Method for coating metallic surfaces, coating composition, and coatings produced in said manner

Abstract

Disclosed is a method for coating surfaces of metallic substrates with an organic, anionically, cationically, or/and radically hardenable anti-corrosive composition that represents a dispersion or solution containing at least two components selected among the group of monomers, oligomers, and polymers which can at least partly be anionically, cationically, or/and radically hardened, the content of at least one monofunctional monomer or/and oligomer in said anti-corrosive composition ranging between 1 and 50 percent by weight. The inventive anti-corrosive composition further comprises at least one photoinitiator used for anionic, cationic, or/and radical crosslinking, and a first, organic corrosion inhibitor. The anti-corrosive composition is applied to the metallic surfaces at a wet film thickness ranging from 1 to 25 micrometers, is optionally dried, and is then anionically, cationically, or/and radically hardened in order to obtain an anti-corrosive coating.

1 - 40 . (canceled)  
   
   
       41 . A process for coating a metallic surface of a metallic substrate comprising applying, an organic, anionically, cationically or/and radically curable anticorrosive composition, to the metallic surface, wherein said anticorrosive composition comprises a dispersion or solution containing at least two components that are at least partially anionically, cationically or radically curable selected from the group of a monomer, an oligomer and a polymer with a total content in the range from 50 to 95 wt. %, 
 wherein at least one monofunctional monomer or/and oligomer is present in an amount of from 1 to 58 wt. %;    from 0.5 to 22 wt. % of at least one photoinitiator for anionic, cationic or/and radical crosslinking if electron beam radiation is not used,    from 0.05 to 6 wt. % of a first organic corrosion inhibitor, and    optionally at least one further organic or/and inorganic corrosion inhibitor with a total content in the range from 0.1 to 12 wt. %,    optionally at least one hardener for a chemical postcure with a content in the range from 0.05 to 8 wt. %,    optionally up to 35 wt. % of an additive,    and optionally water or/and at least one organic solvent in a total content of 0.01 to 5 wt. %, relative in each case to the solids contents in wt. %,    wherein the anticorrosive composition is applied to the metallic surfaces in a wet film thickness in the range from 0.5 to 25 μm; and at least one of anionically, cationically radically curing the composition to form an anticorrosive coating, wherein the anticorrosive coating has a dry film thickness in the range from 0.4 to 20 μm and a chemical resistance of over 20 MEK cycles, determined in the MEK test in accordance with ECCA standard T11 with methyl ethyl ketone wherein the coating has a chemical resistance of at least 40 MEK cycles and whereby the monomers, oligomers and/or polymers are selected such that a narrow distribution of medium-sized chain lengths results when the components are cross-linked.    
   
   
       42 . A process for coating a metallic surface of a metallic substrate comprising applying an organic, anionically, cationically or/and radically curable anticorrosive composition, without applying a pretreatment coat prior to applying the anticorrosive composition, wherein the anticorrosive composition is a dispersion or solution which is applied directly to the metallic surface in a wet film thickness in the range from 0.4 to 25 μm, is optionally dried and is then anionically, cationically or/and radically cured to form an anticorrosive coating which displays a dry film thickness in the range from 0.4 to 20 μm, wherein the anticorrosive coating preferably achieves a flexibility and bond strength of ≦T3, determined by means of a T-bend test in accordance with ECCA standard T7 on hot-galvanised precoated steel sheets of 0.3 mm thickness organically coated in a film thickness of 8 μm, wherein the coating has a chemical resistance of at least 40 MEK cycles and whereby the monomers, oligomers and/or polymers are selected such that a narrow distribution of medium-sized chain lengths results when the components are cross-linked.  
   
   
       43 . The process according to  claim 41 , wherein at least two components selected from the group of monomers, oligomers and polymers, which are at least partially anionically, cationically or/and radically curable, are added to the anticorrosive composition, wherein the content of monomers is in the range from 0 to 60 wt. %, the content of oligomers is in the range from 0 to 60 wt. % and the content of polymers is in the range from 10 to 70 wt. %, wherein on the one hand at least one monomer or/and at least one oligomer and on the other hand at least one polymer is present.  
   
