EP3416754A1 - Procédé de production d'une peinture multicouche - Google Patents

Procédé de production d'une peinture multicouche

Info

Publication number
EP3416754A1
EP3416754A1 EP16705526.8A EP16705526A EP3416754A1 EP 3416754 A1 EP3416754 A1 EP 3416754A1 EP 16705526 A EP16705526 A EP 16705526A EP 3416754 A1 EP3416754 A1 EP 3416754A1
Authority
EP
European Patent Office
Prior art keywords
basecoat
basecoats
weight
wbl
coating
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Withdrawn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
EP16705526.8A
Other languages
German (de)
English (en)
Inventor
Cathrin CORTEN
Dirk EIERHOFF
Patrick WILM
Klaus-Juergen KANNGIESSER
Joerg Schwarz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP3416754A1 publication Critical patent/EP3416754A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4423—Polyesters, esterified polyepoxides
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4461—Polyamides; Polyimides
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4465—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2505/00—Polyamides

Definitions

  • the present invention relates to a process for producing a multicoat paint system in which a basecoat film or several directly successive basecoat films are produced directly on a metallic substrate coated with a cured electrocoating, a clearcoat film is produced directly on one or the uppermost of the multiple basecoat films, and then the one or more basecoat films and the clearcoat film are cured together.
  • the present invention relates to a multi-layer coating, which was prepared by the process according to the invention.
  • Multicoat paint systems on metallic substrates for example multicoat paint systems in the automotive industry, are known.
  • such multicoat paint systems when viewed from the metallic substrate, comprise an electrodeposition coating layer, a layer applied directly to the electrodeposition coating layer, usually referred to as surfacer layer, at least one layer containing color and / or effect pigments and usually referred to as basecoat layer and a clearcoat layer.
  • the electrophoretically applied electrodeposition coating layer basically serves to protect the substrate from corrosion.
  • the surfacer layer serves primarily to protect against mechanical stress, such as, for example, falling rocks, and also to fill in unevennesses in the substrate.
  • the next layer, referred to as the basecoat layer is primarily responsible for the production of aesthetic properties such as color and / or effects such as the flop, while the subsequent clearcoat layer then serves in particular the scratch resistance and the gloss of the multi-layer coating.
  • an electrodeposition paint in particular a cathodic electrodeposition paint
  • the metallic substrate can be pretreated differently prior to the deposition of the electrodeposition coating, for example, known conversion coatings such as phosphate coatings, in particular zinc phosphate coatings, can be applied.
  • the deposition process of the electrocoating generally takes place in corresponding electrocoating pools. After application, the coated substrate is removed from the basin, optionally rinsed and flashed and / or intermediately dried, and finally the applied electrodeposition paint is cured. In this case, layer thicknesses of about 15 to 25 micrometers are desired.
  • the so-called filler is applied directly to the cured electrodeposition coating layer, optionally flashed off and / or intermediately dried and then cured.
  • layer thicknesses of, for example, 25 to 45 micrometers are desired.
  • a so-called basecoat containing color and / or effect pigments is then applied, optionally flashed off and / or intermediately dried, and a clearcoat applied directly to the basecoat film thus prepared without separate curing.
  • the basecoat film and optionally also previously flashed and / or intermediately dried clearcoat film are cured together (wet-in-wet process).
  • the cured basecoat film generally has comparatively small layer thicknesses of, for example, 10 to 20 micrometers, layer thicknesses of, for example, 30 to 60 micrometers are desired for the cured clearcoat film in order to achieve the application-technological properties described.
  • the application of filler, basecoat and clearcoat can be carried out, for example, via the application methods of pneumatic and / or electrostatic spray application known to those skilled in the art. Filler and basecoat are now increasingly used for environmental reasons as aqueous coating materials.
  • this coating layer which is not separately cured, is then often referred to as the basecoat film (and no longer as the filler film) or, in contrast to a second basecoat film applied thereto, is referred to as the first basecoat film.
  • the omission of a separate curing step of the coating agent applied directly to the electrodeposition coating layer is very advantageous from an ecological and economical point of view. Because this leads to energy savings and the entire manufacturing process can of course be much more stringent.
  • the coating layer produced directly on the electrodeposition coating layer is flashed off only at room temperature and / or intermediately dried at elevated temperatures, without curing, which is known to require regularly increased curing temperatures and / or long curing times.
  • EP 0 877 063 A2 discloses aqueous coating compositions which contain a polyamide, usually employed in aqueous compositions, as a rheology aid, which, owing to its intended use in aqueous systems, is distinguished by a comparatively high acid number of usually greater than 30 mg KOH / g.
  • Aqueous coating compositions which have such polyamides with a comparatively high acid number usually used in aqueous compositions are furthermore known from WO 2009/100938 A1 and EP 2 457 961 A1.
  • a disadvantage of the presence of such a polyamide as a rheology aid in aqueous coating compositions is in particular the occurrence of specks in the processing of a corresponding aqueous coating agent in a method as described above.
  • aqueous coating compositions containing a metal silicate commonly used as a rheology aid in aqueous coating compositions such as the commercially available metal silicate "Laponite® RD.”
  • the disadvantage here is the increased occurrence of pinholes and / or poor processing during processing by means of the above described method.
  • aqueous coating compositions which contain a polyamide as sole rheology aid.
  • the polyamide is added in the preparation of the compositions as such, that is, in particular not in the form of a mixture with other components.
  • polyamides with lower acid numbers per se as rheology aids is known in principle, however, such polyamides are generally used in the prior art in solvent-based (based on organic solvents) coating compositions.
  • An advantage would therefore be a process for the production of multicoat paint systems in which a separate curing step as described above for the coating agent applied directly to the electrodeposition coating can be dispensed with and the multicoat paint system produced nevertheless has excellent application-technological, in particular aesthetic properties. Exactly this task is the present invention.
  • the present invention is a multi-layer coating, which was prepared by the method according to the invention.
  • the inventive method allows the production of multi-layer coatings waiving a separate curing step of the coating layer produced directly on the electrodeposition coating layer.
  • this coating layer is referred to in the context of the present invention as a basecoat film.
  • this basecoat film is cured together with optionally further basecoat films below the clearcoat film and the clearcoat film together. Nevertheless, result from the application of the method according to the invention multi-layer coatings, which have excellent application technology, in particular aesthetic properties.
  • the application of a coating agent to a substrate or the production of a coating layer on a substrate are as follows.
  • the respective coating agent is applied such that the coating layer produced therefrom is arranged on the substrate, but does not necessarily have to be in direct contact with the substrate.
  • other layers may be arranged between the coating layer and the substrate.
  • the cured electrodeposition coating layer (E.1) is formed on the metallic substrate (S), but between the substrate and the substrate
  • Electrocoating layer may be arranged as described below conversion coating such as zinc phosphating.
  • the same principle applies to the application of a coating agent (b) to a coating layer (A) produced by means of another coating agent (a) or to the production of a coating layer (B) on another coating layer (A).
  • the coating layer (B) does not necessarily have to be in contact with the coating layer (A), it merely has to be arranged above it, that is to say on the side of the coating layer (A) facing away from the substrate.
  • applying a coating agent directly to a substrate or producing a coating layer directly on a substrate is understood as follows.
  • the respective coating agent is applied such that the coating layer produced therefrom is arranged on the substrate and is in direct contact with the substrate. In particular, no other layer is arranged between the coating layer and the substrate.
  • flash drying, intermediate drying and hardening are to be understood as meaning the term contents familiar to the person skilled in the art in connection with processes for producing multicoat paint systems.
  • bleeding is basically understood to mean the evaporation or evaporation of organic solvents and / or water of a coating agent applied during the production of a coating at usually ambient temperature (ie room temperature), for example 15 to 35 ° C. for a period of for example, 0.5 to 30 minutes.
  • ambient temperature ie room temperature
  • organic solvents and / or water which are contained in the applied coating agent evaporate.
  • the coating material since the coating material is still flowable directly after application and at the beginning of venting, it can run during the venting process.
  • At least one applied by spray application coating agent is usually applied droplet-shaped and not in a homogeneous thickness. However, it is flowable by the organic solvents contained and / or water and can thus form a homogeneous, smooth coating film by the bleeding. At the same time, organic solvents and / or water evaporate successively, so that after the ablation phase, a comparatively smooth coating layer has formed, which contains less water and / or solvent compared to the applied coating composition. However, the coating layer is not yet ready for use after it has been flashed off. It is, for example, no longer flowable, but still soft or sticky, possibly only dried. In particular, the coating layer is not yet cured as described below.
  • Intermediate drying is therefore also understood to mean the evaporation or evaporation of organic solvents and / or water of a coating agent applied during the production of a coating, usually at a temperature of, for example, 40 to 90 ° C., higher than the ambient temperature, for a duration of, for example, 1 to 60 min. Even with intermediate drying, the applied coating agent will thus lose a proportion of organic solvents and / or water. With respect to a particular coating agent is generally considered that the intermediate drying in comparison to bleeding at, for example, higher temperatures and / or for a longer period of time is done, so compared to bleeding and a higher proportion of organic solvents and / or water from the escaped coating layer escapes.
  • the coating agent can already be crosslinked or intertwined with one another as a binder as described below.
  • a proportion of the polymers contained in the coating agent can already be crosslinked or intertwined with one another as a binder as described below.
  • no ready-to-use coating layer is obtained, as is the case with the curing described below.
  • curing is clearly differentiated from flash off and intermediate drying.
  • hardening of a coating layer is understood to mean the transfer of such a layer into the ready-to-use state, that is to say into a state in which the substrate equipped with the respective coating layer can be transported, stored and used as intended.
  • a cured coating layer is thus no longer particularly soft or sticky, but conditioned as a solid coating film, which no longer substantially changes its properties such as hardness or adhesion to the substrate even upon further exposure to curing conditions as described below.
  • coating compositions can basically be cured physically and / or chemically, depending on the constituents contained, such as binders and crosslinking agents.
  • thermal-chemical curing and actinic-chemical hardening may be considered.
  • a coating composition may, for example if it is thermally-chemically curable, be self-crosslinking and / or externally-crosslinking.
  • This coating agent contains polymers (also called polymers) as a binder and optionally crosslinking agents, which can crosslink together accordingly.
  • polymers also called polymers
  • “physically curable” or the term “physical curing” means the formation of a cured coating layer by release of solvent from polymer solutions or polymer dispersions, the curing being achieved by entanglement of polymer chains.
  • Such coating compositions are generally formulated as one-component coating compositions.
  • thermally-chemically curable or the term “thermal-chemical curing” means the crosslinking of a lacquer layer initiated by chemical reaction of reactive functional groups (formation of a hardened coating layer), the energetic activation of this chemical reaction by thermal energy is possible.
  • different functional groups which are complementary to one another can react with one another (complementary functional groups) and / or the formation of the hardened layer is based on the reaction of autoreactive groups, that is to say functional groups which react with each other with groups of their type.
  • suitable complementary reactive functional groups and autoreactive functional groups are known, for example, from German Patent Application DE 199 30 665 A1, page 7, line 28, to page 9, line 24.
  • This crosslinking can be a self-crosslinking and / or an external crosslinking. If, for example, the complementary reactive functional groups are already present in an organic polymer used as a binder, for example a polyester, a polyurethane or a poly (meth) acrylate, self-crosslinking is present.
