EP1844114A1 - Revetements anticorrosion contenant des groupes thioamide - Google Patents

Revetements anticorrosion contenant des groupes thioamide

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Publication number
EP1844114A1
EP1844114A1 EP06707850A EP06707850A EP1844114A1 EP 1844114 A1 EP1844114 A1 EP 1844114A1 EP 06707850 A EP06707850 A EP 06707850A EP 06707850 A EP06707850 A EP 06707850A EP 1844114 A1 EP1844114 A1 EP 1844114A1
Authority
EP
European Patent Office
Prior art keywords
groups
group
weight
use according
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06707850A
Other languages
German (de)
English (en)
Inventor
Hermann Bergmann
Monica Fernandez Gonzalez
Konrad Roschmann
Gerhard Fischer
Marc Schröder
Guido Vandermeulen
Alexander Göthlich
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BASF SE
Original Assignee
BASF SE
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
Priority claimed from DE200510004292 external-priority patent/DE102005004292A1/de
Priority claimed from DE200510061317 external-priority patent/DE102005061317A1/de
Priority claimed from DE200510061319 external-priority patent/DE102005061319A1/de
Priority claimed from DE102005061320A external-priority patent/DE102005061320A1/de
Priority claimed from DE200510061318 external-priority patent/DE102005061318A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1844114A1 publication Critical patent/EP1844114A1/fr
Withdrawn legal-status Critical Current

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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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • 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 new coating compositions for atmospheric corrosion protection.
  • DE-A 29 43 833 discloses the use of thiourea and thiourea derivatives as additives in an aqueous conversion coating composition comprising free sulfuric acid, hydrogen peroxide and silica. Mainly the treatment takes place with phosphorus compounds, thioacetamide is described as a minor component.
  • EP-A 878 519 discloses preferably chromium-free, aqueous compositions for the preparation of anticorrosion coatings which contain 0.2 to 50 g / l of a thiocarbonyl compound, 0.1 to 5 g / l of phosphates and water-soluble binders or binder dispersions. Optionally, 10 to 500 g / l SiO ⁇ may be present.
  • the thiocarbonyl compounds may, for example, be thiourea, thioamides, thioaldehydes or thiocarboxylic acids.
  • the corrosion coatings described therein require heating and drying of the coated material in a hot environment or coating of a previously heated substrate. This requires temperatures between 50 and 250 ° C. Only layer thicknesses of 0.1 to 20 ⁇ m are disclosed; layer thicknesses outside this range are described as ineffective or uneconomical.
  • JP-A 2002-64856, JP-A 2002-241957, JP-A 297384 and JP-A 2003-73856 disclose various aqueous compositions for the preparation of anticorrosion coatings, which are aqueous various aqueous polymer dispersions, other components and thiocarbonyl compounds such as thiourea or Containing ethanethioamide. Thioamides with more than one thioamide group are not disclosed for atmospheric corrosion protection.
  • thioamides have hitherto been disclosed mainly in so-called coil coatings, ie coatings of rolled metal strips which are wound up into rolls (so-called “coils”) after production for storage and transport.
  • coil coatings ie coatings of rolled metal strips which are wound up into rolls (so-called “coils") after production for storage and transport.
  • These metal strips represent the starting material for most flat metal workpieces, for example se automotive parts, body parts, equipment panels, cladding, ceiling panels or window profiles.
  • the suitable metal sheets are formed by means of suitable techniques such as stamping, drilling, folding, profiling and / or deep-drawing. Larger components, such as automobile bodies are optionally joined together by welding several items.
  • Coil coating is the continuous coating of metal strips with mostly liquid coating materials. In this case, 0.2 to 2 mm thick and up to 2 m wide metal strips are transported at a rate of up to 200 m / min through a coil coating system and thereby coated.
  • cold-rolled strips of soft steels or structural steels, electrolytically galvanized sheet, hot-dip galvanized steel strip or strips of aluminum or aluminum alloys can be used.
  • Typical installations include a feed station, a strip accumulator, a cleaning and pretreatment zone, a first coating station together with a baking oven and subsequent cooling zone, a second coating station with oven, laminating station and cooling as well as a belt store and rewinder.
  • Characteristic of coil coatings are thin layers of the coating compositions, which have a dry film thickness of mostly well below 80 microns, often below 60 microns, below 50 microns and even below 40 microns.
  • the sheets are processed with high throughput, which makes short residence times required, so after applying the coating requires drying at elevated temperature required to make the broom ichtungsmasse fast loadable.
  • the object of the present invention was to develop processes for corrosion protection with which components can be coated which can not be coated and dried and / or cured in specially developed systems.
  • the difference between the requirements of the coatings and coating compositions from atmospheric corrosion protection over corrosion protection over coil coating is that the coatings in atmospheric corrosion protection have a significantly higher layer thickness than coil coatings and dried and cured at ambient temperatures, so that drying and curing essential longer periods. During this period, the unhardened coating sensitive to, for example, sprayed water or weathering, so that the coating compositions are clearly different requirements than on coil coating coating materials.
  • a method for applying anticorrosive coatings to metallic surfaces by treating the metallic surface with a formulation comprising at least a binder, a pigment and / or a filler and a corrosion inhibitor, wherein the anticorrosive agent is at least one compound ( D) acts.
  • n is a natural number from 1 to 5
  • R 1 , R 2 , R 3 and R 4 are the following:
  • R 1 and R 2 independently of one another are H or a linear or branched, optionally substituted alkyl radical having 1 to 20 C atoms, cycloalkyl radical having 3 to 12 C atoms or aryl radical having 6 to 12 C atoms, the radicals R 1 and R 2 together with the nitrogen atom can form a five- to 12-membered ring, R 3 is an (n + 1) -valent hydrocarbon radical having 1 to 30 carbon atoms, and R 4 is a functional group.
  • metallic surfaces in particular, can be protected from corrosion which are in contact with atmospheric air during use, but they can also be surfaces which are in contact with water, soil or other corrosive media during use.
  • the metallic surfaces that are to be protected against corrosion by means of the method according to the invention may in principle be any desired surfaces. Preferably, however, it is the surfaces of metallic structures or metal structures or the components required therefor.
  • Metal structures are usually made of structural steel, such as steel beams, steel pipes or steel sheets by riveting, welding or screws to appropriate constructions.
  • the coated articles may be immobile metallic constructions such as buildings, bridges, power pylons, tanks, containers, buildings, pipelines, power plants, chemical plants, ships, cranes, piles, sheet piles, fittings, pipes , Tanks, Fittings, Flanges, Clutches, Halls, Roofs and Structural Steel Act.
  • anti-corrosive coatings are usually painted or sprayed in place. This can be either a first protection or a repair.
  • the drying and curing of such anti-corrosion coatings is carried out under atmospheric conditions, ie at ambient temperature and in the presence of air and usual humidity.
  • the relative humidity can be arbitrary, preferably it is between 10 and 80% and more preferably between 30 and 70%.
  • the corrosion protection of surfaces by anti-corrosive coatings is also referred to as light, medium and heavy corrosion protection.
  • the type of metal can in principle be any metals. In particular, however, are such metals or alloys, which are commonly used as metallic construction materials, and must be protected from corrosion.
  • steel is the surfaces of iron, steel, zinc, zinc alloys, aluminum or aluminum alloys.
  • Steel may contain the usual alloying components known to those skilled in the art. These may be the surfaces of bodies made entirely of said metals or alloys. However, they may also be the surfaces of Zn, Zn alloy, Al or Al alloy coated bodies, which bodies may be made of other materials such as other metals, alloys, polymers or composites.