   
       44 . The process according to  claim 42 , wherein at least two components selected from the group of monomers, oligomers and polymers, which are at least partially anionically, cationically or/and radically curable, are added to the anticorrosive composition, wherein the content of monomers is in the range from 0 to 60 wt. %, the content of oligomers is in the range from 0 to 60 wt. % and the content of polymers is in the range from 10 to 70 wt. %, wherein on the one hand at least one monomer or/and at least one oligomer and on the other hand at least one polymer is present.  
   
   
       45 . The process according to  claim 41 , wherein the monomers or/and oligomers based on unsaturated, optionally aliphatic or/and aromatic compounds, such as unsaturated aliphatic acrylates for example, are added to the anticorrosive composition.  
   
   
       46 . The process according to  claim 42 , wherein the monomers or/and oligomers based on unsaturated, optionally aliphatic or/and aromatic compounds, such as unsaturated aliphatic acrylates for example, are added to the anticorrosive composition.  
   
   
       47 . The process according to  claim 41 , wherein the at least one anionically, cationically or/and radically polymerizable monomer or/and oligomer is selected from the group consisting of an acrylate, a methacrylate, a polyester and a polyurethane.  
   
   
       48 . The process according to  claim 42 , wherein the at least one anionically, cationically or/and radically polymerizable monomer or/and oligomer is selected from the group consisting of an acrylate, a methacrylate, a polyester and a polyurethane.  
   
   
       49 . The process according to  claim 41 , wherein the at least one anionically, cationically or/and radically polymerizable monomer or/and oligomer is selected from the group consisting of butanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, 2-ethylhexyl acrylate, hexanediol dicyl acrylate, hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, polyethylene diacrylate, triethylol propane formal acrylate, trimethyl propane triacrylate, trimethylol propane formal acrylate, triethylol propane acrylate, trimethylol propane acrylate and tripropylene glycol diacrylate.  
   
   
       50 . The process according to  claim 41 , wherein at least one flexibilizing resin or/and at least one modified flexibilizing resin is additionally added to the anticorrosive composition, in particular at least one based on unsaturated aliphatic polymers.  
   
   
       51 . The process according to  claim 42 , wherein at least one flexibilizing resin or/and at least one modified flexibilizing resin is additionally added to the anticorrosive composition, in particular at least one based on unsaturated aliphatic polymers.  
   
   
       52 . The process according to  claim 41 , wherein at least one coupling polymer is present in the anticorrosive composition.  
   
   
       53 . The process according to  claim 42 , wherein at least one coupling polymer is present in the anticorrosive composition.  
   
   
       54 . The process according to  claim 41 , wherein at least one base polymer based on acrylate, epoxide, methacrylate, polyester, polyurethane or/and copolymers thereof is added to the anticorrosive composition.  
   
   
       55 . The process according to  claim 42 , wherein at least one base polymer based on acrylate, epoxide, methacrylate, polyester, polyurethane or/and copolymers thereof is added to the anticorrosive composition.  
   
   
       56 . The process according to  claim 41 , wherein the dispersion or solution of at least one photoinitiator is added to the anticorrosive composition, based on compounds selected from the group comprising amino ketones, benzoin ethers, benzophenones, dimethyl ketals, glyoxylates, hydroxyketones, hydroxyphenones, isopropyl ethers, metallocenes, organic iodine compounds, phenyl ketones, phenyl propanes, phosphine oxides and derivatives thereof, in order to allow an anionic, cationic or/and radical cure.  
   
   
       57 . The process according to  claim 42 , wherein the dispersion or solution of at least one photoinitiator is added to the anticorrosive composition, based on compounds selected from the group comprising amino ketones, benzoin ethers, benzophenones, dimethyl ketals, glyoxylates, hydroxyketones, hydroxyphenones, isopropyl ethers, metallocenes, organic iodine compounds, phenyl ketones, phenyl propanes, phosphine oxides and derivatives thereof, in order to allow an anionic, cationic or/and radical cure.  
   