  • An external crosslinking is present, for example, when a (first) organic polymer containing certain functional groups, for example hydroxyl groups, with a known crosslinking agent, for example a polyisocyanate and / or a melamine resin, responding.
  • the crosslinking agent thus contains reactive functional groups which are complementary to the reactive functional groups present in the (first) organic polymer used as binder.
  • the components to be crosslinked for example organic polymers as binders and crosslinking agents, are present next to one another, that is to say in one component.
  • the prerequisite for this is that the components to be crosslinked only react effectively with one another at elevated temperatures of, for example, above 100 ° C., that is, undergo curing reactions. Otherwise, the components to be crosslinked would have to be stored separately from one another and mixed with one another shortly before application to a substrate, in order to avoid premature, at least proportional, thermochemical curing (compare two-component systems).
  • hydroxy-functional polyesters and / or polyurethanes with melamine resins and / or blocked polyisocyanates may be mentioned as crosslinking agents.
  • the components to be crosslinked for example the organic polymers as binders and the crosslinking agents, are present separately from one another in at least two components which are combined only shortly before application.
  • This shape is selected when the components to be crosslinked are effectively reacting at ambient temperatures or slightly elevated temperatures of, for example, 40 to 90 ° C.
  • hydroxy-functional polyesters and / or polyurethanes and / or poly (meth) acrylates with free polyisocyanates as crosslinking agents may be mentioned.
  • an organic polymer has as binder both self-crosslinking and externally crosslinking functional groups and then combined with crosslinking agents.
  • actinic-chemical hardening or the term “actinic-chemical curing” is to be understood as meaning the hardening using actinic radiation, namely electromagnetic radiation such as near infrared (NIR) and UV radiation, in particular UV radiation, as well as corpuscular radiation such as electron radiation for curing is possible.
  • UV radiation is usually initiated by free-radical or cationic photoinitiators.
  • Typical actinically curable functional groups are carbon-carbon double bonds, which usually radical photoinitiators are used. The actinic hardening is therefore also based on a chemical crosslinking.
  • curing is effected by different mechanisms, which of course also make different conditions necessary during the curing, in particular different curing temperatures and curing times.
  • curing preferably takes place between 15 and 90 ° C. over a period of 2 to 48 hours.
  • the curing of flash-off and / or intermediate drying thus differs possibly only by the duration of the conditioning of the coating layer.
  • a differentiation between flash off and intermediate drying is also not useful. It would be possible, for example, first to ventilate or temporarily dry a coating layer produced by applying a physically curable coating composition at 15 to 35 ° C. for a period of, for example, 0.5 to 30 minutes and then to cure at 50 ° C. for a period of 5 hours.
  • the coating materials to be used in the process according to the invention are preferably thermally-chemically curable, more preferably thermally-chemically curable and externally crosslinking.
  • the curing of thermally-chemically curable one-component systems preferably takes place at temperatures of 100 to 250 ° C., preferably 100 to 180 ° C. for a period of 5 to 60 minutes, preferably 10 to 45 min is carried out, since these conditions are usually necessary to convert the coating layer by chemical crosslinking reactions in a cured coating layer. Accordingly, a pre-cure buffing and / or intermediate drying phase occurs at lower temperatures and / or for shorter times.
  • it may be flashed off at 15 to 35 ° C for a period of, for example, 0.5 to 30 minutes, and / or intermediately dried at a temperature of, for example, 40 to 90 ° C for a period of, for example, 1 to 60 minutes.
  • the curing of thermally-chemically curable two-component systems at temperatures of for example 15 to 90 ° C, in particular 40 to 90 ° C for a period of 5 to 80 minutes, preferably 10 to 50 min can be performed.
  • a pre-cure buffing and / or intermediate drying phase occurs at lower temperatures and / or for shorter times.
  • a pre-curing or intermediate drying phase can, for example, take place at 15 to 35 ° C. for a period of, for example, 0.5 to 30 minutes, but at any rate at lower temperatures and / or for shorter times than the subsequent curing.
  • a thermally-chemically curable two-component system is cured at higher temperatures.
  • a basecoat film or several basecoat films together with a clearcoat cured are present within the layers, for example a one-component basecoat and a two-component clearcoat, the joint curing is of course determined by the curing conditions necessary for the one-component system.
  • a multicoat system is built up on a metallic substrate (S).
  • Substrates containing or consisting of, for example, iron, aluminum, copper, zinc, magnesium and their alloys, as well as steel in a wide variety of shapes and compositions are generally suitable as metallic substrates (S).
  • S metallic substrates
  • Preferred are iron and steel substrates, for example typical iron and steel substrates as used in the automotive industry.
  • the substrates can be shaped as desired, that is, it can be, for example, simple sheets or even complex components such as in particular car bodies and parts thereof.
  • the metallic substrates (S) can be pretreated prior to stage (1) of the process according to the invention in a manner known per se, that is to say for example purified and / or provided with known conversion coatings.
  • a cleaning can be done mechanically, for example by means of wiping, grinding and / or polishing and / or chemically by pickling by etching in acid or alkali baths, for example by means of hydrochloric or sulfuric acid.
  • the cleaning with organic solvents or aqueous cleaners is of course possible.
  • Pretreatment by application of conversion coatings, in particular by means of phosphating and / or chromating, preferably phosphating, can also take place.
  • the metallic substrates are preferably conversion-coated, in particular phosphated, preferably provided with a zinc phosphating.
  • a hardened electrodeposition coating layer (E.1) is applied to the metallic substrate (S) by electrophoretic application of an electrodeposition paint (e.1) to the substrate (S) and subsequent curing of the electrodeposition paint (e.1). produced.
  • the electrodeposition paint (e.1) used in step (1) of the process according to the invention may be a cathodic or anodic electrodeposition paint. It is preferably a cathodic electrodeposition paint.
  • Electrocoating paints have long been known to the skilled person. These are aqueous coating materials which must be capable of being electrophoretically applied to a metallic substrate. In any case, they contain anionic or cationic polymers as binders. These polymers contain functional groups that are potentially anionic, that is, that can be converted into anionic groups, for example, carboxylic acid groups, or functional groups that are potentially cationic, that is, that can be converted into cationic groups, for example, amino groups.
  • the conversion into charged groups is usually achieved by the use of appropriate neutralizing agents (organic amines (anionic), organic carboxylic acids such as formic acid (cationic)), which then produce the anionic or cationic polymers.
  • the electrocoating paints contain typical anti-corrosive pigments.
  • the cathodic electrodeposition paints preferred in the context of the invention preferably contain cationic polymers as binders, in particular hydroxy-functional polyetheramines, which preferably have aromatic structural units.
  • Such polymers are generally obtained by reacting corresponding bisphenol-based epoxy resins with amines such as mono- and dialkylamines, alkanolamines and / or dialkylaminoalkylamines.
  • the electrodeposition coating (e.1) is therefore preferably a chemically-thermally curable coating composition, in which case it is in particular externally crosslinking.
  • the electrocoat material (e.1) is preferably a thermally-chemically curable one-component coating composition.
  • the electrocoating (e.1) contains a hydroxy-functional epoxy resin as a binder and a fully blocked polyisocyanate as a crosslinking agent.
  • the epoxy resin is preferably cathodic, in particular containing amino groups.
  • the electrophoretic application of such an electrocoating paint (e.1) taking place within the scope of step (1) of the method according to the invention is also known.
  • the application is electrophoretically. That is, to be coated metallic workpiece is first dipped in a dip containing the paint and an electric DC field is applied between the metallic workpiece and a counter electrode.
  • the workpiece acts as an electrode which migrates non-volatile constituents of the electrodeposition paint due to the described charge of the polymers used as binders through the electric field to the substrate and deposit on the substrate, whereby an electrodeposition coating layer is formed.
  • the substrate is thus connected as a cathode, where the hydroxide ions formed there by the electrolysis of water neutralize the cationic binder, so that it is deposited on the substrate and forms an electrodeposition coating. It is then an application by the electrophoretic dipping method.
  • the coated substrate (S) is removed from the basin, optionally rinsed with, for example, water-based rinsing solutions, then optionally aerated and / or intermediately dried, and finally the applied electrodeposition coating is cured.
  • the applied electrodeposition paint (e.1) (or the applied, not yet cured electrodeposition coating) is, for example, at 15 to 35 ° C for a period of, for example, 0.5 to 30 minutes and / or at a temperature of preferably 40 to 90 ° C for a period of, for example, 1 to 60 minutes between dried.
  • the applied to the substrate electrodeposition coating (e.1) is preferably at temperatures of 100 to 250 ° C, preferably 140 to 220 ° C for a period of 5 to 60 minutes, preferably 10 bis Cured for 45 minutes, whereby the cured electrodeposition coating layer (E.1) is produced.
  • the electrodeposition coating (e.1) is a chemically-thermally curable one-component coating composition as described above.
  • the electrodeposition coating is a curable coating agent in other ways and / or other Abllust-, embrocknungs- and curing conditions are used.
  • the layer thickness of the cured electrodeposition coating layer is, for example, 10 to 40 micrometers, preferably 15 to 25 micrometers. All layer thicknesses specified in the context of the present invention are understood as dry layer thicknesses. It is therefore the layer thickness of the respective cured layer. If, therefore, it is stated that a lacquer is applied in a certain layer thickness, it is to be understood that the lacquer is applied in such a way that the said layer thickness results after hardening.
  • step (2) of the process according to the invention (2.1) a basecoat film (B.2.1) is prepared or (2.2) there are several directly successive Basecoat layers (B.2.2.x) produced.
  • the layers are produced by applying (2.1) an aqueous basecoat material (also called aqueous basecoat) (b.2.1) directly to the cured electrodeposition coating layer (E.1) or (2.2) applying several basecoats in succession (b.2.2.x). on the cured electrodeposition coating (E.1).
  • the directly successive application of several basecoats (b.2.2.x) to the cured electrodeposition coating layer (E.1) is thus understood to mean that first a first basecoat is applied directly to the electrodeposition coat and then a second basecoat is applied directly to the layer of the first base coat is applied. An optionally third basecoat is then applied directly to the layer of the second basecoat. This process can then be repeated analogously for further basecoats (ie a fourth, fifth, etc. basecoat).
  • the basecoat film (B.2.1) or the first basecoat film (B.2.2.x) is thus arranged directly on the cured electrodeposition coating (E.1) after production.
  • basecoat and basecoat film in relation to the coating agents and coating layers applied in step (2) of the process of the invention are used for the sake of clarity.
  • the basecoat films (B.2.1) and (B.2.2.x) are not cured separately, but cured together with the clearcoat. Curing thus takes place analogously to the curing of so-called basecoats used in the standard method described in the introduction.
  • the coating compositions used in stage (2) of the process according to the invention are not hardened separately, as are the coating compositions designated as fillers in the standard process.
  • the aqueous basecoat (b.2.1) used in step (2.1) is described in detail below. In a first preferred embodiment, however, it is at least chemically-thermally curable, particularly preferably externally crosslinking.
  • the basecoat (b.2.1) is preferably a one-component coating agent.
  • the basecoat material (b.2.1) preferably contains a combination of at least one hydroxyl-functional polymer as binder selected from the group consisting of polyacrylates, polyurethanes, polyesters and copolymers of the abovementioned Polymers, for example polyurethane polyacrylates, and at least one melamine resin as a crosslinking agent.