  • Zinc or aluminum alloys are known in the art. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. In particular, typical constituents of aluminum alloys include Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.
  • the term "zinc alloy” is also meant to include Al / Zn alloys in which Al and Zn are present in approximately the same amount , Depending on the desired application, the skilled person will select the type and amount of alloying components.
  • Zn or aluminum coatings may be applied to steel, for example by hot dip processes, e.g. Hot dip galvanizing, or by Sherardizing be applied. If the component is immobile or the component geometry does not permit it, corresponding layers can also be applied by means of thermal spraying (spray-galvanizing, spray-aluminising).
  • the composition used according to the invention for applying corrosion protection layers to metallic surfaces comprises at least one binder. This can optionally also have crosslinkable groups. Binders for corrosion protection coatings or coatings are known to the person skilled in the art.
  • the composition used according to the invention for applying sweetener compositions comprises at least one binder (A) and crosslinkable components (B).
  • the crosslinkable components may be at least one crosslinker, which is used in addition to a binder or it may be crosslinkable groups which are connected to the binder.
  • the binder can also have crosslinkable groups and, in addition, a crosslinker can be used.
  • binders and crosslinkers can be used separately.
  • the binder then comprises reactive functional groups that can react with complementary reactive functional groups in the crosslinkers.
  • they can also be self-crosslinking binders which comprise reactive functional groups which can enter into crosslinking reactions with groups of their type ("with themselves") or with complementary, reactive functional groups on the same polymer. It is also possible that only the crosslinkers react with each other.
  • the binders (A) may be the usual binders.
  • suitable binders include (meth) acrylate (co) polymers, partially saponified vinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides or polyurethanes.
  • binders include (meth) acrylate (co) polymers, partially saponified vinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides or polyurethanes.
  • the curing can proceed according to various mechanisms. For example, it may be a purely physical curing, caused by the evaporation of the solvent used. It may also be an oxidative cure by reaction of the binder system with the oxygen of the air. Finally, it can also be a chemical crosslinking (reactivation).
  • Reactive binder systems include crosslinkable components. The crosslinkable components may be low molecular weight, oligomeric or polymeric. These may preferably be 1K or 2K systems. Reactive crosslinking systems also include moisture-curing binder systems in which the humidity acts as a hardener component.
  • a binder system can also cure by a combination of different curing methods.
  • the binder and hardener components are mixed in a manner known in the art prior to using the formulation.
  • aqueous-soluble or organic-soluble binder systems can be used. They are preferably water-based binder systems.
  • Binder systems for anticorrosion coatings are known in principle to the person skilled in the art. These may be, for example, epoxy resins, polyacrylates, styrene-acrylate polymers, polyesters, alkyd resins, polyurethanes of the styrene-butadiene polymers.
  • the amount of binder (A) in the formulation is 15 to 70% by weight, based on the amount of all components of the formulation including the solvent. It is determined by the skilled person depending on the desired properties of the coating. The amount is preferably from 20 to 60% by weight and more preferably from 25 to 50% by weight.
  • the polymer of the binder (A) is selected from the group consisting of
  • Polyacrylates (A1) are usually composed of
  • A1a from 40 to 100% by weight, preferably from 60 to 100% by weight, particularly preferably from 80 to 100% by weight, of at least one main monomer having a free-radically polymerizable group,
  • A1c 0 to 4% by weight, preferably 0.01 to 2, particularly preferably at least 0.05 to 1% by weight of at least one crosslinking agent.
  • Main monomers A1a) contain a free-radically polymerizable group and are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, Vinyl ethers of alcohols containing from 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms or mixtures of these these monomers.
  • (Meth) acrylic acid alkyl ester having a Ci-Cio-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are e.g. Vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene .alpha.- and p-methylstyrene, .alpha.-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers there are e.g. Vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • monomers (A1a) are preferably the alkyl (meth) acrylates, preferably (C2 to Cio-alkyl) acrylates and methacrylates and the vinyl aromatic, and mixtures of these compounds into consideration.
  • methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate and styrene and mixtures of these monomers as monomers (A1a) are preferred.
  • copolymerizable monomers A1 b) are other monomers having a free-radically polymerizable group than those mentioned under (A 1a), preferably those which in addition to the free-radically polymerizable double bond at least one, preferably 1 to 3, particularly preferably 1 to 2 and most preferably one more functional group, such as Hydroxy groups, carboxylic acid amide groups or carboxyl groups, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide, ethylenically unsaturated acids or acid anhydrides, in particular carboxylic acids, such as (meth) acrylic acid, crotonic acid or dicarboxylic acids, e.g. Itaconic acid, maleic acid or fumaric acid.
  • a functional group such as Hydroxy groups, carboxylic acid amide groups or carboxyl groups, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide, ethylen
  • (Meth) acrylic acid in this specification means methacrylic acid and acrylic acid.
  • Crosslinkers A1c) are those which have at least two free-radically polymerizable double bonds, preferably 2 to 6, particularly preferably 2 to 4, very particularly preferably 2 to 3 and in particular 2.
  • the at least two free-radically polymerizable double bonds of the crosslinkers A1c) may be selected from the group consisting of (meth) acrylic, vinyl ether, vinyl ester, allyl ether and allyl ester groups.
  • crosslinkers A1c may be the same or different.
  • Examples of compounds A1c) having the same radically polymerizable groups are 1,2-ethanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, 1,4-butanediol di (meth ) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioldi (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1, 4- Cyclohexanediol divinyl ether and divinylbenzene. Preference is given to divinylbenzene, 1,4-butanediol diacrylate and
  • Examples of compounds A1c) with different radically polymerizable groups are allyl acrylate, allyl methacrylate, methallyl acrylate, methacrylyl methacrylate, (meth) acrylic acid but-3-en-2-yl ester, (meth) acrylic acid but-2-en-1-yl ester, (Meth ) Acrylic acid 3-methyl-but-2-en-1-yl ester, esters of (meth) acrylic acid with geraniol, citronellol, cinnamyl alcohol, glycerol mono- or diallyl ether, trimethylolpropane mono-or diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, propylene glycol monoallyl ether , Dipropylene glycol monoallyl ether, 1,3-propanediol monoallyl ether, 1,4-butanediol monoallyl ether, and furthermore itaconic acid diallyl ester
  • the polyacrylates (A1) can be prepared in a manner known per se by the generally known methods of emulsion polymerization from the monomers using the customary emulsifying and dispersing auxiliaries and polymerization initiators.
  • Suitable dispersants for carrying out free-radically aqueous emulsion polymerizations are usually emulsifiers used in amounts of from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight, or protective colloids in amounts of from 5 to 40% by weight, in particular from 5 to 25 wt .-%, based on the monomers, into consideration.
  • Common emulsifiers are, for example, ammonium or alkali metal salts of higher fatty alcohol sulfates, such as Na-n-lauryl sulfate, fatty alcohol phosphates, ethoxylated Cs to C10-alkylphenols having a degree of ethoxylation of 3 to 30 and ethoxylated Cs to C25 fatty alcohols having a degree of ethoxylation of 5 to 50. Conceivable also mixtures of nonionic and ionic emulsifiers. Also suitable are phosphate- or sulfate-containing, ethoxylated and / or propoxylated alkylhenols and / or fatty alcohols. Further suitable emulsifiers are listed in Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 209.
