinylbenzene | 1/0.9/0.1 | Dimethylethanolamine | Water | 24.8 | 27.0 | 8.4 |
| Multipolymer 3 | C | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | Thanomin | Water | - | 17.4 | 8.3 |
| Multipolymer 4 | D | MAn/C 12Alkene/PIB550 | 1/0.8/0.2 | Dimethylethanolamine | Water | 33.5 | 22.0 | 8.5 |
| Multipolymer 5 | E | MAn/C 12Alkene/PIB1000 | 1/0.8/0.2 | Dimethylethanolamine | Water | 22.6 | 26.8 | 8.3 |
| Multipolymer 5a | E | MAn/C 12Alkene/PIB1000 | 1/0.8/0.2 | Dimethylethanolamine | Butyl glycol * | 14.1 | 18.5 | - |
| Multipolymer 6 | F | MAn/C 12Alkene/undecylenic acid | 1/0.9/0.1 | Dimethylethanolamine | Water | - | 25.2 | - |
| Multipolymer 6a | F | MAn/C 12Alkene/undecylenic acid | 1/0.9/0.1 | Dimethylethanolamine | Butyl glycol * | - | 41.2 | - |
| Multipolymer 7a | G | MAn/C 8Alkene | 1/1 | Dimethylethanolamine | Butyl glycol * | - | 19.4 | - |
Note: each K value is according to H.Fikentscher, Cellulose-Chemie, and Vol.13, the method for 58-64 page or leaf and 71-74 page or leaf (1932) records in 25 ℃, the solution of not adjusting the pH value (aqueous solution or butyl glycol) of 1 weight % concentration.The K value is big more, and the molecular weight of polymkeric substance is big more.
* exchange of solvent---data undetermined after the hydrolysis in water
Table 2: with functionalized alcohol (I) or amine (II) deutero-multipolymer
| The multipolymer numbering | Used parent material | Explanation | Solvent | Alkali | Functionalized alcohol (I) or functionalized amine (II) | Mol ratio | Time [h] | Temperature [℃] | Solid content [weight %] | pH |
| Multipolymer 8 | C | 2 | Dioxane/MEK and H 2The O exchange of solvent | DMEA to pH 8.7 | The hydroxy-propionic acid thioamides | 1∶1 | 4 | 100 | 25.1 | 8.7 |
| Multipolymer 9 | C | 2 | MEK and H 2The O exchange of solvent | DMEA to pH 8.7 | Mercaptoethanol | 1∶0.8 | 16 | 90 | 23.3 | 8.4 |
| Copolymer 10 | C | 1 | MEK | - | 2-(2-amino ethoxy) ethanol | 1∶1 | 3 | 78 | 43.0 | - |
| Copolymer 11 | E | 1 | MEK | - | Aminocapronitrile | 1∶1 | 3 | 66 | 48.2 | - |
| Copolymer 12 | E | 2 | MEK | - | The hydroxy-propionic acid thioamides | 1∶1 | 3 | 105 | 47.7 | - |
| Copolymer 13 | E | 2 | MEK and H 2The O exchange of solvent | DMEA to pH 8.2 | The hydroxy-propionic acid thioamides | 1∶1 | 3 | 105 | 19.5 | 8.2 |
| Copolymer 14 | E | 2 | Dioxane/MEK | - | Mercaptoethanol | 1∶0.8 | 25 | 95-99 | 54.4 | - |
| Copolymer 15 | E | 2 | Solvent-free, add H 2O/DMEA and H 2The O exchange of solvent | DMEA | (hydroxyethyl) amino dimethylene phosphonic acids four (triethyl ammonium) salt | 1∶1 | 4.5 | 103 | 20.5 | Do not survey |
DMEA: dimethylethanolamine, MEK: methylethylketone, BG: butyl glycol
Part B---performance test
Use obtained non-to derive and deutero-toxilic acid-olefin copolymer makes a service test.
Test is carried out in three kinds of different roll bending coating materials based on epoxide, acrylate and urethane.
