WO2005078025A1 - Procede pour appliquer des couches de pretraitement integrees contenant un ester d'acide dithiophosphorique sur des surfaces metalliques - Google Patents

Procede pour appliquer des couches de pretraitement integrees contenant un ester d'acide dithiophosphorique sur des surfaces metalliques Download PDF

Info

Publication number
WO2005078025A1
WO2005078025A1 PCT/EP2005/001431 EP2005001431W WO2005078025A1 WO 2005078025 A1 WO2005078025 A1 WO 2005078025A1 EP 2005001431 W EP2005001431 W EP 2005001431W WO 2005078025 A1 WO2005078025 A1 WO 2005078025A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
layer
integrated pretreatment
binder
components
Prior art date
Application number
PCT/EP2005/001431
Other languages
German (de)
English (en)
Inventor
Monica Fernandez Gonzalez
Markus Ruckpaul
Frank Hezel
Markus Hickl
Wolfgang Schrepp
Manfred Essig
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2005078025A1 publication Critical patent/WO2005078025A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds

Definitions

  • the present invention relates to a method for applying integrated pretreatment layers to metallic surfaces, in particular the surfaces of strip metals, by treatment with a composition which contains at least one binder, crosslinking agent, a finely divided inorganic filler and dithiophosphoric acid ester. It also relates to an integrated pretreatment layer which can be obtained by means of the method.
  • suitable metal sheets are formed using suitable techniques such as stamping, drilling, folding, profiling and / or deep drawing. Larger components, such as automobile bodies, may be joined together by welding several individual parts.
  • the raw material for this is usually long metal strips, which are produced by rolling the metal and wound up into rolls (so-called “coils”) for storage and transport.
  • FIG. 1 An example of a typical layer structure of an automobile body is shown in Figure 1.
  • the steel sheet (1) is coated with Zn or a Zn alloy (2). This can be done galvanically or by immersion in liquid zinc, so-called hot-dip galvanizing.
  • a predominantly inorganic pretreatment layer (3) is then applied to improve the corrosion resistance of the zinc layer itself. This can be phosphating and / or chromating with Cr (VI) or Cr (III) compounds. Chromium and phosphate-free pretreatment layers are also known.
  • the pretreatment layer is also called a conversion layer or passivation layer. It is usually very thin (2 - 100 nm). In addition to improving the corrosion resistance of the Zn layer, it is also said to improve the adhesion between metal and subsequent lacquer layers.
  • the pretreatment layer (3) is now coated with an organic primer ("primer") (4).
  • primer organic primer
  • the body is then usually coated with an electro-dip coating (5) and then with the so-called filler (6).
  • the filler layer is a comparatively thick, soft layer that is intended to prevent stone chips or the like from destroying the layers underneath.
  • some or more colored lacquer layers (7) and a clear lacquer layer (8) are applied to the filler for protection.
  • Other lacquer layers and / or coating sequences above the base lacquer (4) are also common for other applications.
  • the anti-corrosion treatment was mainly carried out on the finished metallic workpiece, for example a welded-together automobile body
  • the anti-corrosion treatment has increasingly been carried out on the strip metal itself.
  • At least the pretreatment layer (3) and the organic base coat (4) are already applied to the strip metal. Only then are parts punched out, shaped and, if necessary, welded together. This means increased demands on the applied layers, because they now have to withstand punching, shaping and welding processes without sacrificing quality.
  • the metal strips are coated with the pretreatment layer (3) and the organic base coat (4) in a two-stage process, which is comparatively complex in terms of the required system technology. There has therefore been no lack of attempts to apply a single integrated pretreatment layer (3 ') instead of the separate application of a pretreatment layer (3) and the organic base lacquer (4), which takes over the functions of both layers.
  • a layer structure is shown by way of example and schematically in Figure 2.
  • the production of a coated metal strip is significantly simplified by such a one-step process.
  • Integrated pretreatment layers are known in principle.
  • No. 5,322,870 discloses a composition for forming an integrated pretreatment layer which comprises a polymeric coating agent, a crosslinking agent and additionally alkyl or aryl phosphoric acid esters or alkyl or aryl phosphonic acid esters.
  • the composition can optionally also comprise a pigment.
  • DE-A 19923 084 discloses a chromium-free aqueous coating composition for single-stage coating which contains at least hexafluoro anions of Ti (IV), Si (IV) and / or Zr (IV), a water-soluble or water-dispersible film-forming Contains binders and an organophosphoric acid.
  • the composition can optionally also comprise a pigment and crosslinking agent.
  • WO 02/62907 discloses a composition for a one-step coating, which comprises a binder, a crosslinking agent and a conductive pigment.
  • the binder has phosphoric acid groups.
  • Dithiophosphoric acid esters and their use for corrosion protection are known in principle, for example from WO 97/45503, SU-A 147 31 94, US 3,909,447, US 4,339,349, or WO 99/46338. Their use as a component of integrated pretreatment layers was hitherto unknown.
  • the object of the invention was to provide an improved method for producing integrated pretreatment layers and improved integrated pretreatment layers.
  • A a binder
  • B crosslinkable components, these being crosslinkable groups which are connected to the binder and / or can be at least one additionally used crosslinker
  • C a pigment
  • D a corrosion inhibitor
  • E optionally a solvent
  • the amount of binder is 20 to 70% by weight
  • the filler is 20 to 70% by weight of at least one inorganic, finely divided filler with an average particle size of less than 10 ⁇ m