   
       58 . The process according to  claim 41 , wherein at least one crosslinking agent is added to the anticorrosive composition, based on isocyanate, isocyanurate, melamine resin or/and compounds which can release isocyanate or isocyanurate at elevated temperature, such as e.g. TDI, MDI, HDMI or/and HDI, in particular a water-dispersible polymerizable postcuring compound, in order to allow a chemical postcure, which is preferably intensified by heating.  
   
   
       59 . The process according to  claim 42 , wherein at least one crosslinking agent is added to the anticorrosive composition, based on isocyanate, isocyanurate, melamine resin or/and compounds which can release isocyanate or isocyanurate at elevated temperature, such as e.g. TDI, MDI, HDMI or/and HDI, in particular a water-dispersible polymerizable postcuring compound, in order to allow a chemical postcure, which is preferably intensified by heating.  
   
   
       60 . The process according to  claim 41 , wherein at least one first organic corrosion inhibitor is added to the anticorrosive composition, selected from the group of compounds based on amines, derivatives of an organic acid such as e.g. dicarboxylic acid derivatives, thiols and conductive polymers, in particular based on succinic acid derivatives, ethyl morpholine derivatives, polyamine fatty acid derivatives or/and triazole derivatives.  
   
   
       61 . The process according to  claim 42 , wherein at least one first organic corrosion inhibitor is added to the anticorrosive composition, selected from the group of compounds based on amines, derivatives of an organic acid such as e.g. dicarboxylic acid derivatives, thiols and conductive polymers, in particular based on succinic acid derivatives, ethyl morpholine derivatives, polyamine fatty acid derivatives or/and triazole derivatives.  
   
   
       62 . The process according to  claim 41 , wherein at least one further organic or/and inorganic corrosion inhibitor is added to the anticorrosive composition, selected from the group based on anticorrosive pigments and compounds of titanium, hafnium, zirconium, carbonate, ammonium carbonate, amines, amine derivatives, derivatives of an organic acid, thiols or/and conductive polymers, wherein the anticorrosive pigments are preferably those based on a silica, an oxide or a silicate.  
   
   
       63 . The process according to  claim 41 , wherein a corrosion inhibitor is added to the anticorrosive composition in a ratio of organic to inorganic corrosion inhibitors in the range from 1:8 to 1:20.  
   
   
       64 . The process according to  claim 42 , wherein a corrosion inhibitor is added to the anticorrosive composition in a ratio of organic to inorganic corrosion inhibitors in the range from 1:8 to 1:20.  
   
   
       65 . The process according to  claim 41 , wherein at least one additive is added to the anticorrosive composition, such as e.g. at least one wetting agent, defoaming agent, lubricant, bonding agent, pigments, flow control agents, agents to increase reactivity, surface additives to increase scratch resistance, thixotropic auxiliary agents or/and examples for substrate wetting such as are used in particular for bonding to electrodeposition coatings.  
   
   
       66 . The process according to  claim 42 , wherein at least one additive is added to the anticorrosive composition, such as e.g. at least one wetting agent, defoaming agent, lubricant, bonding agent, pigments, flow control agents, agents to increase reactivity, surface additives to increase scratch resistance, thixotropic auxiliary agents or/and examples for substrate wetting such as are used in particular for bonding to electrodeposition coatings.  
   
   
       67 . The process according to  claim 41 , wherein the anticorrosive composition contains at least one lubricant selected from the group of compounds based on graphite, polyethylene, polypropylene, polytetrafluoroethylene, silane, siloxane and wax, selected in particular from crystalline microwaxes, silanes or/and polysiloxanes.  
   
   
       68 . The process according to  claim 42 , wherein the anticorrosive composition contains at least one lubricant selected from the group of compounds based on graphite, polyethylene, polypropylene, polytetrafluoroethylene, silane, siloxane and wax, selected in particular from crystalline microwaxes, silanes or/and polysiloxanes.  
   
   
       69 . The process according to  claim 41 , wherein the anticorrosive composition contains as additive at least one pigment selected from the group of compounds based on coloured pigment, metal pigment, oxide, phosphate, phosphide, phosphosilicate, silicate, electrically conductive pigment and coated pigment and selected in particular from the group comprising aluminium, aluminium alloys, iron alloys, iron hydroxide, iron oxide, iron phosphate, iron phosphide, graphite, silica, modified silica, optionally modified aluminium silicate, alkaline earth silicate or alumosilicate, hypostoichiometric electrically conductive oxide, carbon black, zinc and more highly corrosion-resistant aluminium- or/and zinc-containing alloy.  
   