Basic components based on the roll bending coating material (organic) of epoxy resin binder
It is as follows to be used to generate the component that the preparation of comprehensive pretreatment layer uses:
| Component | Describe | Quantity [weight part] |
| Tackiness agent with crosslinked group | Based on the epoxy resin binder of dihydroxyphenyl propane (molecular weight 1000g/mol, viscosity 13dPas/s and 50% solid content) | 26.9 |
| Weighting agent | The wetting ability fumed silica (Aerosil 200V, Degussa) | 0.16 |
| Talcum powder Finntalc M5 | 2.9 | |
| White pigment teshirogitlite 2310 | 10.8 | |
| The silica of calcium ion modification (Shieldex , GraceDivision) | 3.0 | |
| Zinc phosphate (Sicor ZP-BS-M, WaardalsKjemi ske Fabriken) | 4.1 | |
| Black pigment (Sicomix Schwarz, BASFAG) | 1.0 | |
| Solvent | Butyl glycol | 5.0 |
Each component is mixed in a suitable stirring tank with described order, and use dissolver to make its pre-dispersed 10 minutes.The mixture that generates moves in the mill (beadmill) that has a cooling jacket, and mixes mutually with the 1.8-2.2mmSAZ granulated glass sphere.Abrasive was ground 1 hour 30 minutes.Then abrasive is separated with granulated glass sphere.
The block hexamethylene vulcabond (Desmodur that under agitation in abrasive, adds 5.9 weight parts with described order
VP LS 2253, Bayer AG) and the commercially available not stanniferous crosslinking catalyst (Borchi of 0.4 weight part
VP 0245, Borchers GmbH).
Basic components based on the roll bending coating material (water-based) of acrylic binder
Used cross-linkable binding agent be anionic amine stabilized, water soluble acrylic acid ester dispersion (solid content is 30 weight %), described dispersion is formed as principal monomer by n-butyl acrylate, vinylbenzene, vinylformic acid and hydroxypropylmethyl acrylate.
In a suitable stirring tank, with described order, with the dispersing additive of 18.8 parts by weight of acrylic ester dispersions, 4.5 weight parts, the flowing regulator with froth breaking effect of 1.5 weight parts, the melamine resin linking agent (Luwipal of 5.5 weight parts
072, BASF AG), the wetting ability pyrogenic silica of 0.2 weight part (Aerosil 200V, Degussa), the silica (Shieldex of the calcium ion modification of the Finntalk M5 talcum powder of 3.5 weight parts, 12.9 weight part teshirogitlites, 2310 white pigments, 8.0 parts by weight of acrylic ester dispersions, 3.5 weight parts
, Grace Division), the zinc phosphate (Sicor of 4.9 weight parts
ZP-BS-M, Waardals Kjemiske Fabriken), 1.2 weight part black pigment (Sicomix
Schwarz, BASF AG) mix, and mixture was used decollator pre-dispersed 10 minutes.The mixture that generates moves in the mill that has a cooling jacket, and mixes mutually with the 1.8-2.2mmSAZ granulated glass sphere.Abrasive was ground 45 minutes.Then abrasive is separated with granulated glass sphere.
Under agitation in abrasive, add the defoamer of 27 parts by weight of acrylic ester dispersions, 1.0 weight parts, the block sulfonic acid of 3.2 per-cents, the defoamer of 1.5 weight parts and the flow control additive of 1.0 weight parts with described order.
Basic components based on the roll bending coating material (water-based) of polyurethane binder
Used crosslinkable tackiness agent is a kind of aqueous polyurethane dispersion (solid content 44 weight %, acid number 25, M
nAbout 8000g/mol, M
wAbout 21000g/mol), described aqueous polyurethane dispersion based on polyester glycol as soft chain segment (M
nAbout 2000g/mol), 4,4 '-two (isocyanato-cyclohexyl) methane and the monomer and the chain weighting agent that contain acidic-group.
In a suitable stirring tank, with described order, with the polyurethane dispersions of 18.8 weight parts, the dispersing additive of 4.5 weight parts, the flowing regulator with froth breaking effect of 1.5 weight parts, the melamine resin linking agent (Luwipal of 5.5 weight parts
072, BASF AG), the wetting ability pyrogenic silica of 0.2 weight part (Aerosil 200V, Degussa), the silica (Shieldex of the calcium ion modification of the polyurethane dispersions of the Finntalk M5 talcum powder of 3.5 weight parts, 12.9 weight part teshirogitlites, 2310 white pigments, 8.0 weight parts, 3.5 weight parts
, Grace Division), the zinc phosphate (Sicor of 4.9 weight parts
ZP-BS-M, Waardals Kjemiske Fabriken), 1.2 weight part black pigment (Sicomix
Schwarz, BASF AG) mix, and mixture was used decollator pre-dispersed 10 minutes.The mixture that generates moves in the mill that has a cooling jacket, and mixes mutually with 1.8-2.2mm SAZ granulated glass sphere.Abrasive was ground 45 minutes.Then abrasive is separated with granulated glass sphere.
Under agitation in abrasive, add the polyurethane dispersions of 27 weight parts, the defoamer of 1.0 weight parts, an acidic catalyst (block tosic acid, Nacure 2500) of 3.2 per-cents, the defoamer of 1.5 weight parts and the flow control additive of 1.0 weight parts with described order.
The interpolation of the used multipolymer of the present invention
Described roll bending coating material derived with 5 weight % above-mentioned separately or non-derivative copolymer (in solid copolymer with respect to the solid ingredient in the preparation) is mixed.For organic coating material, use the above-mentioned copolymer solution that is present in the butyl glycol to be used for this purpose based on epoxide; For water-based coating material, use the aqueous solution or emulsion to be used for this purpose based on acrylate or epoxide.
The coating of steel plate and aluminium sheet
Z type steel plate galvanized is adopted in the coating test, and (OEHDG 2, and Chemeta11) (AA6016 Chemeta11) carries out with the AlMgSi aluminium sheet.These plates clean by currently known methods in advance.
Described roll bending coating material use excellent type scraper plating in the forced convection temperature be 185 ℃ and base material temperature be solidify in 171 ℃ the continuous oven after, can form dry coating thickness is the wet-film thickness of 6 μ m coatings.
For comparing, also prepared the coating of not adding multipolymer.
Be to detect the corrosion inhibition effect of coating of the present invention, steel plate galvanized has been carried out the VDA climatic cycle test (VDA[German automobiles TIA (German Associationof the Automotive Industry)] test chart 621-415 Feb 82) in 10 weeks.
In this test (referring to figure below), at first sample is exposed to SaltSprayTest and carries out 1 day (5%NaCl solution, 35 ℃), and then alternately be exposed to wet condition (40 ℃, relative humidity 100%) and drying conditions (22 ℃, relative humidity 60%) respectively 3 times.Working cycle finished with the stage of 2 days dry conditions.Working cycle is illustrated as follows.
Initial condensation water test room temperature condition
Salt fog
Test
The circulation of 1 week=1
Amount to sequential 10 the such exposure cycles tests of carrying out.
After the corrosion process-exposed finishes,, steel plate is carried out visual assessment by contrasting with preassigned.Both estimated the formation that does not destroy corrosion thing on the coat side, also estimated at the edge and inferior film (subfilm) the corrosive tendency in graticule place.
With do not add corrosion inhibition multipolymer to the basis that compares in the same old way on sample is estimated.
The corrosion inhibition effect of steel plate is carried out according to the SaltSprayTest method of DIN 50021 in addition.
Aluminium sheet is carried out acetic acid salt spray test ESS (DIN 50021, and Jun 88).Corrosion is carried out visual assessment to described plate after exposing and finishing.In this case, estimated the area that annular is peeled off on the coat side on the whole.
In all tests, coated membrane all is an internal connecting type; With regard to the situation of steel plate, in connect and pass zinc coating and arrive the steel plate layer.
For sample is estimated, specify following score value:
0 corrosion failure is identical with control sample
+ to compare corrosion failure less with control sample
++ compare corrosion failure with control sample littler substantially
-to compare corrosion failure bigger with control sample
Test result is depicted schematically in table 3 in 4.
Table 3: corrosion test with the non-dicarboxylic acid units multipolymer of deriving
| Example number | Used multipolymer | Monomer | Mol ratio | The coating system | Steel plate galvanized | Aluminium sheet | |
| The climatic cycle test | SaltSprayTest | The acetic acid salt spray test | |||||
| Example 1 | Copolymer 1 | MAn/C 12Alkene | 1/1 | Acrylate/H 2O | 0 | + | + |
| Example 2 | Copolymer 1 | MAn/C 12Alkene | 171 | Urethane/H 2O | Do not detect | 0 | + |
| Example 3 | Copolymer 1 a | MAn/C 12Alkene | 1/1 | Resins, epoxy/butyl glycol | ++ | + | 0 |
| Example 4 | Multipolymer 2 | MAn/C 12Alkene/vinylbenzene | 1/0.9/0.1 | Acrylate/H 2O | 0 | + | + |
| Example 5 | Multipolymer 3 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | Urethane/H 2O | 0 | Do not detect | ++ |
| Example 6 | Multipolymer 4 | MAn/C 12Alkene/PIB 550 | 1/0.8/0.2 | Acrylate/H 2O | 0 | + | + |
| Example 7 | Multipolymer 5 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | Acrylate/H 2O | 0 | + | + |
| Example 8 | Multipolymer 5 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | Urethane/H 2O | + | Do not detect | + |
| Example 9 | Multipolymer 6 | MAn/C 12Alkene/undecylenic acid | 1/0.9/0.1 | Acrylate/H 2O | + | + | + |
| Example 10 | Multipolymer 6 | MAn/C 12Alkene/undecylenic acid | 1/0.9/0.1 | Urethane/H 2O | ++ | + | ++ |
| Example 11 | Multipolymer 6a | MAn/C 12Alkene/undecylenic acid | 1/0.9/0.1 | Resins, epoxy/butyl glycol | ++ | 0 | ++ |
| Example 12 | Multipolymer 7a | MAn/C 8Alkene | 1/1 | Resins, epoxy/butyl glycol | + | 0 | - |
Table 4: corrosion test with the dicarboxylic acid units multipolymer of deriving
| Example number | Used multipolymer | Monomer | Mol ratio | The functionalized used group of dicarboxylic acid units | Coating system | Steel plate galvanized | Aluminium sheet |
| The climatic cycle test | The acetic acid salt spray test | ||||||
| Example 13 | Multipolymer 8 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -CSNH 2 | Acrylate/dioxane/water | 0 | + |
| Example 14 | Multipolymer 8 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -CSNH 2 | PU/ dioxane/water | 0 | + |
| Example 15 | Multipolymer 9 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -SH | Resins, epoxy/MEK | + | + |
| Example 16 | Copolymer 10 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -OH | Resins, epoxy/MEK | + | + |
| Example 17 | Copolymer 11 | MAn/C 12v/PIB 1000 | 1/0.8/0.2 | -CN | Resins, epoxy/MEK | + | + |
| Example 18 | Copolymer 12 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | Resins, epoxy/MEK | + | + |
| Example 19 | Copolymer 13 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | Acrylate/dioxane/water | Do not detect | + |
| Example 20 | Copolymer 13 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | PU/ dioxane/water | 0 | + |
| Example 21 | Copolymer 14 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -SH | Acrylate/dioxane/water | + | + |
| Example 22 | Copolymer 15 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -PO 3H | Resins, epoxy/MEK | + | - |
Embodiment shows that the present invention uses the non-MAn-olefin copolymer of deriving and derive that the corrosion protection of roll bending coating material is improved.Improve appear in aluminium or two kinds of materials of steel at least a on, but on two kinds of base materials, all observed improvement usually.
Good especially result can be by using relative long-chain alkene and use the alkene that also contains functional group to obtain.
Claims (25)
1. one kind is the method for the comprehensive pretreatment layer of 1 to 25 μ m in the metallic surface plated thickness, may further comprise the steps at least:
(1) with a kind of crosslinkable preparation plating in the metallic surface, described preparation comprises at least
(A) adhesive composition (A) of at least a thermally cross-linkable of 20% to 70 weight % and/or photochemical crosslinking,
(B) at least a mean particle size of 20% to 70 weight % is less than the inorganic filler in small, broken bits of 10 μ m,
(C) at least a corrosion prevention agent of 0.25% to 40 weight % and
(D) randomly, a kind of solvent,
Condition desolventizes the summation meter of outer all components for weight % is based on, and
(2) make coating layer heat cross-linking and/or photochemical crosslinking,
Wherein the corrosion prevention agent is at least a by following monomer structure unit synthetic multipolymer (C):
(c1) at least a monoethenoid unsaturated hydrocarbons (c1a) of 70 to 30 moles of % and/or at least a being selected from are used the X of functional group
1The monomer (c1b) of monoethenoid unsaturated hydrocarbons of modification (c1b ') and vinyl ether (c1b "),
(c2) at least a monoethenoid unsaturated dicarboxylic acid and/or its acid anhydrides (c2a) and/or its derivative (c2b) of 30 to 70 moles of % with 4 to 8 carbon atoms,
Derivative (c2b) is that dicarboxylic acid and general formula are HO-R
1-X
2 nThe ester of alcohol (I) and/or with ammonia and/or general formula be HR
2N-R
1-X
2 nThe acid amides of amine (II) or imide, abbreviation is defined as follows:
R
1: have the alkyl of (n+1) valency of 1 to 40 carbon atom, wherein non-conterminous carbon
Atom also can by 0 and/or N substitute;
R
2: H, C
1To C
10Alkyl or-(R
1-X
2 n)
N:1,2 or 3; With
X
2: a kind of functional group; And
(c3) other olefin type unsaturated monomer of 0 to 10 mole of %, its be different from (c1) and (c2) but can with (c1) and (c2) copolymerization,
Its amount is separately based on the total amount meter of all monomeric units in the multipolymer.
2. the process of claim 1 wherein that the metallic surface is the surface of steel, zinc or zinc alloy, aluminum or aluminum alloy.
3. the process of claim 1 wherein that the metallic surface is the surface of electrogalvanizing steel or electro-galvanized steel.
4. the method for one of claim 1-3, wherein the metallic surface is the roll bending metallic surface, and the comprehensive pretreatment layer is by the continuation method plating.
5. the method for claim 4, wherein the coating process is undertaken by roller coat, spraying plating or dipping method.
6. the method for one of claim 1-5, wherein metallic surface cleaning (0) by other before with the preparation coating cleans it.
7. the method for one of claim 1-6 is wherein crosslinkedly undertaken by hot method, and adhesive composition is selected from polyester, Resins, epoxy, urethane or polyacrylic ester, and uses a kind of other linking agent at least.
8. the method for claim 7, wherein linking agent is blocked isocyanate or active melamine resin.
9. claim 7 or 8 method are wherein crosslinkedly carried out under 100 ℃ to 250 ℃ temperature.
10. the method for one of claim 1-9, wherein the thickness of comprehensive pretreatment layer is 3 to 15 μ m.
11. the method for one of claim 1-10, wherein monomer (c2a) is toxilic acid and/or maleic anhydride.
12. the method for one of claim 1-11, wherein multipolymer (C) comprises the monomer of at least a (c1a) type.
13. the method for claim 12, wherein monomer (c1a) is for having the monoethenoid unsaturated hydrocarbons of 6 to 30 carbon atoms.
14. the method for claim 13, wherein multipolymer also comprises at least a active polyisobutene of 1 to 60 mole of %, based on the amount meter of whole monomers (c1).
15. the method for claim 13, the multipolymer at least a monoethenoid unsaturated hydrocarbons with the X1 of functional group modification that also comprises 1 to 60 mole of % (c1b ') wherein is based on the amount meter of whole monomers (c1).
16. the method for claim 15, wherein monomer (c1b ') is a 10-undecylene carboxylic acid.
17. the method for one of claim 13-16, wherein the monoethenoid unsaturated hydrocarbons has 9 to 27 carbon atoms.
18. the method for one of claim 1-17, the wherein X of functional group
2Be selected from-Si (OR
3)
3(R wherein
3=C
1To C
6Alkyl) ,-OR
4,-SR
4,-NR
42, COOR
4The R of ,-(C=O)
4,-COCH
2COOR
4,-CSNR
4 2,-CN ,-PO
2R
4 2,-PO
3R
4 2,-OPO
3R
4 2(R wherein
4=H, C
1To C
6Alkyl or aryl) or-SO
3H.
19. the method for one of claim 1-17, the wherein X of functional group
2Be selected from-OH ,-SH ,-COOH ,-CSNH
2,-CN ,-PO
3H
2,-SO
3The salt of H or above-mentioned substance.
20. a moulded products, described goods have the metallic surface with the comprehensive pretreatment layer coating of 1 to 25 μ m thickness, can obtain by the method for one of claim 1 to 19.
21. the moulded products of claim 20, wherein the metallic surface is the surface of steel, zinc or zinc alloy, aluminum or aluminum alloy.
22. the moulded products of claim 21, wherein the comprehensive pretreatment layer was also made outer coating with one or more coat films.
23. the moulded products of claim 22, described goods are body of a motor car or car body component.
24. the moulded products of claim 22, described goods are panel component.
25. a preparation that is used at metallic surface plating comprehensive pretreatment layer comprises following at least composition:
(A) adhesive composition (A) of at least a thermally cross-linkable of 20% to 70% weight and/or photochemical crosslinking,
(B) at least a mean particle size of 20% to 70% weight is less than the inorganic filler in small, broken bits of 10 μ m,
(C) at least a corrosion prevention agent of 0.25% to 40% weight and
(D) randomly, a kind of solvent,
Condition desolventizes the summation meter of outer all components for % weight is based on, and
Wherein the corrosion prevention agent is at least a by following monomer structure unit synthetic multipolymer (C):
(c1) at least a monoethenoid unsaturated hydrocarbons (c1a) of 70 to 30 moles of % and/or at least a monomer (c1b) that is selected from monoethenoid unsaturated hydrocarbons with the X1 of functional group modification (c1b ') and vinyl ether (c1b "),
(c2) at least a monoethenoid unsaturated dicarboxylic acid and/or its acid anhydrides (c2a) and/or its derivative (c2b) of 30 to 70 moles of % with 4 to 8 carbon atoms,
Derivative (c2b) is that dicarboxylic acid and general formula are HO-R
1-X
2 nThe ester of alcohol (I) and/or with ammonia and/or general formula be HR
2N-R
1-X
2 nThe acid amides of amine (II) or imide, abbreviation is defined as follows:
R
1: have the alkyl of (n+1) valency of 1 to 40 carbon atom, wherein non-conterminous carbon
Atom also can by 0 and/or N substitute;
R
2: H, C
1To C
10Alkyl or-(R
1-X
2 n)
N:1,2 or 3; With
X
2: a kind of functional group; And
(c3) other olefin type unsaturated monomer of 0 to 10 mole of %, be different from (c1) and (c2) but can with (c1) and (c2) copolymerization,
Its amount is separately based on the total amount meter of all monomeric units in the multipolymer.
Applications Claiming Priority (3)
| 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 |
| DE102005061317.9 | 2005-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101111572A true CN101111572A (en) | 2008-01-23 |
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 Before (2)
| 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 |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059234A (en) * | 2013-01-07 | 2013-04-24 | 辽宁工业大学 | Preparation method of black metal preservative |
Families Citing this family (10)
| 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 |
| RU2663171C2 (en) * | 2012-09-19 | 2018-08-01 | Акцо Нобель Коатингс Интернэшнл Б.В. | Aqueous coating compositions including reaction product of maleic anhydride with unsaturated compound and amine |
| 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 |
Family Cites Families (5)
| 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 |
| GB996489A (en) * | 1961-06-01 | 1965-06-30 | Ethyl Corp | Novel hydroxy thio benzamides |
| 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 |
| JP4568386B2 (en) * | 1997-05-14 | 2010-10-27 | 日本ペイント株式会社 | Rust prevention coating agent and rust prevention treatment method |
-
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
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059234A (en) * | 2013-01-07 | 2013-04-24 | 辽宁工业大学 | Preparation method of black metal preservative |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101111574A (en) | 2008-01-23 |
| DE102005004292A1 (en) | 2006-08-03 |
| CN101111574B (en) | 2010-06-16 |
| CN101111573B (en) | 2012-03-28 |
| CN101155882A (en) | 2008-04-02 |
| CN101111571A (en) | 2008-01-23 |
| CN101111573A (en) | 2008-01-23 |
| CN101111571B (en) | 2011-07-06 |
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