  • the corrosion protection agent is 0 , 25 to 10% by weight of at least one dithiophosphoric ester of the general formula HS 2 P (OR) (OR ') and / or a salt thereof, where R or R' are, independently of one another, a straight-chain or branched alkyl radical having 1 to 30 carbon atoms, which may also have one or more additional functional groups, and / or non-adjacent carbon atoms may be substituted by O or N, and the percentages by weight refer to the sum of all components Obtain an exception for the solvent.
  • integrated pretreatment layers preferably with a thickness of 3 to 15 ⁇ m, have been found on metallic surfaces, which can be obtained by the process.
  • Figure 1 Example of a typical layer sequence of an automobile body with two-stage pretreatment
  • Figure 2 Example of a typical layer sequence of an automobile body with integrated, one-stage pretreatment.
  • the type of metal can be any metal.
  • These can be the surfaces of bodies consisting entirely of said metals or alloys.
  • the bodies can also only be coated with these metals and themselves consist of different types of materials, for example of other metals, alloys, polymers or composite materials.
  • it can be the surface of galvanized iron or steel.
  • it is the surface of a Strip metal, especially around electrolytically galvanized or hot-galvanized steel. It can be a one-sided or a two-sided galvanized metal strip.
  • Zn or Al alloys are known to the person skilled in the art. Depending on the desired application, the person skilled in the art selects the type and amount of alloy components. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical constituents of aluminum alloys include, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. It can also be an Al / Zn alloy in which Al and Zn are present in approximately the same amount. Steel coated with such alloys is commercially available. The steel can contain the usual alloy components known to the person skilled in the art.
  • integrated pretreatment layer in the sense of this invention means that the coating according to the invention is applied directly to the metal surface without a corrosion-inhibiting pretreatment such as passivation or phosphating being carried out beforehand.
  • the integrated pretreatment layer combines the passivation layer with the organic primer in a single layer
  • the term “applied directly” does not rule out that there may still be a thin layer, in particular a thin oxide skin, on the metal surface, which inevitably forms in the presence of air when the metal is handled normally.
  • lacquer layers such as cathodic dip lacquers
  • an additional organic primer is possible in special cases, although it is preferred not to do so.
  • the preparation used according to the invention for the treatment of metal surfaces comprises at least one binder (A) and crosslinkable components (B).
  • the crosslinkable components can be at least one crosslinker which is used in addition to a binder, or it can be groups of crosslinkable groups which are bonded to the binder.
  • the binder can also have crosslinkable groups and a crosslinker can also be used.
  • binders and crosslinkers can be used separately.
  • the binder then comprises reactive functional groups which can react with complementary, reactive functional groups in the crosslinking agents.
  • the binders (A) can be the binders customary in the field of coil coating lacquers.
  • suitable binders include (meth) acrylate (co) polymers, partially saponified polyvinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas,
  • Polyamides Polyimides or polyurethanes. Mixtures of different polymers can of course also be used, provided that the mixture does not cause any undesirable effects.
  • Polyester or epoxy resin-amine adducts are preferably used.
  • the polyesters are particularly suitable for weldable paints and the epoxy-amine adducts are preferred for paints that are not to be welded.
  • Suitable polyesters are, in particular, condensates of low molecular weight dicarboxylic acids and dialcohols.
  • suitable dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, aliphatic cycloaliphatic such as dimer fatty acids, i.e. Reaction products of unsaturated fatty acids with each other, cycloaliphatic dicarboxylic acids such as 1, 4- or 1, 3 cyclohexanedicarboxylic acid, tricyclodecanedicarboxylic acid and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid or phthalic acid. Derivatives of dicarboxylic acids can of course also be used. Anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or tetradehydrophthalic anhydride are particularly suitable.
  • dialcohols examples include aliphatic alcohols such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-butanediol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1-methyl-propanediol-1, 3, 2-butyl 2-ethylpropanediol, pentanediols, hexanediols, octanediols, dodecanediol, hydroxypivalic acid, neopentylglycol esters, cycloaliphatic alcohols such as 1, 4- or 1, 3-cyclohexanedimethanol, TCD alcohol and bis (4-hydroxycyclohexyl) methane or propane and dimerdiols (hydrogenated) , Derivatives of alcohols, such as esters, in particular the corresponding methyl or methyl
  • branched binders can also be used.
  • Suitable monomers for producing branches include tricarboxylic acids or their anhydrides such as trimelitic anhydride or trimesic acid and trial alcohols such as trimethalyolalkanes, for example trimethylolethane or trimethylolpropane.
  • the polyesters can preferably be reacted in whole or in part to form isocyanate-terminated polyesters by reaction with polyisocyanates.
  • the OH number of the polyesters used is usually about 10 to about 200 mg KOH / g, preferably 15 to 120 mg KOH / g, particularly preferably 20 to 80 mg KOH / g and for example about 50 mg KOH / g.
  • the molecular weights are usually 400 to 10,000 g / mol, preferably 500 to 5000 g / mol and particularly preferably 1000 to 4000 g / mol.