   
       70 . The process according to  claim 42 , wherein the anticorrosive composition contains as additive at least one pigment selected from the group of compounds based on coloured pigment, metal pigment, oxide, phosphate, phosphide, phosphosilicate, silicate, electrically conductive pigment and coated pigment and selected in particular from the group comprising aluminium, aluminium alloys, iron alloys, iron hydroxide, iron oxide, iron phosphate, iron phosphide, graphite, silica, modified silica, optionally modified aluminium silicate, alkaline earth silicate or alumosilicate, hypostoichiometric electrically conductive oxide, carbon black, zinc and more highly corrosion-resistant aluminium- or/and zinc-containing alloy.  
   
   
       71 . The process according to  claim 41 , wherein on application the anticorrosive coating displays a viscosity in the range from 80 to 20000 mPa·s, in particular on metal strip in the range from 350 to 10000 mPa·s, measured at a temperature of 25° C. with a Haake VT 500 rotational viscometer with an MV DIN measuring cylinder in accordance with DIN 53019.  
   
   
       72 . The process according to  claim 42 , wherein on application the anticorrosive coating displays a viscosity in the range from 80 to 20000 mPa·s, in particular on metal strip in the range from 350 to 10000 mPa·s, measured at a temperature of 25° C. with a Haake VT 500 rotational viscometer with an MV DIN measuring cylinder in accordance with DIN 53019.  
   
   
       73 . The process according to  claim 41 , wherein on application the anticorrosive composition has a temperature in the range from 5 to 90° C.  
   
   
       74 . The process according to  claim 42 , wherein on application the anticorrosive composition has a temperature in the range from 5 to 90° C.  
   
   
       75 . The process according to  claim 41 , wherein the anticorrosive composition is applied to the metallic surface by pouring without or with a knife, spraying, atomisation, dipping or/and rolling.  
   
   
       76 . The process according to  claim 42 , wherein the anticorrosive composition is applied to the metallic surface by pouring without or with a knife, spraying, atomisation, dipping or/and rolling.  
   
   
       77 . The process according to  claim 41 , wherein surfaces consisting of aluminium, aluminium-containing alloys, chromium, chromium alloys, magnesium alloys, stainless steel, steel, zinc, zinc-containing alloys, tin or/and tin-containing alloys are coated.  
   
   
       78 . The process according to  claim 42 , wherein surfaces consisting of aluminium, aluminium-containing alloys, chromium, chromium alloys, magnesium alloys, stainless steel, steel, zinc, zinc-containing alloys, tin or/and tin-containing alloys are coated.  
   
   
       79 . The process according to  claim 41 , wherein the wet film of the anticorrosive composition is dried at temperatures in the range from 30 to 95° C., preferably by heating in an oven, inductive drying, IR irradiation, NIR irradiation or/and microwave irradiation.  
   
   
       80 . The process according to  claim 42 , wherein the wet film of the anticorrosive composition is dried at temperatures in the range from 30 to 95° C., preferably by heating in an oven, inductive drying, IR irradiation, NIR irradiation or/and microwave irradiation.  
   
   
       81 . The process according to  claim 41 , wherein the largely or completely dry film of the anticorrosive composition is irradiated with UV radiation, e.g. a mercury vapor lamp, in particular in the wavelength range from 180 to 700 nm and is partially, largely or completely crosslinked in this way.  
   
   
       82 . The process according to  claim 42 , wherein the largely or completely dry film of the anticorrosive composition is irradiated with UV radiation, e.g. a mercury vapor lamp, in particular in the wavelength range from 180 to 700 nm and is partially, largely or completely crosslinked in this way.  
   
   
       83 . The process according to  claim 41 , wherein the anticorrosive composition is selected in terms of double bonds of the monomers, oligomers or/and polymers and the content of monomers, oligomers or/and polymers and in terms of the duration, intensity and wavelength of the UV radiation such that a polymeric network having a medium-sized distance between crosslinking points is formed which at the same time has high flexibility and high chemical resistance.  
   