  • Suitable protective colloids are high molecular weight natural substances such as starch, methylcellulose, pectins and gelatin, synthetic substances such as polyvinyl alcohol and polyvinylpyrrolidone. Other protective colloids are described in detail in Houben-Weyl, loc. cit., pp. 411-420.
  • polyurethanes and copolymers of olefinic monomers with (meth) acrylic acid and / or maleic acid are suitable.
  • Suitable polymerization initiators are all those which are capable of initiating a free-radical emulsion polymerization in aqueous media. They are generally used in amounts of 0.1 to 10 wt .-%, preferably from 0.2 to 4 wt .-%, based on the monomers. Typical compounds are inorganic peroxides, for example sodium and ammonium peroxydisulfate and hydrogen peroxide, organic peroxides such as dibenzoyl peroxide or tert-butyl hydroperoxide and azo compounds such as azoisobutyrodinitrile. These initiators are suitable for the customary in the radical emulsion polymerizations reaction temperatures of 50 to 100 0 C.
  • redox systems such as combinations of per compounds and a reducing coinitiator the sodium salt of hydroxymethanesulfinic acid, ascorbic acid or iron-II-salt is preferable.
  • both primary and secondary dispersions can be used according to the invention.
  • the polymerization of the basic monomers takes place directly in the aqueous phase, for example in the form of an emulsion or miniemulsion, in which the monomers are distributed in the aqueous phase with a droplet diameter of 0.1 to 0.2 .mu.m
  • prefabricated secondary emulsions Polymers are dispersed in a further process step, usually by polymerization in an organic solvent, then dispersing the polymer in water optionally followed by a preferably distillative removal of the solvent from the dispersion.
  • Has proven particularly useful a feed process in which one starts from a template consisting of a portion of the monomers, generally up to 20 wt .-%, water, emulsifier and initiator. The remainder of the monomers and optionally regulators in emulsified form and additionally an aqueous solution of further polymerization initiator are added in accordance with the polymerization.
  • the acid groups present in the (co) polymer can still be at least partially neutralized.
  • This can be done, for example, with oxides, hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, preferably with hydroxides to which any one or more counterions may be associated, eg Li + , Na + , K + , Cs + , Mg 2+ , Ca 2 + or Ba 2+ .
  • ammonia or amines especially tertiary amines, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, di-iso-propyl-ethyl-amine, benzyldimethylamine, monoethanolamine, diethanolamine, triethanolamine, hydroxyethyl -Dimethylamine, hydroxyethyl-diethylamine, monopropanolamine, dipropanolamine, tripropanolamine, piperidine, piperazine, N 1 N 1 -dimethylpiperazine, morpholine or pyridine.
  • tertiary amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, di-iso-propyl-ethyl-amine, benzyldimethylamine, monoethanolamine, diethanol
  • 50 to 100 mol% of the acid groups in the (co) polymer are neutralized, particularly preferably 75 to 100 mol%, very particularly preferably 90 to 100 and in particular 100 mol%.
  • the aqueous polymer dispersion of the polyacrylates (A1) preferably has a solids content of from 35 to 65, particularly preferably from 45 to 55,% by weight.
  • the glass transition temperature Tg of the copolymers is preferably in the range from 0 to 60 0 C, more preferably in the range of 5 to 40 0 C (measured by the DSC method according to DIN EN ISO 11357).
  • the binder system is an aqueous or predominantly aqueous dispersion of polyurethanes (A2).
  • Aqueous dispersions of polyurethanes (A2) for the preparation of corrosion protection coatings are known in principle to the person skilled in the art. Details of polyurea brushes and their preparation are disclosed, for example, in "Paints and Coatings, 2.9 Polyurethane Coatings in"Ullmann's Encyclopedia of Technical Chemistry, 6th Edition 2000, Electronic Release Polyurethanes (A2) can be both primary dispersions and secondary dispersions.
  • Polyurethanes for aqueous dispersions can be synthesized in a manner known in principle from customary diisocyanates and diols. With regard to good film formation and elasticity, particular preference is given to diols having a number average molecular weight M n of about 500 to 5000 g / mol, preferably about 1000 to 3000 g / mol. Both polyether and polyester diols can be used for this purpose. The amount of such higher molecular weight diols is usually 10 to 100 mol% with respect to the sum of all diols.
  • the desired hardness and elasticity of the film can be controlled by using, in addition to the diol already mentioned, low molecular weight diols with a number average molecular weight M n of about 60 to 500 g / mol.
  • polyurethanes for aqueous dispersions monomers are additionally used which comprise at least one isocyanate group or an isocyanate-reactive group and additionally at least one hydrophilic group.
  • These may be nonionic groups such as, for example, polyoxyethylene groups, acidic groups such as COOH, sulfonate or phosphonate groups or basic groups such as amino groups. They are preferably acidic groups.
  • the acid groups may preferably be neutralized in whole or in part with suitable bases. Preferred for this purpose are ammonia or amines. Further details of such polyurethane dispersions and their preparation are described in detail in WO 2005/005565, page 4, line 13 to page 14, line 14. Further examples of suitable polyurethanes are disclosed in US 5,707,941 or in WO 2004/101638, especially page 2, line 31 to page 14, line 11.
  • polyurethanes may also be modified polyurethanes.
  • it may be oxidatively curing urethane alkyds.
  • triglycerides of unsaturated fatty acids can be partially hydrolyzed for production. The resulting OH group can react with the isocyanate groups in polyurethane production.
  • Styrene-butadiene polymers (A3) can be synthesized by free-radically initiated aqueous emulsion polymerization of A3a) 19.9 to 80 parts by weight of conjugated aliphatic dienes [monomers
  • the total amount of the ethylenically unsaturated monomers A3a) to A3e) is 100 parts by weight, in the presence of water and 0.1 to 5 parts by weight of emulsifiers, based on the total amount of monomers.
  • Preferred conjugated aliphatic dienes are butadiene, isoprene, pentadiene-1,3-dimethylbutadiene and / or cyclopentadiene, preferably butadiene.
  • vinylaromatic compounds are in particular called styrene, ⁇ -methylstyrene and / or vinyltoluene, preferably styrene.
  • ethylenically unsaturated carboxylic acids and / or dicarboxylic acids there are preferably used ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms such as e.g. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, preferably (meth) acrylic acid and itaconic acid, more preferably acrylic acid.
  • the carboxylic acid amides used are the amides of the abovementioned ethylenically unsaturated carboxylic acids, preferably (meth) acrylamide.
  • Preferred ethylenically unsaturated carboxylic acid nitriles are acrylonitrile and / or methacrylonitrile [monomers A3d)] and as copolymerizable vinyl compounds [monomers A3e)], esters of acrylic and / or methacrylic acid in which the alkyl group contains 22 or fewer carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and allyl esters of saturated monocarboxylic acids, vinyl esters, vinyl ethers, vinyl ketones, dialkyl esters of unsaturated dicarboxylic acids, vinyl acetate and / or vinylpyridine, vinyl chloride, vinylidene chloride.
  • the emulsifiers are preferably used in amounts of from 0.2 to 4.5 parts by weight, based on 100 parts by weight of the abovementioned monomers A3a) to A3e).
  • Particularly suitable emulsifiers are ethoxylated fatty alcohols and sulfuric monoesters of ethoxylated fatty alcohols, each consisting of a straight-chain or branched alkyl radical having 8 to 18 carbon atoms, which is linked via an ether group with a poly- or oligoethyleneoxysequence.
  • Ethylene oxide oligomers which come into consideration as poly- or oligoethyleoxy sequences are those having a degree of polymerization of 2 to 30 ethylene oxide units, preferably 2 to 7 ethylene oxide units.