  • Epoxy-functional polymers can be prepared by the reaction of epoxy-functional monomers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or hexanediol diglycidyl ether with phenols such as bisphenol A, bisphenol F and / or alcohols such as ethoxylated or propoxylated bisphenol A.
  • Epoxy-functional polymers are commercially available, for example under the name Epon ® or Epikote ®.
  • Epoxy resin-amine adducts can be obtained by reacting said epoxy-functional components with phenols or aliphatic or cycloaliphatic dicarboxylic acids, acidic polyesters or alcohols, thiols and amines, in particular secondary amines such as, for example, diethanolamine or N-methylbutanolamine.
  • Emulsion polymers can also be used. These are particularly suitable for water-based formulations.
  • suitable emulsion polymers or copolymers include acrylate dispersions, obtainable in a customary manner from acrylic acid and / or acrylic acid derivatives, for example acrylic acid esters and / or styrene.
  • Dispersions made of polyurethanes, made from aromatic and / or aliphatic diisocyanates and polyester or aliphatic soft segments, are also suitable.
  • the preparation used comprises 20 to 70% by weight of the binder.
  • all percentages by weight relate to the sum of all components of the preparation with the exception of the solvent or the solvent mixture.
  • the amount is preferably 30 to 60% by weight and particularly preferably 40 to 50% by weight.
  • the crosslinking components (B) can have thermally crosslinking groups or photochemically crosslinking groups.
  • Suitable crosslinkers are, for example, crosslinkers based on epoxides in which two or more epoxy groups are connected to one another by means of a linking group. Examples include low molecular weight compounds with two epoxy groups such as hexanediol diglycidyl ether, phthalic acid diglycidyl ether or cycloaliphatic compounds such as 3 ', 4'-epoxycyclohexylmethyl ester, 3,4-epoxicyclohexane.
  • crosslinking agents include melamine-type crosslinker such as kommzerziell available crosslinking agents of Luwipal ® - row.
  • Blocked polyisocyanates are particularly preferably used as crosslinking agents.
  • the isocyanate group is reversibly reacted with a blocking agent.
  • the blocking agent is split off again when heated to higher temperatures. Examples of suitable blocking agents are disclosed in DE-A 199 14 896, column 12, line 13 to column 13, line 2.
  • Polyisocyanates blocked with ⁇ -caprolactam are particularly preferably used.
  • Crosslinkers suitable for photochemical crosslinking are, for example, the Basonat® brands from BASF or oligomeric acrylates.
  • crosslinker 0.5 to 10% by weight, preferably 1 to 8% by weight and particularly preferably 2 to 6% by weight are usually used. Mixtures of different crosslinkers can of course also be used, provided that the properties of the layer are not adversely affected thereby.
  • the preparation used for the method according to the invention further comprises at least one finely divided inorganic filler (C).
  • the filler can also have an additional organic coating, for example for hydrophobing or
  • the filler should not exceed an average particle size of 10 ⁇ m.
  • the average particle size is preferably 10 nm to 9 ⁇ m and particularly preferably 100 nm to 5 ⁇ m. In the case of round or approximately round particles, this information relates to the diameter, in the case of irregularly shaped particles, such as, for example, in the case of needle-shaped particles, to the longest axis.
  • the particle size means the primary particle size. It is of course known to the person skilled in the art that finely divided solids often agglomerate into larger particles which have to be dispersed intensively in order to be used.
  • the particle size is chosen by the person skilled in the art depending on the desired properties of the layer. For example, it also depends on the desired one Layer thickness. As a rule, the person skilled in the art will choose smaller particles with a small layer thickness.
  • electrically conductive pigments or fillers are suitable as fillers. Such additives serve to improve the weldability and to improve a subsequent coating with electrocoat materials.
  • suitable electrically conductive fillers or pigments include phosphides, vanadium carbide, titanium nitride, molybdenum sulfide, graphite, carbon black or doped barium sulfate.
  • Metal phosphides of Zn, Al, Si, Mn, Cr, Fe or Ni are preferably used.
  • Examples of preferred metal phosphides include CrP, MnP, Fe 3 P, Fe 2 P, Ni 2 P, NiP 2 or NiP 3 .
  • Iron phosphides are commercially available, for example, under the name Ferrophos ® .
  • Non-conductive pigments or fillers can also be used, such as finely divided amorphous silicon, aluminum or titanium oxides, which can also be doped with other elements.
  • amorphous silicon dioxide modified with calcium ions can be used.
  • pigments include anti-corrosion pigments such as zinc phosphate, zinc metaborate or barium metaborate monohydrate.
  • the pigments are used in an amount of 20 to 70% by weight. The exact amount is determined by the person skilled in the art depending on the desired properties of the layer. When using conductivity pigments, the amounts used are usually larger than when using non-conductive fillers. Preferred amounts for conductive pigments and fillers are 40 to 70% by weight, preferred amounts for non-conductive pigments 20 to 50% by weight.
  • composition further comprises 0.25 to 10% by weight of at least one dithiophosphoric acid ester (D) of the general formula HS 2 P (OR) (OR ').
  • D dithiophosphoric acid ester
  • OR organic radical-activated polymer
  • a mixture of several different dithiophosphoric esters can of course also be used.
  • the dithiophosphoric acid esters can be used as free acids or preferably as salts thereof.
  • Particularly suitable counterions are monovalent ions such as Mg 2+ , Sr 2 * , Zn 2+ , Ca 2 ⁇ Ba 2+ , Li + , Na + , K + , NH 4 + or also alkylammonium ions of the general formulas NHaR '" * , NH 2 R'y, NHR'Y or NR'Y, where R '"represents a straight-chain or branched aliphatic or aromatic radical, preferably C T to Ce alkyl.