   
       84 . The process according to  claim 42 , wherein the anticorrosive composition is selected in terms of double bonds of the monomers, oligomers or/and polymers and the content of monomers, oligomers or/and polymers and in terms of the duration, intensity and wavelength of the UV radiation such that a polymeric network having a medium-sized distance between crosslinking points is formed which at the same time has high flexibility and high chemical resistance.  
   
   
       85 . The process according to  claim 41 , wherein the anticorrosive composition and the anionically, cationically or/and radically cured dry film produced therewith contains at least one hardener, such that the dry film, optionally after being heated to at least 60° C., is chemically postcured.  
   
   
       86 . The process according to  claim 42 , wherein the anticorrosive composition and the anionically, cationically or/and radically cured dry film produced therewith contains at least one hardener, such that the dry film, optionally after being heated to at least 60° C., is chemically postcured.  
   
   
       87 . The process according to  claim 41 , wherein the substrate coated with the anticorrosive coating can be coated with at least one further paint-like composition, lacquer, paint or/and adhesive.  
   
   
       88 . The process according to  claim 42 , wherein the substrate coated with the anticorrosive coating can be coated with at least one further paint-like composition, lacquer, paint or/and adhesive.  
   
   
       89 . The process according to  claim 41 , wherein the anticorrosive coating applied to the metallic body is formed with the substrate, in particular a metal sheet, wherein the anticorrosive coating remains largely or entirely undamaged.  
   
   
       90 . The process according to  claim 42 , wherein the anticorrosive coating applied to the metallic body is formed with the substrate, in particular a metal sheet, wherein the anticorrosive coating remains largely or entirely undamaged.  
   
   
       91 . The process according to  claim 41 , wherein the formed substrate in the form of a formed, cut or/and stamped metal sheet coated with the anticorrosive coating is joined to another construction element by clinching, gluing, welding or/and at least one other joining process.  
   
   
       92 . The process according to  claim 42 , wherein the formed substrate in the form of a formed, cut or/and stamped metal sheet coated with the anticorrosive coating is joined to another construction element by clinching, gluing, welding or/and at least one other joining process.  
   
   
       93 . The process according to  claim 41 , wherein the metallic surface is cleaned or/and pickled before application of the pretreatment primer coat and optionally rinsed thereafter at least once with water or an aqueous solution.  
   
   
       94 . The process according to  claim 42 , wherein the metallic surface is cleaned or/and pickled before application of the pretreatment primer coat and optionally rinsed thereafter at least once with water or an aqueous solution.  
   
   
       95 . The process according to  claim 41 , wherein the solution or dispersion is applied to a metallic strip carried on a conveyor belt system, in particular to a strip that has just been coated with aluminium, with an aluminium-containing alloy or with a zinc-containing alloy.  
   
   
       96 . The process according to  claim 42 , wherein the solution or dispersion is applied to a metallic strip carried on a conveyor belt system, in particular to a strip that has just been coated with aluminium, with an aluminium-containing alloy or with a zinc-containing alloy.  
   
   
       97 . An organic, anionically, cationically or/and radically curable anticorrosive composition comprising a dispersion or solution comprising at least two components selected from the group consisting of a monomer, an oligomer and a polymer with a content in the range from 50 to 95 wt. %, which are least partially anionically, cationically or/and radically curable, 
 a content of at least one monofunctional monomer or/and oligomer in the range from 1 to 58 wt. % or/and at least one modified flexibilizing resin as well as of isobornyl acylate or/and isoborayl methacrylicate,    wherein the anticorrosive composition contains at least one photoinitiator for anionic, cationic or/and radical crosslinking with a content in the range from 0.5 to 22 wt. %, if electron beam radiation is not used,    together with a first organic corrosion inhibitor in particular with a content in the range from 0.05 to 6 wt. %,    optionally at least one hardener with a content in the range from 0.05 to 8 wt. % for a chemical postcure,    optionally at least one further organic or/and inorganic corrosion inhibitor in particular with a content in the range from 0.1 to 12 wt. %,    optionally up to 35 wt. % of additive(s) such as e.g. additives for substrate wetting such as in particular for bonding to electrodeposition coatings, wetting agents, defoaming agents, lubricants, bonding agents, pigments, flow control agents, agents to increase reactivity, surface additives to increase scratch resistance or/and thixotropic auxiliary agents,    and optionally a total of 0.01 to 5 wt. % of water or/and at least one organic solvent,    relative in each case to solids contents in wt. %.    
   
   
       98 . An organic, anionically, cationically or/and radically cured anticorrosive coating, which displays a dry film thickness in the range from 0.4 to 20 μm, wherein when applied directly to a metallic surface, without the interposition of a pretreatment coat, it displays a flexibility and bond strength of ≦T3, in particular of ≦T2 or even of ≦T1—determined by means of a T-bend test in accordance with ECCA standard T7.  
   
   
       99 . An organic, anionically, cationically or/and radically cured anticorrosive coating on a metallic substrate, which displays a dry film thickness in the range from 0.4 to 20 μm, wherein when applied directly to a metallic surface, without the interposition of a pretreatment coat, it displays a bond strength of ≦Gt 3, determined by means of a cross-hatch adhesion test in accordance with DIN EN 2409 and by tearing off a firmly adhering strip of adhesive tape from the cross-hatch area with visual assessment of the cross-hatch area and its flaking.  
   
   
       100 . An organic, anionically, cationically or/and radically cured anticorrosive coating on a metallic substrate, which displays a dry film thickness in the range from 0.4 to 20 μm, wherein when applied directly to a metallic surface, without the interposition of a pretreatment coat, it displays a corrosion resistance, tested as subsurface migration at a scratch, of ≦5 mm, preferably ≦3 mm, determined in a salt spray test SS to DIN 50021 for 150 h or for 360 h, wherein the anticorrosive coating remains free from blisters.  
   
   
       101 . An organic, anionically, cationically or/and radically cured anticorrosive coating on a metallic substrate, which displays a dry film thickness in the range from 0.4 to 20 μm, wherein when applied directly to a metallic surface, without the interposition of a pretreatment coat, it displays abrasion-free and fault-free cups in a determination of the cupping indentation (cup drawing) by the Erichsen test method using an Erichsen 142-20 universal sheet metal and strip testing machine with deep-drawing cup tool with a punch diameter of 33 mm and a pressing rate of 750 mm/min on blanks of 60 mm diameter made from metallic sheets coated with the anticorrosive coating.  
   
   
       102 . An organic, anionically, cationically or/and radically cured anticorrosive coating on a metallic substrate, having a dry film thickness in the range from 0.4 to 20 μm, wherein when applied directly to a metallic surface, without the interposition of a pretreatment coat, and having a chemical resistance of over 20 MEK cycles, determined in the MEK test in accordance with ECCA standard T11 with methyl ethyl ketone.  
   
   
       103 . An organic, anionically, cationically or/and radically cured anticorrosive coating on a metallic substrate, having a dry film thickness in the range from 0.4 to 20 μm, wherein that it displays a chemical resistance of over 50 MEK cycles, determined in the MEK test in accordance with ECCA standard T11 with methyl ethyl ketone.  
   
   
       104 . An organic cured anticorrosive coating on a metallic substrate, having a dry film thickness in the range from 0.1 to 20 μm, and having a chemical resistance of over 50 MEK cycles—determined in the MEK test in accordance with ECCA standard T11 with methyl ethyl ketone,—and wherein the coating has an elasticity and bond strength in the indentation test to DIN EN ISO 1520 with a ball indentation of at least 6 mm.  
   
   
       105 . A metallic substrate having a surface coated according to the process of  claim 41 .  
   
   
       106 . A metallic substrate having a surface coated according to the process of  claim 42 .  
   
   
       107 . The process according to  claim 42 , wherein at least one further organic or/and inorganic corrosion inhibitor is added to the anticorrosive composition, selected from the group based on anticorrosive pigments and compounds of titanium, hafnium, zirconium, carbonate, ammonium carbonate, amines, amine derivatives, derivatives of an organic acid, thiols or/and conductive polymers, wherein the anticorrosive pigments are preferably those based on a silica, an oxide or a silicate.