  • Particularly preferred fatty alcohol ethers and fatty alcohol ether such called the 8 -C contain, as a fatty alcohol C 8 alkyl. Particular preference is given to lauryloligoethylene oxysulfate, palmityl oligoethylene oxysulfate, stearyloligoethylene oxysulfate and oleylene glycol oxysulfate, the oligoethyleneoxy sequence particularly preferably consisting of 2 to 7 ethylene oxide units.
  • the fatty alcohol used may be both the pure starting compound or else the mixtures of homologous and isomeric alkyl radicals which are frequently obtained from the synthetic fatty alcohols, for example a mixture of C 12 and C 13 fatty alcohols.
  • the degree of ethoxylation expresses only the mean of a distribution.
  • the free acid group of the sulfate radical is usually neutralized as ammonium or alkali metal salt, but the neutralization can also take place during dosing by the base used.
  • esters or half-esters of alkylpolyoxyethylene sulfosuccinates are used as emulsifiers.
  • the sulfosuccinic acid is mono- or di-double esterified with poly- or oligoethylene oxide having 2 to 30 ethylene oxide units, preferably 2 to 7 ethylene oxide units, in particular 2 to 5 ethylene oxide units, the end group of said esters and half esters consisting of an alkyl group having 8 to 18 carbon atoms which is straight-chain or branched.
  • C 8 -C 8 alkyl radicals containing -carbon be mentioned in particular: caprylic, capric, lauryl, myristyl, stearyl and Elaidinalkohol.
  • the free-radically aqueous emulsion polymerization is initiated in a manner known to the person skilled in the art by water-soluble free-radical initiators.
  • organic and / or inorganic peroxides such as e.g. Alkali metal peroxodisulfates and / or azo compounds or combined systems composed of at least one reducing agent and at least one peroxide and / or hydroperoxide, such as e.g.
  • tert-butyl hydroperoxide and the sodium salt of hydroxymethanesulphinic acid or hydrogen peroxide and ascorbic acid or combined systems which further contain a small amount of a metal compound soluble in the polymerization medium, the metallic component of which may occur in several valence states, e.g.
  • Ascorbic acid / iron (II) sulfate / hydrogen peroxide wherein instead of ascorbic also frequently the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite, sodium bisulfite and / or sodium disulfite and instead of hydrogen peroxide tert-butyl hydroperoxide or alkali metal peroxide sulfates and / or Amiumiumperoxodisulfate be used.
  • a water-soluble iron (II) salt a combination of water-soluble Fe / V salts is frequently used.
  • the initiator system may be added continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization.
  • peroxides e.g. Alkali metal peroxodisulfates, such as sodium or ammonium peroxodisulfate.
  • the addition of the radical initiators, usually dissolved in water, into the polymerization reactor generally takes place via a separate feed.
  • the cheapest amount of water-soluble initiators can be easily determined by appropriate preliminary tests.
  • the water-soluble initiators are added in an amount of from 0.1 to 2.0% by weight, based on the total mass of the monomers to be polymerized.
  • the known molecular weight regulators such as mercapto compounds, such as, for example, tertiary dodecyl mercaptan or dimeric ⁇ -methylstyrene, may also be added for the emulsion polymerization.
  • auxiliaries such as complexing agents, for example ethylenediaminetetraacetic acid sodium salt (EDTA-Na), for example for interfering metal ions, inhibitors, for example hydroquinone monomethyl ethers or foam inhibitors, may be added to the emulsion polymerization.
  • complexing agents for example ethylenediaminetetraacetic acid sodium salt (EDTA-Na)
  • inhibitors for example hydroquinone monomethyl ethers or foam inhibitors
  • the molecular weight regulators and the adjuvants are known and described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, p. 297 ff., 1961, Stuttgart.
  • emulsion polymerization for the preparation of the aqueous dispersion of copolymers, it may be advantageous to add up to 15% by weight of the total amount of emulsifier used to the reaction mixture at the beginning of the polymerization and the remaining amount, ie. then add up to 85 wt .-% of the total emulsifiers used within the time in which reaches up to 40% of the total conversion of the feed components.
  • Suitable bases are, in particular, aqueous solutions of alkali metal oxides or hydroxides, very particularly preferably aqueous ammonium hydroxide, sodium hydroxide or potassium hydroxide solutions.
  • the components A3a) to A3e) are fed to the polymerization reactor during the polymerization via a common feed line.
  • the components A3a) to A3e) and at least a subset of the water are mixed during the supply by means of a mixing device to form an emulsion.
  • Suitable mixers are, in particular, dynamic mixers whose mixing elements contain movable parts and static mixers, i. Mixing elements without moving parts in the interior, which work in particular according to the inline principle.
  • Suitable mixers are e.g. in A. Echte, Handbuch der ischen Polymerchemie, VCH Verlagsgesellschaft Weinheim, p. 104 ff. (1993).
  • Suitable dynamic in-line mixers are, for example, the scraped-surface scrubbers described in ZFL-Zeitschrift für Anlagentechnologie und -Verfahrenstechnik (1982) 33 (3), p. 139 ff. Me (2004), on the rotor-stator principle working crushing machines such as Zahnkranzdispergiermaschinen, colloid and Korundanglednmühlen and high-pressure and ultrasonic homogenizers.
  • Suitable dynamic inline mixers are still continuous tube mixers.
  • Suitable static in-line mixers are e.g. in ZFL-Zeitschrift für Anlagentechnologie und-Verfahrenstechnik (1982) 33 (3) p. 139 et seq. Ross ISG mixers, in which the fluid flow is passed through internals with holes that divide it into sub-streams, which are then laterally displaced and recombined in a different order, or static mixers comprising a plurality of identical, fixed mixing elements, the - offset by 90 ° - installed one after the other in a pipe or duct (eg Kenics, Sulzer SMV and Sulzer SMX mixers).
  • shear gap mixers such as the jet dispersants described in EP-B-101 007.
  • mixers are also inline emulsification devices such as membranes, jet mixers, mixing nozzles and curved tubular devices of substantially circular or ellipsoidal cross-section.
  • Alkyd resins (A4) are polycondensation resins of polyols, polybasic carboxylic acids and fatty oils or free natural and / or synthetic fatty acids; at least one polyol must be tri- or higher-functional.
  • dicarboxylic acids examples include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, aliphatic cycloaliphatic such as dinner fatty acids, i. Reaction products of unsaturated fatty acids with each other, cycloaliphatic dicarboxylic acids such as 1, 4- or 1 .S-cyclohexanedicarboxylic acid, tricyc- iodo-decanedioic acid and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid or phthalic acid. Of course, it is also possible to use derivatives of dicarboxylic acids.
  • Anhydrides such as, for example, phthalic anhydride, hexahydrophthalic anhydride or tetradehydrophthalic anhydride, are particularly suitable.
  • dialcohols 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-methylpropanediol 1, 3, 2-butyl-2-ethyl-propanediol, pentanediols, hexanediols, octanediols, dodecanediol, hydroxypivalic neopentyl glycol esters, cycloaliphatic alcohols such as 1, 4- or 1, 3-cyclohexanedimethanol, 3 (or 4), 8 (or 9 ) Bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane Isomer mixtures and bis (4-hydroxycyclohexyl) methane or -propane and
  • Suitable monomers for generating branching include tricarboxylic acids or their anhydrides, such as trimellitic anhydride or trimesic acid, and trialcohols, such as trimethyolalkanes, for example trimethylolethane or trimethylolpropane.
  • Preferred polyhydric alcohols are glycerol, pentaerythritol, trimethylolethane, trimethylopropane, various diols, such as ethane / propanediol, diethylene glycol, neopentyl glycol.
  • Preferred polybasic carboxylic acids are phthalic acid (anhydride) (PSA), isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid, sebacic acid.
  • the oil component or fatty acid are, for example, drying oils, such as linseed oil, oiticica oil or wood oil, semi-drying oils, such as soybean oil, sunflower oil, safflower oil, ricinoleic oil or tall oil, non-drying oils, such as castor oil, coconut oil or peanut oil, or free fatty acids of the above oils or synthetic monocarboxylic acids into consideration.
  • drying oils such as linseed oil, oiticica oil or wood oil
  • semi-drying oils such as soybean oil, sunflower oil, safflower oil, ricinoleic oil or tall oil
  • non-drying oils such as castor oil, coconut oil or peanut oil
  • free fatty acids of the above oils or synthetic monocarboxylic acids into consideration such as castor oil, coconut oil or peanut oil.
  • the molecular weight of typical alkyd resins is between 1500 and 20,000, preferably between 3500 and 6000.
  • the acid number is preferably 2 to 30 mg KOH / g, with water-dilutable resins also 35-65 mg KOH / g.
  • the OH number is generally up to 300, preferably up to 100 mg KOH / g.
  • polymers (A) Naturally, hybrids or mixtures of the abovementioned polymers are conceivable as polymers (A).
  • Preferred polymer dispersions of the invention are those in which the glass transition temperature measured by the DSC method according to DIN EN ISO 11357 of the polymer (A) - in the case of polyacrylates (A1) between 0 and 60 0 C,
  • alkyd resins (A4) is between 0 and 60 0 C.
  • polymer dispersions according to the invention in which the glass transition temperature of the polymer (A) is - in the case of polyacrylates (A1) between 5 and 40 0 C,
  • alkyd resins (A4) between 5 and 40 0 C, is.
  • polymer dispersions in which the water absorption according to DIN 53495 ("Testing of plastics - Determination of water absorption", Method 3 within 24 hours at 23 0 C) of the polymer (A) - in the case of polyacrylates (A1) no longer than 25, preferably not more than 10 and more preferably not more than 5% by weight,
  • polyurethanes (A2) up to 100, preferably up to 50 and preferably preferably up to 30% by weight or
  • styrene-butadiene polymers (A3) not more than 15, preferably not more than 8 and more preferably not more than 3% by weight
  • alkyd resins (A4) not more than 25, preferably not more than 10 and more preferably not more than 5 wt%, is.
  • polymer dispersions in which the particle size, measured with the Malvern® Autosizer 2 C, of the polymer (A)
  • polyacrylates (A1) between 50 and 400 nm, more preferably between 80 and 250 nm,
  • polyurethanes (A2) ⁇ 1000 nm, more preferably ⁇ 500 nm, most preferably ⁇ 200 nm and in particular between 20 and below 200 nm, or
  • alkyd resins (A4) between 50 and 400 nm, more preferably between 80 and 250 nm.
  • the crosslinking components (B) may have thermally crosslinking groups.
  • Suitable thermal crosslinkers are, for example, crosslinkers based on epoxides in which two or more epoxy groups are linked to one another by means of a linking group.
  • Examples include low molecular weight compounds having two epoxy groups such as hexanediol diglycidyl ether, phthalic acid diglycidyl ether or cycloaliphatic compounds such as 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'-epoxycyclohexylmethyl ester.
  • Further examples of suitable crosslinkers include crosslinkers on of aminoplast resins, for example melamine-formaldehyde resins, urea-formaldehyde resins or tris (alkoxycarbonyl) triazines.
  • Blocked polyisocyanates are particularly preferably used as crosslinkers.
  • 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.
  • Blocking agents are described in D.A. Wicks, Z.W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001).
  • Suitable classes of compounds are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates. Preference is given to acetone oxime, butanone oxime, ⁇ -caprolactam, 3,5-dimethylpyrazole, diethyl malonate, phenol and tert-butylbenzylamine.
  • crosslinker is used separately, it is customary to use from 0.5 to 10% by weight, preferably from 1 to 8% by weight and more preferably from 2 to 6% by weight. Of course, mixtures of different crosslinkers can be used, provided that the properties of the layer are not adversely affected.
  • compositions of the invention may further comprise at least one component (C) selected from the group of finely divided fillers, pigments and dyes.
  • the finely divided filler is usually an inorganic filler.
  • Fillers and / or pigments may of course comprise an additional organic coating, for example for hydrophobing or hydrophilization.
  • the filler should not exceed an average particle size of 10 ⁇ m.
  • the average particle size is preferably 10 nm to 8 ⁇ m, more preferably 100 nm to 5 ⁇ m and, for example, 2 to 4 ⁇ m. In the case of round or approximately round particles, this information refers to the diameter, in the case of irregularly shaped particles, such as, for example, acicular particles, to the longest axis.
  • the particle size means the primary particle size. Of course, it will be apparent to those skilled in the art that finely divided solids often agglomerate into larger particles which must be dispersed intensively for use.
  • the particle size is selected by the skilled person depending on the desired properties of the layer.
  • the pigments may in particular be anti-corrosion pigments. They can be both active and passive anticorrosive pigments.
  • active anticorrosive pigments include, in particular, phosphates, phosphate-containing or modified phosphates, such as zinc phosphate-based pigments, zinc aluminum orthophosphate, zinc molybdenum orthophosphate, zinc aluminum molybdenum orthophosphate, calcium hydrogen phosphate, zinc calcium strontium orthophosphate silicate, zinc phosphite.
  • Other examples include combinations of inorganic phosphates with sparingly soluble electrochemically active organic corrosion inhibitors such as zinc phosphate modified with Zn or Ca salts of 5-nitroisophthalic acid.
  • typical organic anti-corrosive pigments such as, for example, Zn or Ca salts of 5-nitroisophthalic acid.
  • Passive anti-corrosive pigments extend the diffusion paths for corrosive components, thereby increasing corrosion resistance.
  • Examples include, in particular, flake-form or lamellar pigments, such as mica, hematite, phyllosilicates, linear polysilicates, such as WoI laston it, talc or metal flakes, such as aluminum or iron flakes.
  • the pigments may also be typical dye and / or effect pigment.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating. Effect pigments are known to the person skilled in the art. Examples include pure metal pigments such as aluminum, iron or copper pigments, interference pigments such as titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and F 2 ⁇ 3), metal oxide coated aluminum, or liquid crystal pigments. Color pigments are, in particular, customary organic or inorganic absorption pigments which can be used in the paint industry. Examples of organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • dyes examples include azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.
  • Fillers can be used to influence the properties of the coating, such as, for example, hardness, rheology or the orientation of the effect pigments. Fillers are often coloristically ineffective; i.e. they have a low intrinsic absorption and the refractive index is similar to the refractive index of the coating medium.
  • Examples of fillers include talc, calcium carbonate, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica, alumina, microspheres or hollow microspheres, e.g. made of glass, ceramic or polymers with sizes of, for example 0.1-10 microns.
  • any solid inert organic particles such as e.g. Urea-formaldehyde condensation products, micronized polyolefin wax or micronized amide wax.
  • the inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case.
  • the proportion of pigments and / or fillers in the polymer dispersion is preferably 15 to 40% by volume, more preferably 20 to 40% by volume and most preferably 20 to 35% by volume. The exact amount will be determined by the skilled person depending on the desired properties of the layer. When using conductivity pigments, the amounts used are usually greater than when using non-conductive fillers.
  • the specification of the pigment or filler fraction is here deviating from other data in% by volume as a measure of the pigment volume concentration (PVC) based on the bulk density of the pigment or filler and the volume of the polymer dispersion.
  • PVC pigment volume concentration
  • the pigment volume concentration is usually defined as the quotient of the total volume of the solid inorganic constituents (pigment and fillers) divided by the total volume of the solid inorganic constituents (pigments and fillers) and the polymer particles of the aqueous binder polymer dispersion; see Ullmanns Enzyklopadie der ischen Chemie, 4th edition, volume 15, p. 668). Of course, mixtures of different pigments can be used.
  • the pigments are usually used in an amount of 20 to 70% by weight. The exact amount will be determined by the skilled person depending on the desired properties of the layer. When using conductivity pigments, the amounts used are usually greater than when using non-conductive fillers.
  • Preferred amounts of conductive pigments and fillers are 40 to 70 wt.%, Preferred amounts of non-conductive pigments 20 to 50 wt.%.
  • Further preferred compounds (D) have 1 to 20 carbon atoms, the carbon atoms optionally contained in the radicals R 1 and R 2 not being included, preferably they have 2 to 20, particularly preferably 3 to 20, very particularly preferably 4 - 20, in particular 5 to 20 and especially 6 to 20 carbon atoms.
  • the compounds (D) preferred are those which have a solubility in n-butyl ether to ethylene glycol mono-(butyl glycol) at 23 0 C of at least 100 g / l.
  • R 1 and R 2 are independently of one another H or a linear or branched, optionally substituted alkyl radical having 1 to 20 C atoms , preferably 1 to 10 C-atoms and particularly preferably 1 to 6 C-atoms.
  • R 1 and R 2 may also be a cycloalkyl radical having 3 to 12 carbon atoms or aryl radical having 6 to 12 carbon atoms, wherein the radicals R 1 and R 2 together with the nitrogen atom form a five- to 12-membered ring.
  • Additional substituents may in particular be oxygen or nitrogen-containing substituents, for example OH groups or Nhfe groups.
  • radicals with at least 3 C atoms non-adjacent, non-terminal C atoms can be replaced by O and / or N atoms.
  • R 1 and R 2 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl and n-hexyl groups. It is preferable that at least one of R 1 and R 2 is H, and particularly preferably both are H.
  • the thioamide group is linked via the (n + 1) -valent hydrocarbon radical R 3 with n functional groups R 4 , where n stands for a natural number from 1 to 5.
  • n stands for a natural number from 1 to 5.
  • n is 1 to 3 and more preferably 1 or 2.
  • R 3 is preferably an (n + 1) -valent aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon radical having from 1 to 30 carbon atoms.
  • Atoms preferably 1 to 20 C-atoms and particularly preferably 1 to 10 C-atoms.
  • the hydrocarbon radical can optionally also be interrupted by heteroatoms, but it is preferably a pure hydrocarbon radical. It is obvious to the person skilled in the art that the values of n that are possible in principle also depend on the number of carbon atoms. As a rule, no more than one functional group per C atom of the hydrocarbon radical R 3 is present on average.
  • the thioamide group and n functional groups R 4 are bonded to the radical R 3 . These may be similar or different func- tional groups.
  • the functional groups R 4 may be, for example, ether groups, imino groups, keto groups, aldehyde groups, -OH, -NH 2 , -NHR 5 , -NR 5 R 5 ' , -COOH, -COOR 5 , -CONH 2 , -CONHR 5 , -CONR 5 R 5 ' , -NHCOR 5 , -NR 5 COR 5 , -NHCONHR 5 , -SH, -CN, -Si (OH) 3 , -SO 3 H, -PO (OH) 2 , -Si (OR 5 K -PO (OR 5 ) 2 or -PS (OR 5 ) 2 , where R 5 and R 5 ' independently of one another are an alkyl radical, preferably a straight-chain or branched alkyl radical having 1 to 6 , preferably 1 to 4 C atoms and very particularly preferably involves -CH 3. Also conceivable are quaternary or quaternized
  • Acidic groups may also be present, at least in part, as anions, and basic groups at least partially in protonated form.
  • functional groups R 4 are those groups which have only N and / or O atoms as heteroatoms.
  • groups include ether groups, imino groups, -OH, -NH 2 , -NHR 5 , -NR 5 R 5 ' , -COOH, -COOR 5 , -CONH 2 , -CONHR 5 , -CONR 5 R 5' , -NHCOR 5 , -NR 5 COR 5 , -NHCONHR 5 ,
  • the functional group is preferably ether groups, -OH and / or -NH 2 .
  • the radical R 3 is a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical.
  • the hydrocarbon radical can optionally also be interrupted by heteroatoms, but it is preferably a pure hydrocarbon radical.
  • Particularly noteworthy here are linear 1, ⁇ -alkylene radicals of the general formula - (CH 2 ) k-, where k stands for a natural number of 1 to 30, preferably 1 to 20 and particularly preferably 1 to 10. It may also be divalent aromatic radicals, such as 1, 4-phenylene, or substituted aromatic radicals of the general
  • Examples of such compounds include 2-hydroxythioacetamide, 3-hydroxythiopropionamide, 4-hydroxythiobutanamide, 5-hydroxythiopentanamide, 6-hydroxythiohexanamide, 7-hydroxythioheptanamide or 8-hydroxythiooctanamide, 9-hydroxythiononamide or 10-hydroxythiodecanamide.
  • R 11 can mean a linear or branched, optionally substituted alkyl radical having 1 to 20 C atoms, preferably 1 to 10 and particularly preferably 1 to 8 carbon atoms. Examples of these are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl , n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl and 2-ethylhexyl.
  • thioamides examples include the methyl, ethyl, iso-propyl, n-butyl, tert-butyl and 2-ethylhexyl ethers of 2-hydroxythioacetamide, 3-hydroxythiopropionamide, 4-hydroxythiobutanamide, 5-hydroxythiopentanamide, 6-hydroxythiohexanamide , 7-hydroxythioheptanamide, 8-hydroxythiooctanamide, 9-hydroxythiononamide and 10-hydroxythiodecanamide.
  • Vin is a vinyl group
  • Ph is a phenyl group
  • j can be from 1 to 250.
  • At least 50 mol%, preferably 70 mol% and particularly preferably 100 mol% of the radicals are ethylene oxide radicals.
  • the compounds may be low molecular weight, oligomeric or polymeric compounds.
  • the linking group R 6 is straight-chain or branched aliphatic, cycloaliphatic, aromatic and / or araliphatic hydrocarbon radicals in which non-adjacent C atoms are substituted by heteroatoms, in particular O and / or N atoms or functional groups or may be interrupted, and which may additionally also have functional groups. Additional functional groups may in particular be the groups R 4 defined above.
  • D 2 is low molecular weight compounds.
  • R 6 has 1 to 30 C atoms, preferably 2 to 20 C atoms and particularly preferably 2 to 10 C atoms, and in these compounds M has the value 2 to 6, preferably 2 to 4 and particularly preferably 2.
  • R 7 here stands for a divalent, linking group which comprises 1 to 30 C atoms.
  • R 7 is, in particular, linear 1, ⁇ -alkylene radicals of the general formula - (CH 2) k -, where k is a natural number of 1 to 30, preferably 2 to 20 and particularly preferably 2 to 8. It may also be divalent aromatic radicals, such as 1, 4-phenylene, or substituted aromatic radicals of the general formula - (CH 2 ) lc- (C 6 H 4 ) - or - (CH 2 ) K- (C 6 H 4 MCH 2 ) K "-, where k 'and k" independently of one another represent a natural number of 1 to 10, preferably 1 to 3.
  • Examples of such compounds D2 include malondithioamide, hexanedithioamide, 1,4-benzodithioamide or 1,2-benzodithioamide.
  • R 7 may furthermore preferably be radicals of the general formula - (CH 2 ) ⁇ -R 8 - (CH 2 ) ⁇ -, where R 8 is a divalent functional group, in particular a P-containing functional group.
  • R 8 is a divalent functional group, in particular a P-containing functional group.
  • examples of such groups include -OP (O) (OR 9 ) O-, -P (O) (OR 9 ) -, -P (S) (OR 9 ) -, -P (S) (SR 9 ) where R 9 is H, a monovalent metal ion or an alkyl radical, preferably a straight-chain or branched alkyl radical having 1 to 6 C atoms
  • (D2) is a polymer which comprises at least two terminal and / or pendant thioamide groups.
  • polymer includes oligomers and includes, in a known manner, high molecular weight compounds obtained from one or more monomers by polymerization, which may be substantially linear or branched polymers
  • the mass M n of the thioamido-containing polymers is usually 300 to 10 000 000 g / mol, preferably 500 to 1 000 000 g / mol, and more preferably 1000 to 100 000 g / mol.
  • the thioamide groups on the polymer can be end groups or they can be pendant groups. Side-chain thioamide groups can be attached directly to the polymer backbone, or they can also be linked to the polymer backbone via a spacer.
  • the polymers can be prepared by first preparing polymers containing nitrile groups and, after the polymerization, reacting the nitrile groups in a manner known in principle with hfeS to form thioamide groups. This is schematically shown below for a polymer having an acrylonitrile unit (scheme (I)).
  • Suitable comonomers include olefins, preferably vinylaromatic compounds such as styrene, ⁇ -methylstyrene or substituted styrenes, furthermore (meth) acrylic acid or (meth) acrylic esters such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl acrylate.
  • Preferred starting materials for carrying out the present invention are, for example, copolymers of styrene and acrylonitrile.
  • the reaction with the H2S can advantageously be carried out in the presence of a base. It can be made, for example, using a pressure apparatus and methanol as a solvent.
  • the degree of conversion can be determined for example by means of 13 C-NMR spectroscopy by comparing the intensity of the CN and CSNH2 signals and should generally be 20 to 100%, preferably 40 to 100%.
  • the compounds (D) can be used in purified form or in the form of educt-containing reaction mixtures, it being possible for the educt content to be up to 90%, preferably up to 75% or less.
  • copolymers of maleic anhydride and comonomers such as (meth) acrylic acid, (meth) crylates, vinyl ethers and / or olefins as starting material for modification have proven useful.
  • it may be styrene-maleic anhydride copolymers.
  • thioamides D1 and / or D2 can be used.
  • the person skilled in the art will make a certain selection of the theoretically possible thioamides, depending on the desired properties of the coating composition. It will be understood by those skilled in the art that not all types of thioamides D1 and / or D2 are equally well suited to all types of binder systems, solvent systems or surfaces.
  • the thioamides can be optimally adapted to specific systems. For example, more hydrophilic or rather hydrophobic compounds D1 and / or D2 can be prepared for targeted use in aqueous paint systems or organic paint systems.
  • the thioamides D1 and / or D2 used according to the invention in a mixture with other thioamides other than the above definition, other thiocarbonyl compounds or generally other anticorrosion agents, provided that no negative properties occur.
  • the proportion of the thioamides used according to the invention should be at least 50% by weight, preferably at least 75% by weight, relative to the total amount of all organic corrosion inhibitors used. Particular preference is given to using only thioamides D1 and / or D2.
  • the thioamides used according to the invention are usually used in an amount of 0.25 to 10% by weight, preferably 0.5 to 8% by weight and more preferably 1 to 6% by weight.
  • the preparation according to the invention generally comprises a suitable solvent in which the components are dissolved and / or dispersed in order to allow a uniform application to the surface. But it is also possible in principle to formulate the preparation solvent-free or substantially solvent-free as a powder coating. Preference is given to the use of a solvent.
  • Suitable solvents are those which are capable of dissolving, dispersing, suspending or emulsifying the compounds of the invention. These may be organic solvents, 5 to 25, preferably 5 to 20, more preferably 5 to 15%, ammonia solution in water or water. Of course, mixtures of different organic solvents or mixtures of organic solvents with water can be used. The person skilled in the art makes a suitable choice from the solvents which are possible in principle, depending on the intended use and on the nature of the compound according to the invention used.
  • organic solvents examples include hydrocarbons such as toluene, xylene or mixtures such as are obtained in refining crude oils such as hydrocarbon fractions of certain boiling ranges, ethers such as THF or polyethers such as polyethylene glycol, ether alcohols such as ethylene glycol mono-n-butyl ether (butyl glycol), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether or propylene glycol monomethyl ether, ether glycol acetates such as butyl glycol acetate or propylene glycol monomethyl ether acetate, ketones such as acetone, alcohols such as methanol, ethanol or propanol, or lactams such as N-methylpyrrolidone, N-ethylpyrrolidone, N- (n-butyl) pyrrolidone or N- cyclohexylpyrrolidone.
  • hydrocarbons such as toluene, xy
  • aromatic or aliphatic hydrocarbons or mixtures thereof examples are toluene or xylene.
  • aromatic hydrocarbon mixtures preferred are those which comprise predominantly aromatic C 7 - to Ci4-hydrocarbons substances include and may comprise a boiling range from 110 to 300 0 C, particularly preferably toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene , Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® brands of ExxonMobil Chemical especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C 9 and Cio-aromatics, boiling range about 154-178 0 C), 150 (boiling range about 182 - 207 0 C) and 200 (CAS no. 64742-94-5), as well as the Shellsol® brands of the company Shell.
  • Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 0 C or Crystal oil 60: CAS No. 64742-82-1.), White spirit (for example likewise CAS No. 64742-.
  • hydrocarbon mixtures 82-1 or solvent naphtha (light: boiling range about 155-180 0 C, heavy: boiling range about 225-300 0 C 1 ) commercially available.
  • the aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • preparations which comprise water or a predominantly aqueous solvent mixture. These are understood as meaning 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 butyl glycol or methoxypropanol.
  • the amount of solvent is chosen by the skilled person depending on the desired properties of the preparation and the desired application method.
  • the weight ratio of the layer components to the solvent is 10: 1 to 1:10, preferably about 2: 1, without the invention being restricted thereto. It is of course also possible to first produce a concentrate and dilute it to the desired concentration on site.
  • the preparation is prepared by thoroughly mixing the components of the preparation with the solvents.
  • the person skilled in the art is familiar with suitable mixing or dispersing aggregates.
  • the preparation may additionally comprise one or more auxiliaries and / or additives (F).
  • auxiliaries and / or additives are used for fine control of the properties of the layer. As a rule, their amount 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 pigments and / or effect pigments, reactive thinners for thermal curing, rheological aids, UV absorbers, light stabilizers, free-radical scavengers, initiators for free-radical polymerization, catalysts for thermal crosslinking, slip additives, polymerization inhibitors, defoamers, Emulsifiers, degassing agents, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming auxiliaries, rheology-controlling additives (thickeners), flame retardants Protective agents, siccatives, skin preventatives, other corrosion inhibitors, waxes and matting agents, as described in the textbook "Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or the German patent application DE 199 14 896 A1, column 13, Line 56 until column 15, line 54, are known.
  • Preferred additives are dibutyltin dilaurate as a thermal crosslinking catalyst.
  • coating compositions are composed as follows:
  • Another object of the present invention is a mixture consisting of
  • At least one dispersed binder (A), at least one compound (D) containing at least one thioamide group (- (C S) -NR 1 R 2 ), and
  • a binder present in water dispersed (A) with at least one compound (D) containing at least one thioamide group (- (C S) -NR 1 R 2 ), and mixed - It is only after completion of the mixing of components (A) and (D), the mixture thus obtained with at least one pigment and / or filler added.
  • the advantage of this preparation process is that the compounds (D) which inhibit corrosion are not deactivated by absorption onto pigments and / or fillers, so that the coating compositions thus obtained have a higher corrosion protection effect.
  • the metallic surface is treated with the preparation.
  • the upper limit for the total layer thickness i. the thickness of all applied anticorrosive layers together is 2 mm, preferably less than 1.5 mm, more preferably less than 1 mm, very preferably less than 800 ⁇ m and in particular less than 500 ⁇ m.
  • the application of the paints of the invention can in any way, for. B. done by brushing or spraying.
  • the curing method depends on the nature of the crosslinker and is usually carried out under atmospheric conditions.
  • the temperature required for curing depends in particular on the crosslinker used. Very reactive crosslinkers can be cured at lower temperatures than less reactive crosslinkers.
  • the coating containing at least one thioamide (D) has a layer thickness after drying of at least 40 .mu.m, preferably at least 50 .mu.m, more preferably at least 60 .mu.m and most preferably at least 80 ⁇ m and a layer thickness of up to 2 mm, preferably less than 1.5 mm, more preferably less than ger than 1 mm, most preferably less than 800 microns and especially less than 500 microns, wherein the coating composition after application to the surface under normal ambient conditions, ie at ambient or at room temperature, in the presence of air and conventional humidity without the Use of additional equipment or facilities to cure.
  • Typical curing temperatures depending on the environment more than 0 to 40 0 C, preferably 5 to 35 ° C, particularly preferably 10 to 30 0 C and most preferably 15 to 25 ° C in the presence of air and usual humidity.
  • the relative humidity can be arbitrary, preferably it is between 10 and 80% and more preferably between 30 and 70%. It will be apparent to those skilled in the art that the time to complete cure of one and the same binder system may vary depending on the actual environmental conditions.
  • the dispersions and preparations according to the invention are particularly preferably used in anticorrosion agents which are used in categories C2 (according to DIN EN ISO 12944) or higher, preferably in corrosivity categories C3 or higher and more preferably in corrosivity categories C4 or higher.
  • the corrosivity categories according to DIN EN ISO 12944 are defined as follows for unalloyed steel or for zinc based on the area-related mass loss or on the thickness decrease after the first year of removal:
  • Zinc mass loss> 0.7 - 5 g / m 2 thickness decrease> 0.1 - 0.7 ⁇ m
  • Zinc mass loss> 5 - 15 g / m 2 thickness decrease> 0.7 - 2.1 ⁇ m
  • Zinc mass loss> 15 - 30 g / m 2 thickness decrease> 2.1 - 4.2 ⁇ m
  • Zinc mass loss> 30 - 60 g / m 2 thickness decrease> 4.2 - 8.4 ⁇ m
  • the performance test data for atmospheric corrosion protection de wur- an anticorrosive formulation based on a commercial aqueous styrenesulfonic rol-acrylate dispersion for paints (Acronal ® Optive 410, Fa. BASF Corp.) are used.
  • the dispersion used has the following properties:
  • styrene-acrylate dispersion 393.4 g of the styrene-acrylate dispersion were added 2.2 g of a commercial defoamer for coating materials (mixture of polysiloxanes and hydrophobic solids in polyglycol;. BYK ® 022, Byk) was added, followed by means of a Disperma- th a mixture consisting of 0.6 g of an anionic dispersing agent (acidic organophosphate a fatty alcohol alkoxylate;. Lutensit ® a-EP from BASF AG), 11, 0 g conc. Ammonia and 58.6 g of water were added.
  • an anionic dispersing agent acidic organophosphate a fatty alcohol alkoxylate
  • Lutensit ® a-EP from BASF AG
  • talc 20 M 2 from Luzenac
  • a filler based on barium sulfate and zinc sulfide g Litopone ® L
  • the primers to be tested were diluted with demineralized water to the desired viscosity (300 to 1000 mPas (ICI Rotothinner Ball)) and mounted on a cleaned, non-galvanized steel sheet (200 x 80 x 0.9 mm) with a box doctor blade;
  • the gap size is chosen so that there is a dry film thickness of 60-85 microns.
  • test sheet After six days of drying at room temperature and a one-day heat treatment at 50 ° C., the reverse side of the test sheet was coated with a solvent-based coating to protect against corrosion and the edges were taped with Tesa® film.
  • test sheet on the side coated with the primer to be tested was scribed with a scribe sting to the substrate.
  • test panels were subjected to a salt spray test in accordance with DIN EN ISO 7253 (test duration 240 h).
  • the sheets are shown in Figure 1 (left Comparative Example 1, middle Example 1, right Example 1 repetition).
  • Example 1 is much less corroded than Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne l'utilisation de matières de revêtement qui contiennent au moins un composé (D) présentant au moins un groupe thioamide (-(C=S)-NR<SUP>1</SUP>R<SUP>2</SUP>) dans le domaine de la protection contre la corrosion atmosphérique.
EP06707850A 2005-01-28 2006-01-26 Revetements anticorrosion contenant des groupes thioamide Withdrawn EP1844114A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE200510004292 DE102005004292A1 (de) 2005-01-28 2005-01-28 Verfahren zum Aufbringen integrierter Vorbehandlungsschichten umfassend Thioamide auf metallische Oberflächen
DE200510061317 DE102005061317A1 (de) 2005-12-20 2005-12-20 Verfahren zum Aufbringen von Dicarbonsäure-Olefin-Copolymere enthaltenden, integrierten Vorbehandlungsschichten auf metallische Oberflächen
DE200510061319 DE102005061319A1 (de) 2005-12-20 2005-12-20 Verfahren zum Aufbringen von Korrosionsschutzschichten umfassend Thioamide auf metallische Oberflächen
DE102005061320A DE102005061320A1 (de) 2005-12-20 2005-12-20 Copolymer umfassend Derivate monoethylenisch ungesättigter Dicarbonsäuren
DE200510061318 DE102005061318A1 (de) 2005-12-20 2005-12-20 Zubereitung und Verfahren zum Aufbringen von Korrosionsschutzschichten
PCT/EP2006/050462 WO2006079643A1 (fr) 2005-01-28 2006-01-26 Revetements anticorrosion contenant des groupes thioamide

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EP1844114A1 true EP1844114A1 (fr) 2007-10-17

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EP (1) EP1844114A1 (fr)
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DE102011056761A1 (de) 2011-12-21 2013-08-08 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Pigmentiertes, feinstrukturiertes tribologisches Kompositmaterial
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US20090156736A1 (en) 2009-06-18
US7981954B2 (en) 2011-07-19
WO2006079643A1 (fr) 2006-08-03
KR101342836B1 (ko) 2013-12-17

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