  • R '" can also include functional groups.
  • ammonium ions include the ammonium ions of amines such as ethanolamine, N- Methylethanolamine, ⁇ /, ⁇ / -dimethylethanolamine, diethanolamine, ⁇ / -methyldiethanolamine, triethanolamine, morpholine, ⁇ / -methylmorpholine or triethylamine.
  • amines such as ethanolamine, N- Methylethanolamine, ⁇ /, ⁇ / -dimethylethanolamine, diethanolamine, ⁇ / -methyldiethanolamine, triethanolamine, morpholine, ⁇ / -methylmorpholine or triethylamine.
  • R and R 'in the dithiophosphoric acid ester can be different or preferably the same.
  • R and R ' are each a straight-chain or branched alkyl radical having 1 to 30 C atoms, which may also have one or more additional functional groups, and / or in which the non-adjacent C atoms are represented by O or N. can be substituted.
  • It is preferably a straight-chain or branched alkyl radical having 2 to 12 carbon atoms, particularly preferably having 3 to 10 carbon atoms.
  • suitable radicals include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, 2-ethylhexyl or n-octyl radicals.
  • Binders also react with the crosslinker and improve the stability of the layer.
  • the functional groups are preferably selected from the group of -OH, -NH 2 , -NHR ", -COOH or-COOR", where R "is a straight-chain or branched alkyl, aralkyl or aryl radical If the radicals R and R 'have functional groups, it is preferably a radical of the general formula - (CH 2 ) n -F, where n is a natural number from 1 to 20, preferably 2 to 12 and particularly preferably 2 to 9 stands.
  • radicals R and R 'in which non-adjacent C atoms are substituted by O and / or N atoms are preferably radicals of the general formula - (CH 2 -CH 2 -0-) mX containing ethylene oxide units.
  • X is H or methyl and m is a number from 1 to 9, or residues containing up to 9 ethyleneimine units which are straight-chain or branched ethyleneimine units. It is known to the person skilled in the art that the number of bound units is in each case average values. Such residues can improve water solubility or water dispersibility for use in aqueous systems.
  • R or R 'can also be a radical of the general formula - [(CH 2 ) k O] r (CH 2 ) k -F', where k is a natural number from 2 to 10, 1 for a natural number from 1 to 20 and F 'stands for a functional group.
  • the functional group F ' is preferably one selected from the group of -OH, -OR ", -COOH or -COOR", where R "has the meaning given above.
  • the dithiophosphoric acid esters are usually used in an amount of 0.25 to 10% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight.
  • the preparation generally comprises a suitable solvent in which the components are dissolved and / or dispersed in order to enable uniform application to the surface.
  • a suitable solvent in which the components are dissolved and / or dispersed in order to enable uniform application to the surface.
  • the use of a solvent is preferred.
  • Suitable solvents are those which are capable of dissolving, dispersing, suspending or emulsifying the compounds according to the invention. It can be organic solvents or water. Mixtures of various organic solvents or mixtures of organic solvents with water can of course also be used. The person skilled in the art makes a suitable selection from the solvents which are possible in principle, depending on the intended use and the type of compound used according to the invention.
  • organic solvents examples include hydrocarbons such as toluene, xylene or mixtures, e.g. obtained from the refining of crude oil and e.g. are commercially available as petroleum ether, kerosene, Solvesso® or Risella®, ethers such as THF or polyethers such as polyethylene glycol, ether alcohols such as butyl glycol, ether glycol acetates such as butyl glycol acetate, ketones such as acetone, alcohols such as methanol, ethanol or propanol.
  • hydrocarbons such as toluene, xylene or mixtures, e.g. obtained from the refining of crude oil and e.g. are commercially available as petroleum ether, kerosene, Solvesso® or Risella®
  • ethers such as THF or polyethers
  • polyethers such as polyethylene glycol
  • ether alcohols such as butyl glycol
  • Preparations can also be used which comprise water or a predominantly aqueous solvent mixture. This should be understood to mean mixtures which comprise at least 50% by weight, preferably at least 65% by weight and particularly preferably at least 80% by weight of water.
  • Other components are water-miscible solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butylglycol or methoxypropanol.
  • the amount of solvent is determined by the person skilled in the art depending on the desired
  • the weight ratio of the layer components to the solvent is 10: 1 to 1:10, preferably approximately 2: 1, without the invention being restricted to this. It is of course also possible to first produce a concentrate and to dilute it to the desired concentration only on site.
  • the preparation is produced by intensively mixing the components of the preparation with the solvents. Suitable mixing or dispersing units are known to the person skilled in the art.
  • the preparation can also comprise one or more auxiliaries and / or additives (F).
  • auxiliaries and / or additives serve to fine-tune the properties of the layer. Their amount generally does not exceed 20% by weight with respect to the buzzer of all components with the exception of the solvents, preferably not 10%.
  • suitable additives are coloring and / or effect pigments, reactive thinners for thermal curing or curing with actinic radiation, rheology aids, UV absorbers, light stabilizers, radical scavengers, initiators for radical polymerization, catalysts for thermal crosslinking, photoinitiators and coinitiators , Slip additives, polymerization inhibitors, defoamers, emulsifiers, degassing agents, wetting and diperging agents, adhesion promoters, leveling agents, film-forming aids, rheology-controlling additives (thickeners), flame retardants, siccatives, skin-preventing agents, other corrosion inhibitors, waxes and matting agents, such as those from the by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or German patent application DE 199 14 896 A1, column 13, line 56, to column 15, line 54.