  • basecoats which only small amounts of less than 5 wt .-%, preferably less than 2.5 wt .-%, based on the Total weight of the basecoat, on crosslinking agents such as melamine resins in particular.
  • crosslinking agents such as melamine resins
  • no crosslinking agents are included.
  • An advantage of the non-use of crosslinking agents and the consequently lower complexity of the paint lies in the increase of formulation freedom for the basecoat. Also storage stability may be better due to the avoidance of possible reactions of the reactive components.
  • the basecoat (b.2.1) can be applied by the methods known to those skilled in the art for the application of liquid coating compositions, for example by dipping, knife coating, spraying, rolling or the like.
  • spray application methods are used, such as compressed air spraying (pneumatic application), airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air (hot spraying).
  • the basecoat (b.2.1) is applied via the pneumatic spray application or the electrostatic spray application.
  • the application of the basecoat (b.2.1) thus produces a basecoat film (B.2.1), ie a layer of the basecoat (b.2.1) applied directly to the electrodeposition coating (E.1).
  • the applied basecoat (b.2.1) or the corresponding basecoat film (B.2.1) is flashed off after application, for example, at 15 to 35 ° C for a period of, for example, 0.5 to 30 minutes and / or at a temperature of preferably 40 to 90 ° C for a period of, for example, 1 to 60 minutes between dried. Preference is first vented at 15 to 35 ° C for a period of 0.5 to 30 min and then inter-dried at 40 to 90 ° C for a period of, for example, 1 to 60 min.
  • the described Abllust- and Intermediate drying conditions apply in particular to the preferred case that the basecoat (b.2.1) is a chemically-thermally curable one-component coating composition. However, this does not exclude that the basecoat (b.2.1) is a curable coating material in other ways and / or other ablating and / or intermediate drying conditions are used.
  • the basecoat film (B.2.1) is not cured within step (2) of the process according to the invention, that is preferably not exposed to temperatures above 100 ° C. for a period of more than 1 minute, especially preferably not at temperatures above 100 ° C. exposed. This results clearly and directly from the below described step (4) of the method according to the invention. Since the basecoat film is only cured in stage (4), it can not be cured in stage (2), because then curing in stage (4) would no longer be possible.
  • aqueous basecoats (b.2.2.x) used in step (2.2) of the process according to the invention are also described in detail below.
  • at least one of the basecoats used in step (2.2) is in any case chemically-thermally curable, in particular preferably externally crosslinking. Again, this applies to all basecoats (b.2.2.x).
  • at least one basecoat (b.2.2.x) is preferably a one-component coating composition, and this is more preferably the case for all basecoats (b.2.2.x).
  • At least one of the basecoats (b.2.2.x) preferably contains a combination of at least one hydroxy-functional polymer as binder selected from the group consisting of polyacrylates, polyurethanes, polyesters and copolymers of said polymers, for example polyurethane polyacrylates, and at least one melamine resin crosslinking agent. Again, this applies to all basecoats (b.2.2.x).
  • At least one basecoat (b.2.2.x) which only contains small amounts of less than 5% by weight, preferably less than 2.5% by weight. based on the total weight of the basecoat, on crosslinking agents such as in particular melamine resins. Again preferred in this embodiment is that no crosslinking agents are included.
  • the basecoats (b.2.2.x) can be applied by the methods known to those skilled in the art for the application of liquid coating compositions, for example by dipping, knife coating, spraying, rolling or the like.
  • spray application methods are used, such as compressed air spraying (pneumatic application), airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air (hot spraying).
  • the basecoats (b.2.2.x) are applied via the pneumatic spray application and / or the electrostatic spray application.
  • the basecoats and basecoats are generally characterized by (b.2.2.x) and (B.2.2.x), while in naming the specific individual basecoats and basecoats, the x can be replaced by correspondingly appropriate other letters.
  • the first basecoat and the first basecoat film can be labeled a, the topmost basecoat and the topmost basecoat film can be labeled z. These two basecoats or basecoats are present in the stage (2.2) in any case.
  • Optionally interposed layers may be consecutively labeled b, c, d and so on.
  • a basecoat film (B.2.2.a) is thus produced directly on the cured electrodeposition paint film (E.1).
  • the at least one further basecoat film (B.2.2.x) is then prepared directly on the basecoat film (B.2.2.a). If several further basecoat films (B.2.2.x) are produced, these are prepared directly in succession. For example, exactly one more base coat layer (B.2.2.x) can be produced, which then directly in the finally produced multicoat paint system is arranged below the clearcoat layer (K) and thus can be referred to as basecoat film (B.2.2.Z) (see also Figure 2).
  • the basecoats (b.2.2.x) can be identical or different. It is also possible to produce several basecoat films (B.2.2.x) with the same basecoat and one or more further basecoat films (B.2.2.x) with one or more other basecoats.
  • the applied basecoats (b.2.2.x) are usually flashed off on their own and / or with each other and / or inter-dried. Preference is also in the context of stage (2.2) at 15 to 35 ° C for a period of 0.5 to 30 min and flashed at 40 to 90 ° C for a period of, for example, 1 to 60 minutes between dried.
  • stage (2.2) at 15 to 35 ° C for a period of 0.5 to 30 min and flashed at 40 to 90 ° C for a period of, for example, 1 to 60 minutes between dried.
  • the sequence of flash-offs and / or intermediate drying of one or more base coat layers (B.2.2.x) can be adapted depending on the requirements of the individual case.
  • the above-described preferred stripping and intermediate drying conditions apply in particular to the preferred case that at least one basecoat (b.2.2.x), preferably all basecoats (b.2.2.x) are chemically-thermally curable one-component coating compositions.
  • the basecoats (b.2.2.x) are curable coating agents in other ways and / or that other ablating and / or intermediate drying conditions are used.
  • first basecoat film is prepared by applying a first basecoat and another basecoat film by applying the same basecoat, then obviously both layers are based on the same basecoat.
  • the application is obviously carried out in two stages, so that the corresponding basecoat in the sense of the method according to the invention corresponds to a first basecoat (b.2.2.a) and another basecoat (b.2.2.z).
  • the described construction is often also referred to as a single-layer basecoat layer structure produced in two jobs. Since, however, due to the technical conditions in a paint shop between the first job and the second job, a certain period of time always elapses, during which the substrate, for example the automobile body, is conditioned at, for example, 15 to 35 ° C. and thus vented, the characterization of this structure as a two-layer basecoat construction is formally more distinct.
  • the described process control is thus assigned to the second variant of the method according to the invention.
  • first basecoat film by, for example, electrostatic spray application (ESTA) or pneumatic application of a first basecoat directly on the cured electrodeposition coating, to vent and / or intermediate dry as described above and then to apply a second basecoat film directly by applying a second basecoat different from the first basecoat manufacture.
  • the second basecoat can also be applied by electrostatic spray application or by pneumatic application, whereby a second basecoat film is produced directly on the first basecoat film.
  • electrostatic spray application ESA
  • pneumatic application pneumatic application
  • step (2.2) is preferably selected when first a color-preparing basecoat layer as described in more detail below is to be prepared directly on the electrodeposition coat layer and then a basecoat layer having a color and / or effect as described in greater detail below is produced directly on the first basecoat film shall be.
  • the first basecoat film is then based on the paint-primer basecoat, the second basecoat film on the color and / or effect basecoat. It is also possible, for example, to apply this second basecoat material in two stages as described above, whereby two further, directly successive basecoat films are then formed directly on the first basecoat film, both based on the same basecoat.
  • a color-preparing basecoat film, a further coat based on a color and / or effect basecoat and a further coat based on a second color and / or effect basecoat can be prepared. Between and / or after the individual and / or after all three orders can be ventilated again and / or intermediately dried.
  • preferred embodiments comprise that two or three basecoat films are produced in stage (2.2) of the process according to the invention. It is then preferred that the basecoat layer prepared directly on the cured electrodeposition coating layer is based on a color-preparing basecoat.
  • the second and optionally present third layer are based either on one and the same color and / or effect basecoat or on a first color and / or effect basecoat and a different second color and / or effect basecoat.
  • the basecoat films (B.2.2.x) are not cured within stage (2) of the process according to the invention, that is to say preferably not exposed to temperatures above 100 ° C. for a period of more than 1 minute, preferably not temperatures above 100 ° C. C exposed. This results clearly and directly from the below described step (4) of the method according to the invention. Since the basecoat films are only cured in stage (4), they can not be cured in stage (2), because then curing in stage (4) would no longer be possible.
  • the application of the basecoats (b.2.1) and (b.2.2.x) takes place in such a way that the basecoat film (B.2.1) and the individual basecoat films (B.2.2.x) have a layer thickness after curing in step (4) of, for example, 5 to 50 micrometers, preferably 6 to 40 micrometers, particularly preferably 7 to 35 micrometers.
  • a layer thickness after curing in step (4) of, for example, 5 to 50 micrometers, preferably 6 to 40 micrometers, particularly preferably 7 to 35 micrometers.
  • the individual basecoat films have rather comparatively lower layer thicknesses, the overall structure then again having layer thicknesses which are of the order of magnitude of one basecoat film (B.2.1). lie.
  • the first basecoat film (B.2.2.a) preferably has film thicknesses of 5 to 35, in particular 10 to 30 micrometers
  • the second basecoat film (B.2.2.z) preferably film thicknesses of 5 to 35 micrometers, in particular 10 to 30 micrometers, the total layer thickness does not exceed 50 microns.
  • a clearcoat film (K) is prepared directly on (3.1) the basecoat film (B.2.1) or (3.2) of the topmost basecoat film (B.2.2.z). This preparation is carried out by appropriate application of a clearcoat (k).
  • the clearcoat (k) may be a transparent coating agent known per se to the person skilled in the art in this sense. Under transparent is to be understood that a layer formed with the coating agent is not color-covering, but is constituted so that the color of the underlying base paint assembly is visible. As is known, however, this does not exclude that a clearcoat in minor amounts may also contain pigments which may, for example, support the color depth of the overall structure.
  • aqueous or solvent-containing transparent coating compositions which may be formulated both as one-component and as two-component or multi-component coating compositions.
  • powder slurry clearcoats Preference is given to solvent-based clearcoats.
  • the clearcoats (k) used can in particular be thermally-chemically and / or chemically-actinically curable. In particular, they are thermally-chemically curable and externally crosslinking.
  • the clearcoats therefore usually and preferably contain at least one (first) polymer as binder with functional groups and at least one crosslinker with a functionality complementary to the functional groups of the binder. At least one hydroxy-functional poly (meth) acrylate polymer is preferably used as the binder and a free polyisocyanate as the crosslinking agent. Suitable clearcoats are described, for example, in WO 2006042585 A1, WO 2009077182 A1 or WO 2008074490 A1.
  • the clearcoat (k) is applied by the methods known to those skilled in the application of liquid coating compositions, for example by dipping, knife coating, spraying, rolling or the like.
  • spray application methods are used, such as compressed air spraying (pneumatic application), and electrostatic spray application (ESTA).
  • the clearcoat (k) or the corresponding clearcoat film (K) is preferably flashed after the application at 15 to 35 ° C for a period of 0.5 to 30 minutes or intermediate dried.
  • Such ablating or intermediate drying conditions apply in particular to the preferred case that the clearcoat (k) is a chemically-thermally curable two-component coating composition.
  • this does not exclude that the clearcoat (k) is a curable coating agent in other ways and / or other flash or intermediate drying conditions are used.
  • the layer thickness of the clearcoat layer after curing in step (4) has a layer thickness of, for example, 15 to 80 micrometers, preferably 20 to 65 micrometers, particularly preferably 25 to 60 micrometers.
  • the joint curing is preferably carried out at temperatures of 100 to 250 ° C, preferably 100 to 180 ° C for a period of 5 to 60 minutes, preferably 10 to 45 min.
  • Such curing conditions apply in particular to the preferred case that the basecoat film (B.2.1) or at least one of the basecoat films (B.2.2.x), preferably all basecoat films (B.2.2.x) are based on a chemically-thermally curable one-component coating composition , As described above, such conditions are usually required to achieve curing of such a one-component coating composition as described above. If, for example, the clearcoat material (k) is also a chemically-thermally curable one-component coating composition, the corresponding clearcoat film (K) is of course also cured under these conditions. The same obviously applies to the preferred case that the clearcoat (k) is a two-component chemical-thermally curable coating agent.
  • the above does not exclude that the basecoats (b.2.1) and (b.2.2.x) and the clearcoats (k) are otherwise curable coating agents and / or other curing conditions are used.
  • step (4) of the process according to the invention results (see also FIGS. 1 to 3).
  • the basecoat (b.2.1) contains a special pre-dispersed mixture (vdM).
  • This mixture contains at least one polyamide (P) having an acid number of less than 20 mg KOH / g, at least one polymeric resin other than the polyamide (H), and water and at least one organic solvent.
  • the components mentioned are described below.
  • the mixture (vdM) is predispersed.
  • the basecoat (b.2.1) contains this predispersed mixture. This means that the components which the mixture (vdM) should contain after its completion, are dispersed to the same mixture before the mixture is added as such in the context of the preparation of the basecoat. It is therefore essential to the invention that the mixture (vdM) is added as such.
  • the phrase "the base coat contains the predispersed blend” is synonymous with the phrase "the pre-dispersed blend is used as such in the manufacture of the base coat".
  • Preparation of the basecoat (b.2.1) thus comprises the following steps: (i) dispersing the components which the mixture (vdM) is to contain before these components are brought into contact with the further constituents of the basecoat (ie predispersion). (ii) addition of the predispersed mixture (vdM) to the otherwise finished basecoat (b.2.1) or presentation of the mixture (vdM) and addition of the further constituents of the basecoat (b.2.1) or addition of the mixture (vdM) to a part of the other Components of the basecoat (b.2.1) and addition of the remaining part of the other constituents of the basecoat (b.2.1).
  • dispersion is to be understood as follows based on the expert knowledge familiar to the person skilled in the art. It is the conversion of a mixture of different components, at least some of which are not completely miscible with each other and thus form different phases when simply combined, in a macroscopically homogenized form.
  • dispersion is understood as a generic term for the homogenization of immiscible phases, that is, for example, includes solid-liquid and liquid-liquid systems.
  • a certain microscopic phase separation may or may not be present in the mixture.
  • this may for example also have emulsion character.
  • the terms macro- and microscopic stand here obviously for a visible with the eye or just not visible phase separation or homogenization.
  • dispersion takes place by introduction of energy into a mixing system, as a result of which the droplets of the different phases are successively reduced and thus the interface between the two phases is successively increased. Overcoming the interfacial tension or creating an enlarged interface requires energy. This energy is regularly introduced mechanically, in particular via shear forces. The introduction of the shear forces takes place regularly via the stirring of the system, for example in typical stirring units such as a dissolver.
  • a predispersion or the preparation of a predispersed mixture can also be carried out, for example, by adding typical auxiliaries (additives). Mention may be made here in particular of further typical surface-active additives (emulsifiers) described in more detail below. The use of such additives is preferred in the context of the present invention. Also possible the use of defoamers known per se, which can suppress foaming that is possible due to the introduction of energy.
  • the polyamide (P) two components of the mixture (vdM) are the polyamide (P) and water.
  • the polyamide is not soluble in water, especially because of its low acid number. For this reason, it can not be converted into a macroscopically homogeneous mixture (vdM) with water without the described predispersion. Accordingly, the polyamide (P) as such is not to be effectively integrated into the aqueous basecoat (b.2.1).
  • a direct addition in the production of the basecoat leads to incompatibilities, which lead to, for example, specks in the coating finally produced. All the more surprising was that the addition in the form of the predispersed mixture leads to such excellent aesthetic properties of the resulting multi-layer coating.
  • the polyamide provided per se for coating compositions based on organic solvents shows an excellent effect as rheological aids in the systems according to the invention which are based on water-based coating agents.
  • the predispersing of the mixture (vdM) is preferably carried out at a temperature in the range of 15 to 30 ° C over a period of 5 to 60 minutes, preferably over a period of 5 to 30 minutes.
  • the dispersion can be carried out by means of commercially available devices, in particular dissolvers, for example with the device "Dispermat® LC30" from VWA-Getzmann, Germany Such devices usually have a stirring disk (toothed disk) in a stirred container the diameter of the stirring disk to the diameter of the stirred container in a range of 1: 1, 1 to 1: 2.5.
  • the peripheral speed of the stirring disk in carrying out the predispersion in a range of 15 to 25 m / s, particularly preferably 15 to 20 m / s
  • the filling height of the stirred tank is preferably in a range of 60 up to 90%, based on the total height of the stirred tank.
  • the diameter of the stirring disc is greater than the distance of the stirring disc to the bottom of the stirred container.
  • the mixture (vdM) may contain varying amounts and types of polyamides (P), polymeric resins (H) and organic solvents, as well as varying amounts of water.
  • the components can be easily matched to one another by a person skilled in the art in order then to obtain a macroscopically homogeneous (that is, predispersed) mixture. It is advantageous, for example, to use as the polymeric resin (H) such that should be integrated into the aqueous basecoat as a binder or crosslinking agent anyway. In this way, a higher freedom of formulation is gained.
  • the polyamide (P) has an acid number of less than 20 mg KOH per g.
  • the polyamide (P) has an acid number of less than 15 mg KOH per g, more preferably less than 10 mg KOH per g, most preferably less than 8 mg KOH per g and even more preferably ⁇ 7 mg KOH per g, on.
  • Polyamide (P) preferably has an acid number in a range from 0 to less than 20.0 mg KOH per g, more preferably in a range from 0.1 to less than 15.0 mg KOH per g, most preferably in a range from 0 , 1 to less than 10.0 mg KOH per g, and more preferably in a range of 0.1 to less than 8.0 mg KOH per g.
  • the polyamide (P) has an acid number in a range from 0.1 to less than 10 mg KOH per g, more preferably in a range from 0.1 to 9 mg or from 0.5 to 9 mg KOH per g, most preferably in a range from 0.1 to 8 mg or from 0.5 to 8 mg KOH per g, more preferably in a range from 0.1 to ⁇ 7 mg or from 0.5 to ⁇ 7 mg KOH per g.
  • the acid number is determined according to the method described below.
  • any conventional polyamide known to those skilled in the art can be used as long as this polyamide has an acid number of less than 20 mg KOH per g.
  • the corresponding polyamide may be a polyamide homo- or copolymer act. It is also possible to use a mixture of two or more different polyamides (P).
  • the polyamide (P) preferably has an amine number of less than 9 mg KOH per g, particularly preferably less than 8 mg KOH per g, most preferably of ⁇ 7 mg KOH per g.
  • the polyamide used as the polymeric resin (P1) has an amine number in a range of 0.1 to less than 10 mg KOH per g, more preferably in a range of 0.1 to 9 mg, or from 0.5 to 9 mg KOH per g, most preferably in a range from 0.1 to 8 mg or from 0.5 to 8 mg KOH per g, more preferably in a range from 0.1 to ⁇ 7 mg or from 0.5 to ⁇ 7 mg KOH per g.
  • the person skilled in the art is familiar with determination methods for determining the amine number.
  • the amine number is determined according to DIN 1 6945 (date: March 1989).
  • the polyamide (P) has a number average molecular weight in a range of 100 g / mol to 5,000 g / mol, more preferably in a range of 150 g / mol to 4,000 g / mol, most preferably in a range of 200 g / mol to 3,000 g / mol, more preferably in a range of 250 g / mol to 2,000 g / mol, most preferably in a range of 400 g / mol to 1,500 g / mol
  • the polyamide (P) is obtainable by reacting at least one polycarboxylic acid (C1a) with at least one polyamine (C1b), optionally in the presence of at least one monocarboxylic acid, in particular at least one C12-C24 monocarboxylic acid, and / or at least one monoamine, for example a C2-Ci2 monoamine.
  • the polyamide (P) is obtainable by reacting at least one polycarboxylic acid (C1a) selected from the group consisting of aliphatic C3-C22 dicarboxylic acids, polymers such as dimers and trimers of aliphatic C12-C24 monocarboxylic acids, and mixtures thereof, with at least one aliphatic C2-C12 diamine (C1b).
  • the reaction of at least one polycarboxylic acid (C1a) and at least one polyamine (C1b) is carried out in a preferably organic solvent.
  • polyamide (P) is obtainable by reacting at least one polycarboxylic acid (C1a), preferably at least one polycarboxylic acid selected from the group consisting of aliphatic C3-C22 dicarboxylic acids, polymers such as dimers and trimers of aliphatic Ci2-C24 monocarboxylic acids, and mixtures thereof , with at least one polyamine (C1 b), preferably with at least one aliphatic C2-Ci2-diamine (C1 b), wherein the reaction product then obtained is optionally subsequently reacted with at least one monoamine and / or a monocarboxylic acid, thereby the acid number and optionally also adjust the amine number.
  • C1a polycarboxylic acid
  • polymers such as dimers and trimers of aliphatic Ci2-C24 monocarboxylic acids
  • mixtures thereof at least one polyamine (C1 b), preferably with at least one aliphatic C2-Ci2-diamine (C1 b)
  • Polyamides (P) are commercially available. Examples which may be mentioned are the commercially available products Thixatrol® P220X-MF, Disparlon® A6900-20X, Disparlon® A650-20X, Disparlon® A670-20M, Disparlon F-9030, Luvotix® AB, Luvotix® PA 20 XA, Luvotix® R-RF , Luvotix® HT-SF, Luvotix® HAT 400, Luvotix® HT, Troythix® 250 XF, Byk-430, and Byk-431.
  • Suitable polymeric resins (H) are the resins known to the person skilled in the art in this connection. Depending on the individual case, it may be suitable for the relevant (co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins.
  • suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.
  • suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resins, epoxy resin-amine adducts, amino resins such as melamine resins, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyethers. polyurethanes.
  • the resin component and its proportion of the mixture (vdM) can easily be matched by the person skilled in the art to the further components and their proportions, in order then to obtain a macroscopically homogeneous (that is, predispersed) mixture.
  • Preferred polymeric resins (H) are polyesters, especially those having an acid number in a range of 20 to 50 mg KOH per g and an OH number in a range of 20 to 300 mg KOH per g.
  • the polyesters particularly preferably have an acid number in a range from 20 to 45 mg KOH per g, very particularly preferably in a range from 25 to 40 mg KOH per g, particularly preferably in a range from 30 to 38 mg KOH per g, on.
  • the polyesters particularly preferably have an OH number in a range from 25 to 250 mg KOH per g, very particularly preferably in a range from 25 to 200 mg KOH per g, particularly preferably in a range from 25 to 150 mg KOH per g or in a range of 30 to 120 mg KOH per g, on.
  • the determination of the OH number is carried out according to the method described below.
  • the polyesters preferably have a number-average molecular weight in a range from 500 g / mol to 100 000 g / mol, more preferably in a range from 700 g / mol to 90 000 g / mol, very particularly preferably in a range of 1000 g / mol to 80 000 g / mol, more preferably in a range of 1000 g / mol to 60 000 g / mol or in a range of 2000 g / mol to 60 000 g / mol or in a range of 2000 g / mol to 50,000 g / mol, most preferably in a range of 2,000 g / mol to 10,000 g / mol or in a range of 2,000 g / mol to 6,000 g / mol.
  • the polyester is at least obtainable by reacting at least one polymerized aliphatic C 12-24 monocarboxylic acid with at least one diol and / or polyol.
  • the corresponding polyester may be a polyester homo- or copolymer.
  • the term "at least available” is understood to mean that, in addition to the at least one polymerized aliphatic C 12 -C 24 -monocarboxylic acid and the at least one diol and / or polyol, further starting components are optionally used to prepare the polyester (P2)
  • at least one C12-C24 aliphatic monocarboxylic acid and / or at least one dicarboxylic acid and / or at least one a tricarboxylic acid selected from the group consisting of aliphatic C3-C12 dicarboxylic acids, cycloaliphatic C5-C12 dicarboxylic acids, aromatic C8-C12 dicarboxylic acids, aliphatic C5-C12 tricarboxylic acids, cycloaliphatic C6-C12 tricarboxylic acids and aromatic C9-C12 tricarboxylic acids.
  • lactones or hydroxycarboxylic acids are also to be mentioned.
  • polymerized aliphatic C 12-24 monocarboxylic acid is preferably understood as meaning a polymer, in particular a dimer and / or trimer of an aliphatic C 12-24 monocarboxylic acid.
  • preparation processes for the preparation of polymers, especially dimers and trimers, of aliphatic C 12-24 monocarboxylic acids i. to provide polymerized aliphatic Ci2-C24 monocarboxylic acids, such as dimerized, trimerized and / or higher polymerized, in particular dimerized and / or trimerized, aliphatic C12-C24 monocarboxylic known, for example from DE 25 06 21 1 A1, US 2,793,219 A and US Pat. No. 2,955,121 A.
  • As starting material for the preparation of such polymerized aliphatic C12-C24 monocarboxylic acids at least monounsaturated aliphatic C12-C24 monocarboxylic acids are used.
  • the resulting polymerized as dimerized and trimerized aliphatic Ci2-C24 monocarboxylic acids can be separated from each other by distillation and also in each case from higher-value polymerization and optionally subjected to further reaction reactions such as hydrogenation.
  • the at least one used for preparing the polyester polymerized aliphatic Ci2-C24 monocarboxylic acid is a dimerized and / or trimerized, especially at least one dimerized, Ci2-C24 monocarboxylic acid.
  • a dimerized monocarboxylic acid is therefore in particular a dicarboxylic acid.
  • dimerized and trimerized C12-C24 monocarboxylic acids are commercially available.
  • dimerized fatty acids are the products Empol 1003, Empol 1005, Empol 1008, Empol 1012, Empol 101 6, Empol 1026, Empol 1028, Empol 1061, Empol 1062, Pripol 1006, Pripol 1009, Pripol 1012, Pripol 1013, Pripol 1017 Pripol 1022, Pripol 1025, Pripol 1027 from Croda and, for commercially available trimerized fatty acids, the products Empol 1043 from BASF and Pripol 1040 from Croda.
  • the polyester is preferably obtainable at least by reacting at least one aliphatic polymerized, preferably at least one dimerized and / or trimerized, aliphatic C 12-24 monocarboxylic acid and optionally at least one aliphatic C 12-24 monocarboxylic acid with at least one C 2 C 20 polyol and / or C 2 -C2o-diol.
  • the polymerized aliphatic C12-C24 monocarboxylic acid obtainable from the at least one polymerized aliphatic C12-C24 monocarboxylic acid used for the preparation of the polyester used as polymeric resin (P2) are present in the polyester in an amount ranging from 10 to 80 mol%, preferably 10 to 60 mol -%, particularly preferably 10 to 40 mol%, based on the total weight of the polyester, before.
  • the polymerized aliphatic C 12-24 monocarboxylic acid used is not completely integrated into the polyester, but rather in the reaction of the at least one polyol and / or diol with the at least one polymerized aliphatic C 12-24 monocarboxylic acid With elimination of water by formation of ester bonds for the construction of structural units present in the polyester comes.
  • the at least one polymerized aliphatic C 12-24 monocarboxylic acid used to prepare the polyester used as polymeric resin (P2) is particularly preferably a dimerized and / or trimerized C 12-24 monocarboxylic acid and the structural unit obtainable therefrom is present in the polyester in an amount in one Range from 12 to 38 mol%, very particularly preferably in a range from 14 to 36 mol% or in a range from 1 6 to 34 mol% or in a range from 18 to 32 mol% % or in a range of 20 to 30 mol% or in a range of 22 to 28 mol%, particularly preferably in a range of 23 to 26 mol%, each based on the total weight of the polyester.
  • polyesters such as, for example, polyols, such as diols or further dicarboxylic acids or monocarboxylic acids or else lactones and hydroxycarboxylic acids, are known to the person skilled in the art and require no further mention at this point.
  • polyesters which can be used as polymeric resin (H) and their preparation, for example from DE 40 09 858 A1.
  • Suitable organic solvents which are present in addition to water in any case in the mixture (vdM), the components known to the expert in this context in question.
  • organic solvents are (hetero) cyclic, (hetero) aliphatic or (hetero) aromatic hydrocarbons, monohydric or polyhydric alcohols, ethers, esters, ketones and amides, such as.
  • N-methylpyrrolidone N-ethylpyrrolidone, dimethylformamide, toluene, xylene, butanol, ethyl and butyl glycol and their acetates, butyldiglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone or mixtures thereof.
  • the emulsifiers already mentioned above, preferably in the mixture (vdM), hereinafter also referred to as emulsifiers (E), may be the components known to the person skilled in the art in this connection.
  • the emulsifiers are preferably selected from the group consisting of lecithins and C 12-24 fatty alcohol polyglycol ethers.
  • the polyglycol ethers used may be completely or partially etherified with C 12-24 fatty alcohols.
  • a suitable lecithin, ie a suitable phospholipid, is for example Lipotin® A, which is commercially available. Also suitable is soy lecithin.
  • Suitable C12-C24 fatty alcohol polyglycol esters are, for example, the commercially available products Lutensol® ON 60 and Lutensol® XP 70. As a consequence, preferred proportions and ratios of the compulsory or preferred components contained in the mixture (vdM) are specified.
  • the relative weight ratio of the polymeric resins (H) to the component (E) is preferably in the range from 50: 1 to 1.5: 1, particularly preferably Range of 35: 1 to 1, 75: 1, most preferably in the range of 30: 1 to 1, 5: 1, particularly preferably in the range of 10: 1 to 2: 1.
  • the at least one emulsifier (E) in the mixture (vdM) in an amount of 0.1 to 10 wt .-%, particularly preferably from 0.1 to 7.5 wt .-%, most preferably from 1, 5 to 5 wt .-%, each based on the total weight of the mixture (vdM) before.
  • the relative weight ratio of the polymeric resins (H) and the polyamides (P) in the mixture (vdM) to each other is in a range of 20: 1 to 1: 1, more preferably in a range of 17.5 to 1.2: 1, most preferably in a range of 15: 1 to 2: 1.
  • the polyamide (P) in the mixture (vdM) in an amount in a range of 0.1 to 15 wt .-%, particularly preferably from 0.2 to 12.5 wt .-%, most preferably from 0 From 5 to 10% by weight, more preferably from 0.75 to 9% by weight, most preferably from 1 to 8% by weight, or from 1 to 7% by weight, based in each case on the total weight of the mixture, available.
  • the at least one polymeric resin (H) in the blend (vdM) is in an amount ranging from 5.0 to 40 wt%, more preferably from 7.5 to 35.0 wt%, each on the total weight of the mixture, present.
  • the determination or determination of the proportion of various components such as a polymeric resin or a polyamide on a mixture (vdM) or a basecoat is determined by the determination of the solid (also called non-volatile content, solids content or solids content) of the dispersion, Solution or dissolution of the respective component added to the mixture or basecoat.
  • solids content is to be understood as meaning the proportion by weight which remains under evaporation as a residue under defined conditions (measurement method see example part).
  • the proportion of organic solvents in the mixture (vdM) is for example from 5 to 60 wt .-%, preferably 10 to 55 wt .-%, each based on the total weight of the mixture.
  • the proportion of water in the mixture can vary widely and is for example from 2 to 70 wt .-%, each based on the total weight of the mixture.
  • the above-described components namely the polyamides (P), the resins (H), the emulsifiers (E) and water and organic solvents at least 90 wt .-%, preferably at least 95 wt .-% of the mixture (vdM) ,
  • the proportion of the mixture (vdM), based on the total amount of the basecoat (b.2.1), is preferably from 5 to 30 wt .-%, particularly preferably 7.5 to 25 wt .-%.
  • the procedure is preferably such that the at least one polyamide (P) in a proportion of 0.05 to 5 wt .-%, particularly preferably in an amount in a range of 0.1 to 4.0 wt .-%, completely particularly preferably in an amount in a range from 0.15 to 3.0% by weight, more preferably in an amount in a range from 0.2 to 2.0% by weight, based in each case on the total weight of the basecoat material ( b.2.1), contained in the basecoat.
  • P polyamide
  • the abovementioned principle applies to all the components of the basecoat material mentioned and their ranges of proportions, for example the pigments mentioned below or also the crosslinking agents mentioned below, such as melamine resins.
  • the basecoat (b.2.1) to be used according to the invention preferably contains at least one pigment.
  • at least one pigment By this are to be understood per se known coloring and / or optically effecting pigments.
  • color pigments and effect pigments are those skilled in the art, for example, in Römpp Lexikon coatings and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 176 and 451 described.
  • coloring pigment and color pigment as well as the terms optically effecting pigment and effect pigment are interchangeable.
  • Preferred effect pigments are, for example, platelet-shaped metallic effect pigments such as platelet-shaped aluminum pigments, gold bronzes, fire-colored bronzes and / or iron oxide aluminum pigments, pearl pigments such as fish-silver, basic lead carbonate, bismuth oxychloride and / or metal oxide mica pigments and / or other effect pigments such as platelet-shaped graphite, platelet-shaped iron oxide, multilayer Effect pigments from PVD films and / or liquid crystal polymer Pigments. Particular preference is given to platelet-shaped metallic effect pigments, in particular platelet-shaped aluminum pigments.
  • Typical color pigments include, in particular, inorganic color pigments, such as white pigments, such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
  • inorganic color pigments such as white pigments, such as titanium dioxide, zinc white, zinc sulfide or lithopone
  • Black pigments such as
  • the proportion of the pigments is preferably in the range from 1, 0 to 40.0 wt .-%, preferably 2.0 to 35.0 wt .-%, particularly preferably 5.0 to 30.0 wt .-%, each based on the total weight of the aqueous basecoat (b.2.1).
  • the aqueous basecoat (b.2.1) contains at least one polymer as a binder, in particular at least one polymer selected from the group consisting of polyurethanes, polyesters, poly (meth) acrylates and / or copolymers of said polymers, especially polyesters, poly (meth) acrylates and / or polyurethane-poly (meth) acrylates.
  • At least one polymer as a binder is always proportionally or completely contained by the addition of the mixture (vdM).
  • at least one further polymer is used as binder, which is not added in the form of the mixture (vdM).
  • the basecoat material (b.2.1) preferably comprises at least one polymer selected from the group consisting of polyurethanes, polyesters, poly (meth) acrylates and / or copolymers of said polymers, which is not present in the form of the mixture (vdM).
  • Preferred polyesters are described, for example, in DE 4009858 A1 in column 6, line 53 to column 7, line 61 and column 10, line 24 to column 13, line 3 or WO 2014/033135 A2, page 2, line 24 to page 7, line 10 and page 28, line 13 to page 29, line 13 described.
  • Preferred polyurethane-poly (meth) acrylate copolymers ((meth) acrylated polyurethanes) and their preparation For example, in WO 91/15528 A1, page 3, line 21 to page 20, line 33 and DE 4437535 A1, page 2, line 27 to page 6, line 22 described.
  • the polymers described as binders are preferably hydroxy-functional and more preferably have an OH number in the range from 15 to 200 mg KOH / g, more preferably from 20 to 150 mg KOH / g.
  • the basecoats contain at least one hydroxy-functional polyurethane-polyacrylate copolymer, more preferably at least one hydroxy-functional polyurethane-poly (meth) acrylate copolymer and at least one hydroxy-functional polyester.
  • poly (meth) acrylates in particular those which can be prepared by multistage free-radical emulsion polymerization of olefinically unsaturated monomers in water.
  • poly (meth) acrylate-based polymeric resins which by
  • the proportion of polymers as binders which are not added in the form of the mixture (vdM) to the basecoat can vary widely and is preferably in the range from 1.0 to 25.0% by weight, preferably 3.0 to 20.0 Wt .-%, particularly preferably 5.0 to 15.0 wt .-%, each based on the total weight of the basecoat (b.2.1).
  • the basecoat (b.2.1) may contain at least one typical crosslinking agent known per se. If it contains a crosslinking agent, it is preferably at least one aminoplast resin and / or at least one blocked polyisocyanate, preferably an aminoplast resin.
  • the aminoplast resins melamine resins are particularly preferred.
  • the basecoat (b.2.1) contains crosslinking agents, the proportion of these crosslinking agents, in particular aminoplast resins and / or blocked polyisocyanates, more preferably amino resins, including preferably melamine resins, preferably in the range of 0.5 to 20.0 wt .-%, preferably 1, 0 to 15.0 wt .-%, particularly preferably 1, 5 to 10.0 wt .-%, each based on the total weight of the basecoat (b.2.1).
  • crosslinking agents in particular aminoplast resins and / or blocked polyisocyanates, more preferably amino resins, including preferably melamine resins, preferably in the range of 0.5 to 20.0 wt .-%, preferably 1, 0 to 15.0 wt .-%, particularly preferably 1, 5 to 10.0 wt .-%, each based on the total weight of the basecoat (b.2.1).
  • the basecoat (b.2.1) may contain at least one other additive (additive).
  • additives are residue-free or substantially residue-free, thermally decomposable salts, of the polymers mentioned above, different physical, thermal and / or actinic radiation curable polymers as binders, other crosslinking agents, organic solvents, reactive diluents, transparent pigments, fillers, molecularly soluble dyes , Nanoparticles, light stabilizers, antioxidants, deaerators, emulsifiers, slip additives, polymerization inhibitors, radical polymerization initiators, adhesion promoters, flow control agents, film-forming aids, sag-control agents (SCAs), flame retardants, corrosion inhibitors, waxes, siccatives, biocides and matting agents.
  • SCAs sag-control agents
  • the solids content of the basecoat may vary according to the requirements of the case. In the first place, the solids content depends on the viscosity required for application, in particular spray application. It is of particular advantage that the basecoat material to be used according to the invention can nevertheless have a viscosity at comparatively high solids, which permits adequate application.
  • the solids content of the basecoat is at least 1 6.5%, preferably at least 18.0%, more preferably at least 20.0%.
  • preferred basecoats have a viscosity of 40 to 150 mPa ⁇ s, in particular 70 to 120 mPa ⁇ s, at 23 ° C. and a shear stress of 1000 l / s (For more details on the measuring method, see the example section).
  • a viscosity in this range at the specified shear stress is referred to as the spray viscosity (processing viscosity).
  • coating compositions are applied at spray viscosity, that is to say they have a viscosity under the conditions then present (high shear stress) which, in particular, is not too high in order to allow effective application. This means that the adjustment of the spray viscosity is important in order to be able to apply a paint at all by spraying methods and to ensure that a complete, uniform coating film can be formed on the substrate to be coated.
  • the basecoat (b.2.1) to be used according to the invention is aqueous, ie it is a system which contains as solvent mainly water and organic solvents only in minor proportions.
  • the proportion of water in the basecoat (b.2.1) is preferably from 35 to 75 wt .-%, more preferably 45 to 70 wt .-%, each based on the total weight of the basecoat.
  • the percentage sum of the solids of the basecoat and the proportion of water in the basecoat is at least 70% by weight, preferably at least 75% by weight. Preferred among these are ranges of from 75 to 95% by weight, in particular from 80 to 90% by weight.
  • preferred basecoats contain principally polluting components, in particular organic solvents, in relation to the solids of the basecoat, at only small proportions.
  • the ratio of the volatile organic content of the basecoat material (in% by weight) and the solids content of the basecoat material (analogous to the above representation here in wt. %) from 0.1 to 1.5, more preferably from 0.2 to 1.0.
  • the volatile organic content is the proportion of the basecoat which is calculated neither in relation to the proportion of water nor to the solids.
  • the basecoat (b.2.1) is that it can be prepared without the use of organic solvents harmful to health and the environment such as N-methyl-2-pyrrolidone, dimethylformamide, dioxane, tetrahydrofuran and N-ethyl-2-pyrrolidone , Accordingly, the basecoat preferably contains less than 10% by weight, preferably less than 5% by weight, more preferably less than 2.5% by weight of organic solvents selected from the group consisting of N-methyl-2-pyrrolidone, Dimethylformamide, dioxane, tetrahydrofuran and N-ethyl-2-pyrrolidone. Preferably, the basecoat is completely free of these organic solvents.
  • the preparation of the basecoats can be carried out using the customary and known for the production of basecoats mixing methods and mixing units.
  • At least one of these basecoats has the features essential to the invention described for the basecoat (b.2.1). This means in particular that at least one of the basecoats (b.2.2.x) contains at least one mixture (vdM).
  • the preferred features and embodiments described in the description of the basecoat (b.2.1) also preferably apply to at least one of the basecoats (b.2.2.x). Preferably, the above applies to all basecoats used (b.2.2.x).
  • a first basecoat material (b.2.2.a) is first applied, which may also be referred to as a color-preparing basecoat material. It thus serves as a basis for at least one subsequent color and / or effect basecoat layer, that is, a layer which can then optimally fulfill their function of dyeing and / or effecting.
  • a color-preparing basecoat is substantially free of colored pigments and effect pigments. Especially preferred contains such a basecoat less than 2 wt .-%, preferably less than 1 wt .-% of colored pigments and effect pigments, each based on the total weight of the aqueous basecoat.
  • the color-preparing basecoat preferably contains black and / or white pigments in this embodiment, particularly preferably both types of these pigments. It preferably contains 5 to 30 wt .-%, preferably 10 to 25 wt .-% of white pigments and 0.01 to 1, 00 wt .-%, preferably 0.1 to 0.5 wt .-% black pigments, each based on the total weight of the basecoat.
  • the resulting white, black and especially gray color which can be adjusted by the ratio of white and black pigments in different brightness levels, represents an individually adaptable basis for the then following basecoat layer construction, so that the color and / or the effect of the following basecoat construction can be optimally used.
  • the pigments are known to the person skilled in the art and also described above. Titanium dioxide is preferred as white pigment, carbon black being preferred as black pigment. As already described, however, this basecoat may of course also contain colored and / or effect pigments. This variant is particularly suitable if the resulting multicoat system is to have a high chromatic hue, for example a very deep red or yellow. If pigments in a correspondingly colored color are also added to the color-preparing basecoat, a further improved coloring can be achieved.
  • the color and / or effect basecoat (s) for the second or the second and third basecoat layers within this embodiment are adjusted according to the ultimately desired color scheme of the overall structure. If a white, black or gray color is desired, the at least one further basecoat material contains the corresponding pigments and, with regard to the pigment composition, ultimately resembles the paint-priming basecoat material. If a colorful and / or effect coating is desired, for example a varnished varnish or a metallic effect varnish, corresponding colored and / or effect pigments are used in amounts of, for example, from 1 to 15% by weight, preferably from 3 to 10% by weight. , in each case based on the total weight of the basecoat used. Colored pigments belong to the group of color pigments, the latter also including achromatic color pigments, such as black or white pigments. Such basecoats can Of course, for brightness adjustment additionally still black and / or white pigments included.
  • the inventive method allows the production of multi-layer coatings on metallic substrates waiving a separate curing step. Nevertheless, the use of the method according to the invention results in multicoat paint systems which have optical or aesthetic properties, so that even higher layer thicknesses of the corresponding basecoat films can be built up without any aesthetic loss of quality.
  • Solid content solids, non-volatile content
  • the non-volatile content is determined in accordance with DIN EN ISO 3251 (date: June 2008). In this case, 1 g of sample are weighed into a previously dried aluminum dish and dried for 60 minutes at 125 ° C in a drying oven, cooled in a desiccator, and then weighed back. The residue based on the total amount of the sample used corresponds to the nonvolatile fraction. If necessary, the volume of the nonvolatile fraction can be determined according to DIN 53219 (date: August 2009).
  • the layer thicknesses are determined according to DIN EN ISO 2808 (date: May 2007), method 12A using the measuring instrument MiniTest® 3100 - 4100 from ElektroPhysik.
  • the acid value is determined in accordance with DIN EN ISO 21 14 (date: June 2002), the procedure being in accordance with "Procedure A.”
  • the acid number corresponds to the mass of potassium hydroxide in mg, which is used to neutralize 1 g of sample under the in
  • the acid number of a carboxy-functional component in an otherwise carboxyl group-free sample, for example a polyamide in a as Commercially available solution of the polyamide can be obtained by appropriate conversion (consideration of the solid, that is the actual active substance of the sample or the amount of polyamide in the solution). It is also possible to isolate the component, for example the polyamide, beforehand and then to determine the acid number of the polyamide itself, that is to say ultimately the solid of the solution obtainable, for example, as a commercial product.
  • the OH number is determined in accordance with DIN 53240-2 (date: November 2007).
  • the OH groups are reacted by acetylation with an excess of acetic anhydride. Subsequently, the excess acetic anhydride is split by addition of water to acetic acid and titrated back all the acetic acid with ethanolic KOH.
  • the OH number indicates the amount of KOH in mg which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of sample. Determination of the number average and the weight average molecular weight
  • the determination of the number average molecular weight (M n ) is carried out by means of gel permeation chromatography (GPC). The determination method is based on DIN 55672-1 (date: August 2007). In addition to the number average molecular weight, this method can also be used to determine the weight-average molecular weight (M w ) and the polydispersity (ratio of weight-average molecular weight (M w ) to number-average molecular weight (M n )).
  • the eluent used is tetrahydrofuran. The determination is made against polystyrene standards.
  • the column material consists of styrene-divinylbenzene copolymers.
  • the samples are first sheared for 5 minutes at a shear rate of 1000 s -1 (loading phase) and then for 8 minutes at a shear rate of 1 s _1 (discharge phase) .
  • the mean viscosity level during the stress phase (high shear viscosity) and the level after 8 minutes unloading phase (Low shear viscosity) are determined from the measured data and the values are compared before and after storage by calculating the respective percentage changes.
  • Variant A First water-based paint as a wedge, second water-based paint as a constant coat
  • a 30 x 50 cm steel sheet coated with a hardened standard KTL (CathoGuard® 800 from BASF Coatings) is carried along on one longitudinal edge two adhesive strips (Tesaband, 19 mm) provided in order to determine layer thickness differences after coating.
  • the first aqueous basecoat is electrostatically applied as a wedge with a target layer thickness (layer thickness of the dried material) of 0-30 ⁇ . This is followed by venting for 3 minutes at room temperature, before the second aqueous basecoat is also applied electrostatically in a single application after removal of one of the two adhesive strips.
  • the target layer thickness (layer thickness of the dried material) is 13-1 6 ⁇ . After renewed flash-off time of 4 minutes at room temperature, the assembly is oven-dried in a circulating air oven at 60 ° C for 10 minutes.
  • a commercially available two-component clearcoat material (ProGloss® from BASF Coatings GmbH) having a target layer thickness (layer thickness of the dried material) of 40-45 ⁇ m is applied manually to the intermediate dried structure by means of a flow cup gun.
  • the resulting clearcoat is flashed for 10 minutes at room temperature (18 to 23 ° C); then curing in a convection oven at 140 ° C for another 20 minutes.
  • Variant B First water-based paint as a constant coat, second water-based paint as a wedge
  • a 30 x 50 cm steel sheet coated with a hardened standard cathodic electrocoat (CathoGuard® 800 from BASF Coatings) is provided on one longitudinal edge with two adhesive strips (Tesaband, 19 mm) in order to be able to determine layer thickness differences after the coating.
  • the first aqueous basecoat is applied electrostatically with a target layer thickness (layer thickness of the dried material) of 18-22 ⁇ m. This is followed by venting for 3 minutes at room temperature, before the second aqueous basecoat is also applied electrostatically in a single application as a wedge after removing one of the two adhesive strips.
  • the target layer thickness (layer thickness of the dried material) is 0-30 ⁇ . After renewed flash-off time of 4 minutes at room temperature, the assembly is oven-dried in a circulating air oven at 60 ° C for 10 minutes.
  • a commercially available two-component material is manually applied to the temporarily dried structure by means of a flow cup gun.
  • Clearcoat ProGloss® BASF Coatings GmbH
  • target layer thickness layer thickness of the dried material
  • the resulting clearcoat is flashed for 10 minutes at room temperature (18 to 23 ° C); then curing in a convection oven at 140 ° C for another 20 minutes.
  • multicoat paint systems are prepared in accordance with the methods for painting water-based paint wedge assemblies (Variant A or B, respectively) and then evaluated visually according to the following general specification:
  • the dry layer thickness of the entire water-based paint system, consisting of the first and the second aqueous basecoat, is controlled and for the basecoat layer thickness wedge the areas of 0-20 ⁇ and 20 ⁇ are marked to the end of the wedge on the steel sheet.
  • the evaluation of the pinholes is done visually in the two separate areas of the waterborne paint wedge. For each area, the number of pinholes is counted. All results are normalized to an area of 200 cm 2 . In addition, if necessary, it is recorded from which dry layer thickness of the waterborne base wedge no more needle sticks occur.
  • multicoat paint systems are prepared according to the methods for painting water-based paint wedge assemblies (variants A or B) and then evaluated according to the following general specification:
  • the dry film thickness of the entire aqueous basecoat composition consisting of the one or the first and the second waterborne basecoat, is controlled and for the basecoat film thickness wedge become the ranges of 15-20 ⁇ and 20- 25 ⁇ or 10-15 ⁇ , 15 -20 ⁇ , 20-25 ⁇ , 25-30 ⁇ and optionally 30- 35 ⁇ marked on the steel sheet.
  • the determination or evaluation of the layer thickness-dependent course is carried out with the help of the measuring device Wave scan by Byk / Gardner within the four previously determined basecoat layer thickness ranges.
  • DOI characteristic "distinctness of imgage"
  • the corresponding water-based paint is applied by means of a 150 ⁇ box doctor on a glass plate of dimensions 9 x 15 cm.
  • the waterborne basecoat is applied by means of two-coat application on a steel panel measuring 32 ⁇ 60 cm coated with a hardened standard cathodic electrocoat (CathoGuard® 800 from BASF Coatings); the application in the first step is carried out electrostatically with a target layer thickness of 8-9 ⁇ , in the second step is pneumatically applied after a 2-minute flash off at room temperature with a target layer thickness of 4-5 ⁇ . The resulting aqueous basecoat film is then dried after renewed flash off at room temperature for 5 minutes in a convection oven for 5 minutes at 80 ° C. On the dried Waterborne basecoat is a commercially available two-component clearcoat (ProGloss BASF Coatings GmbH) with a target layer thickness of 40-45 ⁇ applied.
  • CathoGuard® 800 from BASF Coatings
  • the resulting clearcoat is flashed off for 10 minutes at room temperature; then curing in a convection oven at 140 ° C for another 20 minutes.
  • a formulation constituent therefore has the main designation "melamine-formaldehyde resin” and if a commercial product is indicated, then the melamine-formaldehyde resin is used as precisely this commercial product shall be.
  • a preparation rule for a formulation component and, for example, a polymer dispersion having a certain solids results in this preparation, then precisely this dispersion is used.
  • the term "polymer dispersion” or merely the active substance for example “polymer”, “polyester” or “polyurethane-modified polyacrylate” was chosen as the main name. This must be taken into account if the amount of the active substance (the polymer) is to be deduced. All parts given in the tables are parts by weight.
  • Disparlon® ® 6900-20X available from Kusomoto
  • Disparlon® AQ630 available from Kusomoto
  • Disparlon® AQ600 available from Kusomoto ⁇
  • the polyamide in the commercial product Disparlon® AQ630 from Kusumoto Chemicals, Ltd. (non-volatile content of the commercial product: 18% by weight) has an acid number of 75 mg KOH / g.
  • the polyamide in the commercial product Disparlon® A670-20M from Kusumoto Chemicals, Ltd. (Non-volatile content of the commercial product: 20% by weight) has an acid value of 9 mg KOH / g.
  • the polyamide in the commercial product Disparlon® 6900-20X from Kusumoto Chemicals, Ltd. (Non-volatile content of the commercial product: 20% by weight) has an acid value of 9 mg KOH / g.
  • aqueous phase The components listed in Table A under "aqueous phase" are stirred together in the order indicated to an aqueous mixture, then stirred for 10 minutes and adjusted to a pH of 8 and a spray viscosity of 90 mPa.s using deionized water and dimethanolamine. s at a shear stress of 1291 s ⁇ measured with a rotary viscometer (Rheolab QC device with tempering system C-LTD80 / QC Anton Paar) at 23 ° C, set.
  • Aqueous phase Aqueous phase:
  • Polyurethane-modified polyacrylate manufactured according to
  • the white paste is made from 50 parts by weight of titanium rutile 2310, 6 parts by weight of a polyester prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 24.7 parts by weight of a patent application EP 022 8003 B2, S. 8, Z. 6 to 18 prepared binder dispersion, 10.5 parts by weight of deionized water, 4 parts by weight of 2,4,7,9-tetramethyl-5-decynediol, 52% in BG (available from BASF SE), 4.1 parts by weight of butylglycol , 0.4 parts by weight of 10% dimethylethanolamine in water and 0.3 parts by weight of Acrysol RM-8 (available from The Dow Chemical Company). Production of black paste
  • the black paste is composed of 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyldiglycol and 12 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10%
  • the yellow paste is made from 37 parts by weight of Bayferrox 3910 (available from Lanxess), 49.5 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, lines 26 to 25, Z. 24, 7.5 parts by weight Disperbyk®-184 (available from BYK-Chemie GmbH) and 6 parts by weight of deionized water.
  • Bayferrox 3910 available from Lanxess
  • aqueous phase The components listed in Table B under "aqueous phase" are stirred together in the order listed to form an aqueous mixture, which is then stirred for 10 minutes and brought to a pH of 8 and a spray viscosity of 10 ⁇ 10 using deionized water and dimethanolamine 10 mPa-s at a shear stress of 1000 s _1 , measured with a rotary viscometer (Rheolab QC device with tempering system C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • Aqueous phase 3% NaMg layered silicate solution 13.54
  • Example D column 16, lines 37-59 of the 4.40 4.40 4.40 4.40 4.40
  • the black paste is composed of 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyldiglycol and 12 parts by weight of deionized water.
  • 1 .2C Preparation of aqueous basecoats WBL B7 and B9 (comparison) and WBL B8 and WBL 10 (according to the invention)
  • aqueous phase The components listed in Table C under "aqueous phase" are stirred together in the order given to an aqueous mixture, then stirred for 10 minutes and with the aid of deionized water and dimethanolamine to a pH of 8 and an injection viscosity of 60 ⁇ 5 mPa-s (WBL B7, WBL B9) or 80 ⁇ 5 mPa-s (WBL B8, WBL B10) at a shear load of 1000 s "1 , measured with a rotary viscometer (Rheolab QC with temperature control system C-LTD80 / QC Anton Paar) at 23 ° C, set.
  • Aqueous phase Aqueous phase:
  • Isopar® L available from Exxon Mobile 0.82 0.82 0.82 0.82
  • the black paste is composed of 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyldiglycol and 12 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10%
  • the barium sulfate paste is composed of 39 parts by weight of a polyurethane dispersion prepared according to EP 0228003 B2, page 8, lines 6 to 18, 54 parts by weight of barium sulfate (blanc fixe micro from Sachtleben Chemie GmbH), 3.7 parts by weight of butyl glycol and 0.3 part by weight Agitan 282 (available from Münzing Chemie GmbH) and 3 parts by weight of deionized water.
  • the steatite paste is from 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight of Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercial grade Polyethers (Pluriol® P900, available from BASF SE) and 1 6.45 parts by weight of deionized water.
  • aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight of Agitan 282 (available from Münzing Chemie GmbH),
  • aqueous phase The components listed under "aqueous phase" in Table D are stirred together in the order listed to form an aqueous mixture, which is then stirred for 10 minutes and brought to a pH of 8 and a spray viscosity of 90 ⁇ 5 using deionized water and dimethanolamine mPa-s at a shear stress of 1000 s _1 , measured with a rotary viscometer (device Rheolab QC with tempering C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • Aqueous phase Aqueous phase:
  • the white paste is composed of 34 parts by weight of titanium rutile 2310, 43.3 parts by weight of an aqueous dispersion of a poly (meth) acrylate emulsion polymer having a nonvolatile content of 26-28%, 3.9 weight percent butyl glycol, 1.6.7 weight parts of deionized water and 2 , 1 part by weight of Disperbyk®-184 (available from BYK-Chemie GmbH).
  • the yellow paste is composed of 47 parts by weight of Sicotan Yellow L 1912, 45 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to page 25, line 24, 2.7% by weight of 1-propoxy-2 propanol, 2.8 parts by weight of deionized water, 1.5 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH) and 1 part by weight of Aerosil R 972 (available from Evonik Industries).
  • the black paste is made from 40 parts by weight of Bayferrox 318 M (available from Lanxess), 39 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to page 25, line 24, 2.0% by weight 1 -Propoxy-2-propanol, 1 1, 1 parts by weight of deionized water, 0.5 parts by weight of Agitan 282 (available from Münzing Chemie GmbH), 4.4 parts by weight of Pluriol® P900 (available from BASF SE) and 3 parts by weight of 10% dimethylethanolamine in Water produced.
  • Bayferrox 318 M available from Lanxess
  • the steatite paste is from 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight of Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE) and 1.65 parts by weight of deionized Water produced.
  • aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight of Agitan 282 (available from Münzing Chemie GmbH), 1.45
  • aqueous phase The components listed under "aqueous phase" in Table E are stirred together in the order listed to form an aqueous mixture, which is then stirred for 10 minutes and brought to a pH of 8 and an injection viscosity of 85 ⁇ 5 using deionized water and dimethanolamine mPa-s at a shear stress of 1000 s _1 , measured with a rotary viscometer (device Rheolab QC with tempering C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • Hydrosol A170 available from DHC Solvent Chemie GmbH 0.54 0.54 Pluriol® P900, available from BASF SE 0.54 0.54
  • Tinuvin ® 384-2 available from BASF SE 0.80 0.80
  • Tinuvin ® 123 available from BASF SE 0.40 0.40
  • the white paste is composed of 34 parts by weight of titanium rutile 2310, 43.3 parts by weight of an aqueous dispersion of a poly (meth) acrylate emulsion polymer having a nonvolatile content of 26-28, 3.9% by weight of butyl glycol, 1.6.7 parts by weight of deionized water and 2, 1 part by weight of Disperbyk®-184 (available from BYK-Chemie GmbH).
  • the yellow paste is composed of 47 parts by weight of Sicotan Yellow L 1912, 45 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to page 25, line 24, 2.7% by weight of 1-propoxy-2 propanol, 2.8 parts by weight of deionized water, 1.5 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH) and 1 part by weight of Aerosil R 972 (available from Evonik Industries).
  • the black paste is composed of 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyldiglycol and 12 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10%
  • the steatite paste is from 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight Disperbyk®-184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE) and 1 Made 6.45 parts by weight of deionized water.
  • an aqueous binder dispersion prepared according to WO 91/15528, p. 23, Z. 26 to p. 25, Z. 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts
  • aqueous phase The components listed under "aqueous phase" in Table F are stirred together in the order indicated to give an aqueous mixture, which is then stirred for 10 minutes and adjusted to a pH of 8 and a spray viscosity of 1 liter using deionized water and dimethanolamine 0 ⁇ 1 0 mPa-s (WBL B15) or 140 ⁇ 1 0 mPa-s (WBL B16) at a shear stress of 1 000 s ⁇ measured with a rotary viscometer (Rheolab QC with tempering system C-LTD80 / QC from the company Anton Paar) at 23 ° C.
  • Aqueous phase Aqueous phase:
  • NACU E 2500 available from King Industries, Inc. 0.42 0.42
  • the black paste is composed of 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyldiglycol and 12 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester, prepared according to Example D, column 1 6, Z. 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10%
  • the blueprint was made from 69.8 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 12.5 parts by weight of Paliogen® Blue L 6482 (available from BASF SE), 1, 5 Parts by weight of a 10% aqueous dimethylethanolamine solution, 1, 2 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE) and 15 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 12.5 parts by weight of Paliogen® Blue L 6482 (available from BASF SE), 1, 5 Parts by weight of a 10% aqueous dimethylethanolamine solution, 1, 2 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE) and 15 parts by weight of deionized water.
  • the barium sulfate paste is composed of 39 parts by weight of a polyurethane dispersion prepared according to EP 0228003 B2, page 8, lines 6 to 18, 54 parts by weight of barium sulfate (blanc fixe micro from Sachtleben Chemie GmbH), 3.7 parts by weight of butyl glycol and 0.3 part by weight Agitan 282 (available from Münzing Chemie GmbH) and 3 parts by weight of deionized water.
  • a polyurethane dispersion prepared according to EP 0228003 B2, page 8, lines 6 to 18, 54 parts by weight of barium sulfate (blanc fixe micro from Sachtleben Chemie GmbH), 3.7 parts by weight of butyl glycol and 0.3 part by weight Agitan 282 (available from Münzing Chemie GmbH) and 3 parts by weight of deionized water.
  • the steatite paste is composed of 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to page 25, line 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight Disperbyk®-184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE) and 1 Made 6.45 parts by weight of deionized water.
  • an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to page 25, line 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV), 0.4 parts by weight Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight Disperbyk®
  • aqueous phase in Table G are stirred together in the order indicated to form an aqueous mixture, and in the next step, an organic mixture is prepared from the components listed under “organic phase” in Table G and selected from “mixed lacquer”.
  • the organic mixture and the mixing varnish are mixed for 10 minutes before this mixture is then added to the aqueous mixture, then it is stirred for 1 0 minutes and brought to pH 8 with the aid of deionized water and dimethanolamine and a spray viscosity of 85 ⁇ 5 mPa-s at a shear stress of 1000 s ⁇ measured with a rotary viscometer (Rheolab QC device with tempering system C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • Aqueous phase ⁇
  • Table 2.1 Results of investigations regarding stability (segregation) and specks WBL B1 WBL B2 WBL B3 WBL B4 WBL B5 WBL B6
  • WBL B1 containing phyllosilicate
  • WBL B2 to be used according to the invention
  • the basecoats which have polyamides having a high acid number WBL B3 to WBL B6
  • WBL B3 to WBL B6 surprisingly show distinct weaknesses in terms of specks and stability; an increase in the amount of the polyamide leads to no improvement.
  • These polyamides are therefore to be used as a rheology aid in waterborne paints significantly worse.
  • the system containing phyllosilicate was used.
  • the waterborne basecoats WBL B7 to WBL B10 consistently show a very good needle stick robustness.
  • both aqueous basecoats show comparable behavior.
  • a basecoat material to be used according to the invention comprising a mixture (vdM) comprising a polyamide having a low acid number (WBL B12)
  • vdM mixture
  • WBL B12 polyamide having a low acid number
  • a basecoat material to be used according to the invention comprising a predispersed mixture comprising a low acid number polyamide (WBL B14) in comparison with the layered silicate-containing reference (WBL B13) leads to a significant improvement in the course, in particular of short waves and of DOI.
  • Paint finish Water-based paint as wedge WBL to WBL B16
  • the aqueous basecoat WBL B16 to be used according to the invention has a significantly better pinhole robustness than the layered silicate-based waterborne basecoat WBL B15.
  • Paint finish 2. Water-based paint constant WBL B15 WBL BIß
  • Paint finish Water-based paint as wedge WBL to WBL B16
  • WBL A2 When WBL A2 is used as the first aqueous basecoat, a significantly lower needle-point level is found for the layered silicate-containing reference (WBL B15); however, slight advantages in the use of the basecoat WBL B16 to be used according to the invention can still be seen.
  • the basecoat WBL B 17 to be used according to the invention has an outstanding quality in terms of storage stability and speck formation.
  • a basecoat WBL B18 which contains the same low acid number polyamide as WBL B 17, but in which the polyamide is introduced directly and not in the form of a predispersed mixture (vdM), has markedly poorer properties.
  • FIG. 1 Schematic structure of a multi-layer coating (M) according to the invention arranged on a metallic substrate (S) comprising a cured electrodeposition coating layer (E.1) and a basecoat film (B.2.1) and a clearcoat film (K) which have been cured together.
  • S metallic substrate
  • E.1 a cured electrodeposition coating layer
  • B.2.1 basecoat film
  • K clearcoat film
  • FIG. 1 Schematic structure of a multi-layer coating (M) according to the invention arranged on a metallic substrate (S) comprising a cured electrodeposition coating layer (E.1), two basecoat films (B.2.2.x), namely a first basecoat film (B.2.2.a) and one above it arranged, topmost basecoat film (B.2.2.z), and a clearcoat film (K), which were cured together.
  • E.1 a cured electrodeposition coating layer
  • B.2.2.x two basecoat films
  • B.2.2.a first basecoat film
  • B.2.2.z topmost basecoat film
  • K clearcoat film
  • FIG. 1 Schematic structure of a multi-layer coating (M) according to the invention arranged on a metallic substrate (S) comprising a cured electrodeposition coating layer (E.1), three basecoat films (B.2.2.x), namely a first basecoat film (B.2.2.a), one above it arranged basecoat film (B.2.2.b) and a topmost basecoat film (B.2.2.z), and a clearcoat film (K), which were cured together.
  • E.1 a cured electrodeposition coating layer
  • B.2.2.x three basecoat films
  • B.2.2.a first basecoat film
  • B.2.2.b basecoat film
  • B.2.2.z topmost basecoat film
  • K clearcoat film

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Abstract

La présente invention concerne un procédé permettant de réaliser une peinture multicouche sur un substrat métallique. Selon ce procédé, une couche de peinture de base ou plusieurs couches de peinture de base directement consécutives sont produites directement sur un substrat métallique revêtu d'une couche électrophorétique de peinture durcie, une couche de vernis transparent est produite directement sur la couche de peinture de base ou sur la couche de peinture de base supérieure des couches consécutives, et ensuite la ou les couches de peinture de base et la couche de vernis transparent sont durcies conjointement. Le procédé selon l'invention est caractérisé en ce qu'au moins une peinture de base utilisée pour la production des couches de peinture de base comporte au moins un mélange prédispersé (vdM) contenant au moins un polyamide (P) présentant un indice d'acide inférieur à 20 mg KOH/g, au moins une résine polymère (H) différente dudit polyamide, de l'eau et au moins un solvant organique.
EP16705526.8A 2016-02-19 2016-02-19 Procédé de production d'une peinture multicouche Withdrawn EP3416754A1 (fr)

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JP7318109B2 (ja) * 2019-07-29 2023-07-31 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 光輝コート層を含む多層コーティングの生成方法及び前記方法で得られる多層コーティング
CN114585692A (zh) * 2019-10-23 2022-06-03 巴斯夫涂料有限公司 具有改善的针孔稳定性的着色水性涂料组合物
JP7739416B2 (ja) * 2020-08-18 2025-09-16 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 多層コーティング系製造のための２ウェットコーティング法
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