  • Preferred additives are dibutyltin dilaurate as a catalyst for thermal crosslinking.
  • the metallic surface is treated with the preparation.
  • the surface can be cleaned before treatment.
  • the treatment according to the invention is carried out immediately after a metallic surface treatment, for example electrolytic galvanizing or hot-dip galvanizing of steel strips, the strips can generally be brought into contact with the treatment solution according to the invention without prior cleaning.
  • the metal strips to be treated have been stored and / or transported before the coating according to the invention, they are usually provided with anti-corrosion oils or at least largely soiled that cleaning before the coating according to the invention is necessary.
  • the cleaning can be carried out according to methods known to the person skilled in the art with customary cleaning agents.
  • the surface of the metal is treated with the preparation, for example by spraying, dipping or rolling on.
  • the workpiece can be drained to remove excess treatment solution; With sheet metal, metal foils or the like, excess treatment solution can also be squeezed or doctored off, for example.
  • excess treatment solution can also be squeezed or doctored off, for example.
  • at least parts of the polymer used and further components of the preparation are chemisorbed from the surface of the metal, so that a firm bond is established between the surface and the components.
  • the treatment with the preparation is generally carried out at room temperature, without the principle that higher temperatures should be excluded.
  • the treatment can be a so-called "no-rinse” process, in which the treatment solution is dried directly in a drying oven without rinsing immediately after application.
  • the coating can be carried out on one side or on both sides.
  • the coating is very particularly preferably carried out by means of a continuous process.
  • the coil coating can be carried out, for example, by means of a continuously operating coil coating system, as described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 55, "coil coating", or in German patent application DE 196 32426 A1 Of course, differently designed systems can also be used.
  • the speed of the metal strip is selected by a person skilled in the art in accordance with the application and hardening properties of the preparation used. As a rule, speeds of 10 to 150 m / min, preferably 12 to 120 m / min, particularly preferably 14 to 100 m / min, very particularly preferably 16 to 80 and in particular 20 to 70 m / min have proven successful.
  • roller coating is particularly advantageous and is therefore preferably used according to the invention.
  • Each roller coating application step can be carried out with several rollers. Preferably two to four and in particular two rollers are used.
  • the rotating pick-up roller is immersed in a supply of the paint according to the invention and thus takes over the paint to be applied. This is transferred from the pick-up roller directly or via at least one transfer roller to the rotating application roller. From this, the paint is transferred to the belt by wiping in the same direction or in opposite directions.
  • the lacquer according to the invention can also be pumped directly into a nip between two rollers, which experts also refer to as a nip feed.
  • the opposite wiping or the reverse roller coating method is advantageous and is therefore used with preference.
  • the circulation speeds of the take-up roller and the application roller can vary very greatly from coating process to coating process.
  • the application roller has an orbital speed which is 110 to 125% of the belt speed
  • the take-up roller has an orbital speed which is 20 to 40% of the belt speed.
  • any solvent present in the layer is removed and the layer is crosslinked. This can be done in two separate steps, but can also be done simultaneously.
  • the layer is preferably heated using a suitable device. Drying can also be done by contacting a gas stream. Both methods can be combined.
  • the curing method depends on the nature of the crosslinking agent and is usually carried out thermally. However, curing can also take place with actinic radiation or in combination thermally and with actinic radiation.
  • actinic radiation is understood here and below to mean electromagnetic radiation, such as near infrared, visible light, UV radiation or X-rays, in particular UV radiation, or corpuscular radiation, such as electron beams.
  • the temperature required for curing depends in particular on the crosslinking agent used. Very reactive crosslinkers can be used at lower temperatures are cured as less reactive crosslinkers.
  • the temperature of the layer for curing is usually between 120 and 250 ° C.
  • the coating layers according to the invention are preferably heated during thermal curing by convection heat transfer, irradiation with near or far infrared and / or in the case of tapes based on iron by electrical induction.
  • the heating time i.e. the duration of the thermal curing varies depending on the paint used according to the invention. It is preferably 10 s to 2 min.
  • convection ovens with a length of 30 to 50, in particular 35 to 45 m, are required.
  • the ambient air temperature is preferably 350 ° C.
  • the thermal curing of the lacquer layers according to the invention can also be supported by irradiation with actinic radiation.
  • curing can also be carried out using actinic radiation alone, as is described, for example, in German patent application DE 198 35206 A1.
  • the method according to the invention makes it possible to obtain an integrated pretreatment layer on a metallic surface, in particular the surface of iron, steel, zinc or zinc alloys, aluminum or aluminum alloys.
  • a metallic surface in particular the surface of iron, steel, zinc or zinc alloys, aluminum or aluminum alloys.
  • it also includes the fillers, dithiophosphoric acid esters and optionally other components.
  • components detached from the metal surface and deposited again such as customary amorphous oxides of aluminum or zinc and possibly other metals, can also be present.
  • the composition of the passivation layer does not appear to be homogeneous, but rather has concentration gradients.
  • the thickness of the integrated pretreatment layer is determined by the person skilled in the art depending on the desired properties of the layer. As a rule, there is a thickness of 3 to 15 ⁇ m, even if in special cases the thicknesses can still lie outside these ranges. A thickness of 4 to 10 ⁇ m is preferred, and 5 to 8 ⁇ m is particularly preferred. The thickness results from the amount of the composition applied in each case. Additional layers of paint can be applied to the metallic surface with an integrated pre-treatment layer.
  • the coated tape and further layers can be applied in other systems.
  • the coils can be wound into coated coils and then processed further at another location; however, they can also be processed directly from the coil coating. They can be laminated with plastics or provided with removable protective films.
  • the tapes provided with the integrated pretreatment layer can also be shredded and processed into molded parts without further painting. Different molded parts can also be joined together by welding. Examples of suitable shaping processing methods are presses and
  • the resulting profile elements and molded parts such as scratch-resistant, corrosion-resistant, weather-resistant and chemical-stable, can easily be overpainted with a wide variety of paints.
  • the paint without conductive pigments can be used as a KTL replacement if it is applied in a layer thickness of about 10-15 ⁇ m.
  • the components were mixed in the order given in a suitable stirring vessel and predispersed with a dissolver for ten minutes.
  • the resulting mixture was transferred in a bead mill with a cooling jacket and mixed with 1.8-2.2 mm SAZ glass beads.
  • the millbase was ground to a Hegmann grain size of 10 to 15 ⁇ m for 25 minutes. The ground material was then separated from the glass beads.
  • the millbase was added with stirring in the order given, 3.55 parts by weight of bisphenol-A-epichlorohydrin (Epikote ® 834 from Shell Resins), 1, 78 parts by weight of a commercial self-crosslinking urethane resin (Desmodur ® VPLS 2253 from Bayer AG), 0, 1 part by weight of dibutyltin dilaurate and 4.26 parts by weight of Solvesso ® 150 were added.
  • the components were mixed in a suitable stirred vessel in the order given and predispersed with a dissolver for ten minutes.
  • the resulting mixture was transferred in a bead mill with a cooling jacket and mixed with 1.8-2.2 mm SAZ glass beads.
  • the millbase was milled for 1 h 30 'minutes. The ground material was then separated from the glass beads.
  • the regrind was added with 5.9 parts by weight of a commercially available self-crosslinking urethane resin (Desmodur 18 VPLS 2253 from Bayer AG) and 0.4 parts by weight of a commercially available crosslinking catalyst (Borchi ® VP0245 from Bayer AG) with stirring in the order given.
  • a commercially available self-crosslinking urethane resin Desmodur 18 VPLS 2253 from Bayer AG
  • a commercially available crosslinking catalyst (Borchi ® VP0245 from Bayer AG)
  • the formulations obtained were applied to metal surfaces directly using doctor blades.
  • the surfaces have not been passivated beforehand.
  • Either steel plates of type Z (hot-dip galvanized steel manufactured according to the standards DIN EN 10 142 and 01 147) or aluminum plates of type A 6016 were used.
  • the surfaces were degreased before use.
  • the steel surface was first provided with a Cr-free passivation layer in a known manner.
  • the passivation layer contains Zr-Ti salts and an organic binder.
  • the integrated pre-treatment layers were then hardened in a continuous dryer.
  • the circulating air temperatures in the dryer, the object temperatures and the resulting dry layer thicknesses are summarized in Table 1.
  • Table 1 Compilation of the samples produced The corrosion resistance of the samples obtained from examples and comparative examples was assessed using a weathering test. A climate change test according to VDA 621-415 was carried out to test the steel samples. The corrosion tests for aluminum were carried out according to the DIN standard 50021-ESS (according to ASTM B287 test).
  • the metal plates were evaluated as follows: • 1-3 ⁇ red rust in the scratch, edges and surface, blistering in more than 90% of the surface • 4-5 ⁇ red rust in the scratch and / or edges, a lot of white rust on the surface, Blistering in 50% of the surface • 6-7 ⁇ No red rust, little white rust on the surface, blistering in -25% of the surface 8-10 ⁇ No red rust, very little / no white rust on the surface, blistering in less than 15% of the surface flats of the tests are summarized in Table 2.
  • the metal plates with integrated pretreatment layers which contain dithiophosphoric acids, have less surface corrosion and less infiltration at the scratch and the edges than the metal plates with coatings without dithophosphoric acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour appliquer des couches de prétraitement intégrées sur des surfaces métalliques en traitant au moyen d'une composition contenant au moins un liant, un agent de réticulation, une charge inorganique à fines particules et un ester d'acide dithiophosphorique. La présente invention porte également sur une couche de prétraitement intégrée obtenue selon ce procédé.
PCT/EP2005/001431 2004-02-16 2005-02-12 Procede pour appliquer des couches de pretraitement integrees contenant un ester d'acide dithiophosphorique sur des surfaces metalliques WO2005078025A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410007744 DE102004007744A1 (de) 2004-02-16 2004-02-16 Verfahren zum Aufbringen integrierter Vorbehandlungsschichten umfassend Dithiophosphorsäureester auf metallische Oberflächen
DE102004007744.4 2004-02-16

Publications (1)

Publication Number Publication Date
WO2005078025A1 true WO2005078025A1 (fr) 2005-08-25

Family

ID=34832727

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/001431 WO2005078025A1 (fr) 2004-02-16 2005-02-12 Procede pour appliquer des couches de pretraitement integrees contenant un ester d'acide dithiophosphorique sur des surfaces metalliques

Country Status (2)

Country Link
DE (1) DE102004007744A1 (fr)
WO (1) WO2005078025A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007125038A2 (fr) 2006-04-26 2007-11-08 Basf Se Procédé d'application de couches anticorrosion sur des surfaces métalliques
US20160168390A1 (en) * 2005-02-10 2016-06-16 Basf Se Use of dithiophosphinic acid and/or its salts for producing anti-corrosion coatings that are devoid of chrome

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008000919B4 (de) * 2008-04-01 2014-01-09 Siegenia-Aubi Kg Verfahren zur Aufbringung eines zusätzlichen Korrosionsschutzes auf ein metallisches Bauteil und nach dem Verfahren hergestellter verzinkter Beschlag

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909447A (en) * 1972-07-17 1975-09-30 Petrolite Corp Mixtures of thiophosphates, oxygen phosphates and pyrophosphates
US4560716A (en) * 1983-08-30 1985-12-24 Kabushiki Kaisha Toyota Chuo Kenkyusho Rust preventing epoxy resin compositions
JPH03223295A (ja) * 1989-12-28 1991-10-02 Idemitsu Kosan Co Ltd ジアルキルジチオリン酸亜鉛塩及びそれを含有する潤滑油組成物
RU1473194C (ru) * 1987-01-28 1993-10-15 Предприятие П/Я Р-6476 Промотор адгезии покрытий из полимеров к металлу
US5322870A (en) * 1992-12-29 1994-06-21 Board Of Regents, Northern Illinois University Additive package for in situ phosphatizing paint, paint and method
US6139610A (en) * 1996-01-05 2000-10-31 Wayne Pigment Corp. Hybrid pigment grade corrosion inhibitor compositions and procedures
US20020151635A1 (en) * 2001-02-08 2002-10-17 Gray Ralph C. Curable, weldable coating compositons

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909447A (en) * 1972-07-17 1975-09-30 Petrolite Corp Mixtures of thiophosphates, oxygen phosphates and pyrophosphates
US4560716A (en) * 1983-08-30 1985-12-24 Kabushiki Kaisha Toyota Chuo Kenkyusho Rust preventing epoxy resin compositions
RU1473194C (ru) * 1987-01-28 1993-10-15 Предприятие П/Я Р-6476 Промотор адгезии покрытий из полимеров к металлу
JPH03223295A (ja) * 1989-12-28 1991-10-02 Idemitsu Kosan Co Ltd ジアルキルジチオリン酸亜鉛塩及びそれを含有する潤滑油組成物
US5322870A (en) * 1992-12-29 1994-06-21 Board Of Regents, Northern Illinois University Additive package for in situ phosphatizing paint, paint and method
US6139610A (en) * 1996-01-05 2000-10-31 Wayne Pigment Corp. Hybrid pigment grade corrosion inhibitor compositions and procedures
US20020151635A1 (en) * 2001-02-08 2002-10-17 Gray Ralph C. Curable, weldable coating compositons

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199146, Derwent World Patents Index; Class A60, AN 1991-335139, XP002326029 *
DATABASE WPI Section Ch Week 199412, Derwent World Patents Index; Class A82, AN 1994-098583, XP002326030 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160168390A1 (en) * 2005-02-10 2016-06-16 Basf Se Use of dithiophosphinic acid and/or its salts for producing anti-corrosion coatings that are devoid of chrome
US10472525B2 (en) * 2005-02-10 2019-11-12 Basf Coatings Gmbh Use of dithiophosphinic acid and/or its salts for producing anti-corrosion coatings that are devoid of chrome
WO2007125038A2 (fr) 2006-04-26 2007-11-08 Basf Se Procédé d'application de couches anticorrosion sur des surfaces métalliques
WO2007125038A3 (fr) * 2006-04-26 2008-01-24 Basf Ag Procédé d'application de couches anticorrosion sur des surfaces métalliques
US8420219B2 (en) 2006-04-26 2013-04-16 Basf Se Method for the application of corrosion-resistant layers to metallic surfaces

Also Published As

Publication number Publication date
DE102004007744A1 (de) 2005-09-08

Similar Documents

Publication Publication Date Title
EP2013297B1 (fr) Procédé d'application de couches anticorrosion sur des surfaces métalliques
EP2296830B1 (fr) Procédé de revêtement de bandes de métal
DE102005004292A1 (de) Verfahren zum Aufbringen integrierter Vorbehandlungsschichten umfassend Thioamide auf metallische Oberflächen
EP1527143B1 (fr) Matieres d'enduction et leur utilisation pour realiser des enductions soudables
EP1851276B1 (fr) Un procédé pour appliquer des couches de protection contre la corrosion depourvues de chrome comprenant d'acides dithiophosphiniques et/ou de leurs sels
WO2007020220A1 (fr) Composition polymere anticorrosion
EP1468053B1 (fr) Vernis de couchage sur bande contenant un melange anticorrosion
WO2001044382A1 (fr) Procede pour le trempage electrophoretique anodique et peinture pour trempage electrophoretique
DE102007001653A1 (de) Leitfähige, organische Beschichtungen mit geringer Schichtdicke und guter Umformbarkeit
EP1844114A1 (fr) Revetements anticorrosion contenant des groupes thioamide
EP1844112A1 (fr) Procede d'application, sur des surfaces metalliques, de couches anticorrosion comprenant des thioamides
EP1468052B1 (fr) Matieres de revetement et leur utilisation pour la production de revetements a souder
WO2012013560A1 (fr) Procédé de revêtement anticorrosion de surfaces métalliques utilisant du polyester contenant du phosphore
WO2005078025A1 (fr) Procede pour appliquer des couches de pretraitement integrees contenant un ester d'acide dithiophosphorique sur des surfaces metalliques
EP1877360A1 (fr) Materiau de revetement, procede de fabrication et utilisation pour la fabrication de revetements adhesifs anticorrosion
EP2598583B1 (fr) Procédé de revêtement anticorrosion de surfaces métalliques utilisant des composés de faible poids moléculaire contenant du phosphore
DE102005061319A1 (de) Verfahren zum Aufbringen von Korrosionsschutzschichten umfassend Thioamide auf metallische Oberflächen
EP1887022A1 (fr) Substrat ayant une surface metallique et une couche de pretraitement appliquée ci-dessus contenant un derive d'acide phosphinique
EP2203527B1 (fr) Procédé de traitement anti-corrosion et d'assemblage de pièces métalliques
DE102005061317A1 (de) Verfahren zum Aufbringen von Dicarbonsäure-Olefin-Copolymere enthaltenden, integrierten Vorbehandlungsschichten auf metallische Oberflächen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase