DE10060399A1 - Aqueous effect-forming water borne coating composition, useful for automobiles, doors, windows and furniture, is prepared by mixing separate aqueous dispersions - Google Patents

Abstract

An aqueous effect-forming coating composition containing at least one water soluble or dispersible binding agent and an effect pigment is prepared by: (1) mixing the pigment with the binding agent in an aqueous medium; (2) forming a second dispersion of the pigment; and (3) mixing the two dispersions with the aqueous solution or dispersion of at least one water soluble or dispersible binding agent. An aqueous effect-forming coating composition (I) containing: (a) at least one water soluble or dispersible binding agent; and (b) an effect pigment. is prepared by: (i) dispersal of a first portion of the pigment (B) or a mixture of the first pigment (B) in a water miscible organic solvent and an aqueous solution or dispersion of a water soluble dispersible binding agent (A); (ii) dispersal of a second portion of the pigment (B) or a second pigment in a mixture of water miscible organic solvent and a non- or slightly water-miscible sovlent; and (iii) mixing the dispersions from (i) and (ii) with the aqueous solution or dispersion of at least one water soluble or dispersible binding agent.

Description

The present invention relates to a new, aqueous, effect Coating material, especially a metallic water-based paint. In addition, the The present invention a process for the preparation of the new, aqueous, effect The coating material. Furthermore, the present invention relates to the use of the new, aqueous, effect coating material for the production or multilayer, effect-giving paintwork.

Aqueous, effect-imparting coating materials, in particular metallic water-based paints, Metallic water-based paints based on polyurethane, for example, are made from Patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431 A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, Column 5, lines 31 to 45, known. They are mainly used for manufacturing effect-giving multi-layer coatings according to the wet-on-wet process, in which the Metallic water-based paint applied to a substrate and the resulting wet layer dried, but is not hardened. The resulting basecoat is then covered with a clear coat, after which the basecoat and clearcoat be hardened together. But you can also use it to make Solid color finishes are used.

During the application and curing of the aqueous, effect-imparting coating materials can lead to the formation of so-called clouds, i.e. H. of light-dark shades, come. These are an indication of deficiencies in the dispersion and / or orientation of the effect pigments, in particular metallic effect pigments, in the coating. Cloudy paint finishes are especially the case with particularly high-quality products that  Do not have large-area paintwork, such as automobiles accepted because such paint defects give the impression of poor quality of the overall product (e.g. automobile).

While it is known that the cloudiness to a certain extent is due to the addition of Aerosil, talc, white or matting pastes for aqueous, effect-giving Coating materials can be reduced, but the addition of such pastes has been frequent an adverse effect on the color tone (color shift) and the metallic effect (Reduction).

This can counteract the reduction in the metallic effect in some cases that coarser aluminum flakes are used. Coarser aluminum flakes however, result in a lower gloss. In addition, this method is with others platelet-like effect pigments such as mica pigments often cannot be used because the corresponding coarser pigments are not available.

It has been assumed that the following parameters cause and / or influence cloudiness:

• The static viscosity of the aqueous coating material,
• - the kinematic viscosity of its droplets,
• - its surface tension,
• - the surface tension of the substrate,
• The covering of the surface of the effect pigments,
• - the evaporation properties of the solvents or cosolvents,
• - The flight speed and kinetic energy of the droplets of the aqueous Coating material,
• - the diameter of the droplets or
• - the distribution of the droplet diameters.

In-depth studies have shown, however, that the variation of these parameters is the Cloudiness leaves unaffected.  

The object of the present invention is to provide a new, aqueous, effect To provide coating material that no longer has the disadvantages of the prior art longer, but which delivers single and multi-layer, effect paint, which have no or a significantly lower light-dark shade (clouds) than that Have coatings of the prior art. The new, watery, effect coating materials and the new, single and multi-layer, effect-giving paint finishes otherwise the beneficial Property profile of the known, aqueous, effect coating materials and have single-layer and multi-layer, effect paint systems produced from it, if not surpass this. Furthermore, the new, aqueous, effect coating materials in a simple manner with the help of conventional and known Starting products with as little material modification as possible of the known ones Coating materials are available so that they can be produced in existing devices, can be handled, applied and hardened.

In addition, it was the object of the present invention to develop a new method Manufacture of aqueous, effect-giving coating materials to find the minimal modification of the known methods for producing such Coating materials supplies new, aqueous, effect-giving coating materials, which for the Production of single and multi-layered, effect-giving, completely or essentially cloud-free paint finishes are suitable.

Accordingly, the new, aqueous, effect-imparting coating material was found, comprising at least one water-soluble or dispersible binder and at least one effect pigment, which can be prepared by:

• A) a first part of the effect pigment or at least a first effect pigment in a mixture
  • - At least one water-miscible organic solvent and
  • - disperses an aqueous solution or dispersion of at least one water-soluble or dispersible binder and
  • - A second part of the effect pigment or at least a second effect pigment in a mixture
  • - At least one water-miscible organic solvent and
  • - At least one solvent that is immiscible or only slightly miscible with water
  dispersed, after which
• B) the dispersions (I) and (II) with the aqueous solution or dispersion at least of a water-soluble or dispersible binder.

In the following the new aqueous, effect coating material as "Coating material of the invention" referred to.

In addition, the new process for producing the coating material of the invention was found, in which

• A) a first part of the effect pigment or at least a first effect pigment in a mixture
  • - At least one water-miscible organic solvent and
    • - An aqueous solution or dispersion of at least one water-soluble or dispersible binder
  dispersed and
• B) a second part of the effect pigment or at least a second effect pigment in a mixture
  • - At least one water-miscible organic solvent and
  • - At least one solvent that is immiscible or only slightly miscible with water
  dispersed, after which
• C) the dispersions (I) and (II) with the aqueous solution or dispersion at least of a water-soluble or dispersible binder.

The following is the new process for producing the invention Coating material referred to as the "inventive method".

Further objects according to the invention are evident from the description.

In view of the prior art, it was surprising and not for the person skilled in the art predictable that the object underlying the present invention could be solved that part of the to be used according to the invention Effect pigments in the form of a dispersion (II) to that containing the binders Dispersion (III) added, since it was expected that this measure the optical quality (Appearance) of those produced from the coating materials of the invention effect coatings deteriorated rather than improved.

With the optical effects caused by the coating material according to the invention, are preferably metallic effects and / or dichroic optical effects, but especially metallic effects (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, "effect pigments" and pages 380 and 381 "metal oxide Mica pigments "to" metal pigments ").

Examples of suitable effect pigments are metallic effect pigments such as those commercially available Aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as Pearlescent or interference pigments, platelet-shaped effect pigments based on Iron oxide, which has a color from pink to brownish red, liquid crystalline Effect pigments or fluorescent pigments (daylight pigments) such as bis (azomethine) -  Pigments. In addition, varnish and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, 1998, pages 176, "effect pigments" and pages 380 and 381 "metal oxide Mica pigments "to" metal pigments ", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A 1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417 567 A1, US 4,828,826 A or US 5,244,649 A.

Metallic effect pigments are preferably used, in particular Aluminum effect pigments (see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 24 and 25, "aluminum pigments" used.

The aluminum effect pigments are leafing pigments (see Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, page 351, "Leafing-Pigments") or non- Leafing pigments (see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 412, "Non-Leafing Pigments"). They are platelet-shaped, in essentially round shape (silver dollar type) or of platelet-shaped, essentially elongated shape.

Is only one for the production of the coating material of the invention Applied effect pigment, a first part of it is in a mixture of at least a water-miscible organic solvent and an aqueous solution or Dispersion of at least one water-soluble or dispersible binder dispersed (dispersion I).

Are at least two for the production of the coating material of the invention different effect pigments, at least one of them is used Production of the dispersion (I) described above used (first effect pigment). In addition to the first effect pigment, the dispersion (I) can also contain part of the second effect pigment (see below) included.

In the context of the present invention, water-miscible organic Solvents varnish-like solvents understood in every ratio with water are miscible, such as ethylene glycol, propylene glycol, butyl glycol and their methyl, ethyl  or propyl ether, ketones such as acetone or diacetone alcohol, cyclic ethers such as Tetrahydrofuran or dioxane or amides such as N, N-dimethylformamide or N- Methylpyrrolidone (see Paints Coatings and Solvents, Edit. Dieter Stoye and Werner Friday, second edition, Wiley-VCH, and Weinheim, New York, 1998, pages 329 and 330).

Examples of suitable water-soluble or dispersible binders are described below. Water-soluble or dispersible are preferred Polyester used.

The content of the dispersion (I) in effect pigment or effect pigments can be very wide vary and depends on the one hand on the hiding power of the effect pigment and according to the intensity of the optical effect you want to achieve. Preferably included the dispersions (I), based in each case on their total amount, 10 to 80, preferably 12 to 75, particularly preferably 14 to 70, very particularly preferably 16 to 65 and in particular 18 to 60% by weight of effect pigment or effect pigments.

The content of the dispersion (I) in water-soluble or dispersible binders can also vary very widely and depends primarily on the dispersibility of the Effect pigments on the one hand and the dispersibility of the binders on the other. The binders are preferably used in an amount of, based in each case on the Total amount of dispersion (I), 10 to 60, preferably 11 to 55, particularly preferably 12 up to 50, very particularly preferably 13 to 45 and in particular 14 to 40% by weight.

The preparation of the dispersion (I) does not offer any special features, but rather takes place by mixing the starting products, the usual and known Methods and devices for mixing liquid and solid products, such as Mixing kettle, dissolver or Ultraturrax can be used. Mixing is like this carried out gently so that the effect pigments used in each case are not damaged become.

Is only one for the production of the coating material of the invention Effect pigment used, the second part of it in a mixture of at least  a water-miscible organic solvent and at least one with water or dispersed to a small extent miscible solvent (dispersion II).

Are at least two for the production of the coating material of the invention different effect pigments, at least one of them is used Production of the dispersion (II) (second effect pigment) used.

Examples of suitable water-miscible organic solvents are those above . described

Use organic solvents that are immiscible or only slightly miscible in water at 20 ° C, based on water and solvent, preferably less than 10, preferably less than 9 and in particular less than 8% by weight of water. Conversely, takes Water at 20 ° C, based on water and solvent, preferably less than 6, preferably less than 5 and in particular less than 4% by weight.

Examples of suitable organic ones which are immiscible or only slightly miscible in water Solvents are ketones such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone or Trimethylcyclohexanone, ethers such as dibutyl ether, esters such as isopropyl acetate, butyl acetate, Ethyl glycol acetate or butyl glycol acetate or higher alcohols such as hexanol, Cyclohexanol, trimethylcyclohexanol or 2-ethyl-1-hexanol (isooctanol) (see Paints Coatings and Solvents, Edit. Dieter Stoye and Werner Freitag, second edition, Wiley- VCH, and Weinheim, New York, 1998, pages 329 and 330). Of these, the higher ones Alcohols, especially 2-ethyl-1-hexanol, are advantageous and are therefore preferred used.

The content of the effect pigment in the dispersion (II) can vary very widely and is directed also according to the parameters described above for dispersion (I). The dispersion (II) preferably contains 10 to 80, based on its total amount, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight of effect pigment or pigments.  

The content of the dispersion (II) is not or only to a small extent with water miscible organic solvents can vary very widely. The upper limit forms that amount of solvent that is just in the coating material of the invention does not yet cause segregation. Preferably, each based on the total amount of dispersion (II), 1 to 80, preferably 2 to 75, particularly preferably 3 to 70, very particularly preferably 4 to 65 and in particular 5 to 60% by weight used.

The preparation of the dispersion (II) is made like the dispersion (I), except that none Binder is applied.

The dispersions (I) and (II) described above are mixed with the aqueous solution or the dispersion (III) of at least one which is soluble or dispersible in water Binder united. The dispersion (II) is preferably added before the dispersion (I) the dispersion (III) combined.

The dispersion (III) contains at least one water-soluble or water-dispersible Binder.

The binders can be physical, thermal or thermal and actinic Radiation can be hardened. The latter is also referred to by experts as "dual cure".

In the context of the present invention, the term "physical hardening" means the Hardening a layer of a coating material by filming Solvent release from the coating material, the link within the Coating via loop formation of the polymer molecules of the binders (to which Term cf. Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or the film adaptation takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 and 275). No crosslinking agents are usually necessary for this. Possibly can the physical hardening by atmospheric oxygen, heat or by radiation with actinic radiation are supported.  

If the binders are thermally curable, they can be thermally crosslinked or self-cross-linking, in particular cross-linking. As part of the present Invention, the term "self-crosslinking" denotes the property of a binder engage in cross-linking reactions with themselves. The prerequisite for this is that in the Binders already have both types of complementary reactive functional groups are included, which are necessary for thermal crosslinking, or reactive functional groups that can react "with themselves". As an external network on the other hand denotes those binders in which the one type of complementary reactive functional groups, and the other kind in a hardener or crosslinking agent available. In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Härtung", pages 274 to 276, in particular Page 275, below.

In the context of the present invention, electromagnetic radiation is actinic Radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, especially UV radiation, and corpuscular radiation such as To understand electron radiation.

The binders are oligomeric and polymeric resins. Resins are among oligomers understood that contain at least 2 to 15 monomer units in their molecule. in the In the context of the present invention, polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule. additional becomes these terms on Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomere", page 425.

Examples of suitable binders are statistical, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or Polycondensation. These terms are supplemented by Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "polyaddition resins (polyadducts)", and pages 463 and 464,  "Polycondensates", "Polycondensation" and "Polycondensation Resins", as well as pages 73 and 74, "Binder".

Examples of suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, especially (meth) acrylate copolymers, especially polyurethane modified (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or polycondensation resins are polyesters, Alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resins, epoxy resin Amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether Polyurethanes or polyester-polyether-polyurethanes, especially polyester and Polyurethanes.

The self-crosslinking thermally curable or dual-cure binders contain reactive ones functional groups with groups of their kind or with complementary reactive functional groups can undergo crosslinking reactions. The externally networking thermally curable or dual-cure binders contain reactive functional groups, those with complementary reactive functional groups in crosslinking agents are present, can crosslink reactions. Examples of suitable according to the invention Complementary reactive functional groups to be used are as follows Overview compiled. In the overview, the variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) residue; the variables R 'and R "stand for the same or different ones aliphatic radicals or are mutually to an aliphatic or heteroaliphatic Ring linked.

Overview

Examples of complementary functional groups

The selection of the respective complementary groups depends on the one hand on the fact that they in the manufacture, storage and application of the invention Coating materials no undesirable reactions, especially no premature ones Crosslinking, entering and / or possibly not curing with actinic radiation may disturb or inhibit, and on the other hand in which temperature range the Networking should take place.

Preferred in the coating materials of the invention Crosslinking temperatures of 60 to 180 ° C applied.

In the case of multi-component systems, in particular Two-component systems in which the binders are used until shortly before application are stored separately from the crosslinking agents, crosslinking temperatures of 60 applied up to 100 ° C. Binders with thio, hydroxyl, primary and secondary amino as well as the imino groups and crosslinking agents free isocyanate groups used.

In the case of the one-component systems in which the binders with the crosslinking agents are present, crosslinking temperatures above 100 ° C. are preferably used.

Therefore, binders with thio, hydroxyl, N-methylolamino-N- Alkoxymethylamino, imino, carbamate, allophanate, epoxy or carboxyl groups, preferably hydroxyl or epoxy groups, in particular epoxy groups, on the one hand and preferably crosslinking agents with anhydride, carboxyl, epoxy, blocked Isocyanate, urethane, methylol, methylol ether, siloxane, carbonate, amino, hydroxy  and / or beta-hydroxyalkylamide groups, preferably epoxy, hydroxy, beta Hydroxyalkylamide, unblocked isocyanate, urethane or alkoxymethylamino groups, on the other hand applied.

In the case of self-crosslinking binders, especially methylol, methylol ether and / or N-alkoxymethylamino groups used.

The binders contain functional groups which make them water-dispersible and / or water-soluble. These are either

• 1. functional groups by neutralizing agents and / or Quaternizing agents can be converted into cations, or
• 2. functional groups which are converted into anions by neutralizing agents can, and / or anionic groups and / or
• 3. nonionic hydrophilic groups, especially poly (alkylene ether) groups.

Examples of suitable functional groups (f1) by neutralizing agents and / or Quaternizing agents that can be converted into cations are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary amino groups or secondary sulfide groups.

Examples of suitable cationic groups (f1) are primary, secondary, tertiary or quaternary ammonium groups, tertiary sulfonium groups or quaternary Phosphonium groups, preferably quaternary ammonium groups or tertiary Sulfonium groups, but especially tertiary sulfonium groups.

Examples of suitable functional groups (f2) which are neutralized by Anions that can be converted are carboxylic acid, sulfonic acid or Phosphonic acid groups, especially carboxylic acid groups.  

Examples of suitable anionic groups (f2) are carboxylate, sulfonate or Phosphonate groups, especially carboxylate groups.

Examples of suitable neutralizing agents for functional convertible into cations Groups (f1) are inorganic and organic acids such as sulfuric acid, hydrochloric acid, Phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or Citric acid.

Examples of suitable neutralizing agents for functional anions convertible into anions Groups (f2) are ammonia or amines, such as. B. trimethylamine, triethylamine, Tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, Diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, Dimethylisopropylamine, dimethylisopropanolamine or triethanolamine. Is preferred Dimethylethanolamine and / or triethylamine are used as neutralizing agents.

The complementary reactive functional groups described above can according to the usual and known methods of polymer chemistry in the binder to be built in. This can be done, for example, by the incorporation of monomers which corresponding reactive functional groups, and / or with the help polymer-analogous reactions happen.

Examples of suitable olefinically unsaturated monomers with reactive functional groups, by means of which these groups can be introduced into the (meth) acrylate copolymers

• 1. Monomers which carry at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule, such as
  • - Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol esterified with the acid, or by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleinate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-inden dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofumarate or monoitaconate; Reaction products from cyclic esters, such as. B. epsilon caprolactone and these hydroxyalkyl or cycloalkyl esters;
  • - olefinically unsaturated alcohols such as allyl alcohol;
  • - Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • - Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or an equivalent amount of acrylic and / or methacrylic acid instead of the reaction product then during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;
  • - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate;
  • - N, N-di (methoxymethyl) aminoethyl acrylate or methacrylate or N, N-di (butoxymethyl) aminopropyl acrylate or methacrylate;
  • - (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl), - N-ethoxymethyl and / or N, N-di (ethoxyethyl) - (meth) acrylamide;
  • - Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; further examples of suitable monomers containing carbamate groups are described in the patents US-A-3,479,328, US-A-3,674,838, US-A-4,126,747, US-A-4,279,833 or US-A-4,340,497;
• 2. Monomers which carry at least one acid group per molecule, such as
  • - Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • - Olefinically unsaturated sulfonic or phosphonic acids or their partial esters;
  • - Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester; or
  • - Vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers).
• 3. monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, Methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or Itaconic acid or allyl glycidyl ether.

Higher functional monomers of the type described above are generally described in minor quantities used. In the context of the present invention are under minor amounts of higher functional monomers to understand such amounts which are not for crosslinking or gelling of the copolymers, in particular the  (Meth) acrylate copolymers, unless you specifically want cross-linked polymers Make microparticles.

Examples of suitable monomers for the introduction of reactive functional groups in Polyesters or polyester polyurethanes are 2,2-dimethylolethyl or propyl amine are blocked with a ketone, the resulting ketoxime group after incorporation is hydrolyzed again; or compounds containing two hydroxyl groups or two pri mary and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or at least one Contain sulfonic acid group, such as dihydroxypropionic acid, dihydroxysuccinic acid, Dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2- Dimethylolbutyric acid, 2,2-dimenthylolpentanoic acid, α, δ-diaminovaleric acid, 3,4- Diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid or 2,4-diamino diphenylethersulfonsäure.

An example of the introduction of reactive functional groups via polymer analogues Reactions is the reaction of hydroxyl-containing resins with phosgene, whereby Resins containing chloroformate groups result, and the polymer-analogous reaction the resins containing chloroformate groups with ammonia and / or primary and / or secondary amines to resins containing carbamate groups. Further examples Suitable methods of this type are described in US Pat. Nos. 4,758,632 A, 4,301,257 A or US 2,979,514 A.

The dual-cure binders also contain on average at least one, preferably at least two, group (s) with at least one with actinic radiation activatable bond (s) per molecule.

In the context of the present invention, one with actinic radiation activatable bond understood a bond that when irradiated with actinic Radiation becomes reactive and with other activated bonds of its kind Polymerization reactions and / or crosslinking reactions, the after radical and / or ionic mechanisms take place. Examples of suitable bindings are carbon-hydrogen single bonds or carbon-carbon,  Carbon-oxygen, carbon-nitrogen, carbon-phosphorus or Carbon-silicon single bonds or double bonds. Of these, they are Carbon-carbon double bonds are particularly advantageous and are therefore very particularly preferably used according to the invention. For brevity, they will be in the hereinafter referred to as "double bonds".

Accordingly, the group preferred according to the invention contains one double bond or two, three or four double bonds. More than one double bond can be used the double bonds are conjugated. According to the invention, however, it is advantageous if the Double bonds isolated, in particular each one individually, in the here in question standing group. According to the invention, it is particularly advantageous two especially one to use double bond.

On average, more than one group can be activated with actinic radiation applied per molecule, the groups are structurally different from each other or from same structure.

If they are structurally different from one another, this means within the scope of the present one Invention that two, three, four or more, but especially two, with actinic Radiation-activatable groups can be used, which differ from two, three, four or more, but in particular derive two monomer classes.

Examples of suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, Vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, Isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.

The groups are preferably via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups, to the respective Basic structures of the binders bound. This is usually done by usual and known polymer-analogous reactions such as the reaction of pendant Glycidyl groups with the olefinically unsaturated monomers described above,  which contain an acid group, from pendant hydroxyl groups with the Halides of these monomers, containing hydroxyl groups with double bonds Isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1- methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or from Isocanate groups with the hydroxyl-containing monomers described above.

In the case of polyurethanes and polyesters, the groups can be introduced with the aid of compounds which contain at least one, in particular one, of the isocyanate-reactive or acid-reactive functional groups described above and at least one, in particular one, bond which can be activated with actinic radiation. Examples of suitable compounds of this type are

• - 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4- Hydroxybutyl, bis (hydroxymethyl) cyclohexane, neopentyl glycol, Diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol acrylate, methacrylate, ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether, isopropenyl ether or -butenylether;
• - trimethylolpropane mono-, glycerol mono-, trimethylolethane mono-, Pentaerythritol mono-, homopentaerythritol mono-, pentaerythritol di-, Homopentaerythritol, trimethylolpropane, glycerol, trimethylolethane, Pentaerythritol tri or homopentaerythritol triacrylate, methacrylate, ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether, isopropenyl ether or butenyl ether; or
• - Reaction products from cyclic esters, such as. B. epsilon-caprolactone, and hydroxyl-containing monomers described above; or
• - 2-aminoethyl (meth) acrylate and / or 3-aminopropyl (meth) acrylate.

The binders described above are common and known compounds and are described in detail, for example, in patent applications EP 0 089 497 A1, EP 0 256 540 A1,  EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1; EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431 A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1, EP 0 817 684, column 5, lines 31 to 45, DE 44 37 535 A1, Page 7, line 8, to page 8, line 49, EP 0 787 195 A1, DE 40 05 961 A1, DE 41 10 520 A1, EP 0 752 455 B1, DE 198 55 455 B1, DE 199 488 121 A1, DE 198 469 171 A1, EP 0 788 523 B1 or WO 95/12626.

The content of dispersion (III) in the binders described above can be very high vary widely. The content is preferably in each case based on the total amount the dispersion (III), 1 to 80, preferably 2 to 70, 3 to 60, particularly preferably 4 to 50, very particularly preferably 5 to 40 and in particular 6 to 30% by weight.

In addition, the dispersion (III) can be customary and known coloring, electrical conductive or magnetically shielding pigments, soluble dyes and / or fillers contain.

Examples of suitable inorganic color pigments are 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.

Examples of suitable organic color pigments are monoazo pigments, Bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, Quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments,  Indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, Thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, Phthalocyanine pigments or aniline black.

In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", Pages 451 to 453 "Pigments" to "Pigment Volume Concentration", page 563 "Thioindigo Pigments", page 567 "Titanium dioxide pigments", pages 400 and 467, "Naturally occurring pigments", Page 459 "Polycyclic Pigments", page 52, "Azomethine Pigments", "Azo Pigments", and page 379, "Metal Complex Pigments".

Examples of suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.

Examples of suitable magnetically shielding pigments are pigments based on them of iron oxides or chromium dioxide.

Suitable soluble organic dyes are lightfast organic dyes with a little or no tendency to migrate from the inventive Coating materials and the coatings produced from them. The The specialist can tend to migrate on the basis of his general specialist knowledge estimate and / or with the help of simple preliminary tests, for example in Determine the framework of tinting tests.

Examples of suitable organic and inorganic fillers are chalk, calcium sulfates, Barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as Aluminum hydroxide or magnesium hydroxide or organic fillers such as Plastic powder, especially made of polylamide or polyacrylonitrile. In addition, on Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998; Pages 250 ff., "Fillers" referenced.

It can be advantageous to use mixtures of platelet-shaped inorganic fillers such as talc or mica and non-platelet-shaped inorganic fillers such as chalk,  Dolomite calcium sulfate, or barium sulfate to use because of this the viscosity and the flow behavior can be adjusted well.

The pigments, dyes and fillers described above can be in finely divided, not in opaque form.

The dispersion (III) can also further additives such as nanoparticles, thermal or reactive diluents curable with actinic radiation, those described above with Water miscible and / or organic miscible only to a small extent Solvents, UV absorbers, light stabilizers, radical scavengers, thermolabile radicals Initiators, photoinitiators and coinitiators, crosslinking agents, catalysts for the thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, ent foaming agents, emulsifiers, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming aids, rheology-controlling additives (thickeners), flame retardants, Desiccants, drying agents, skin preventing agents, corrosion inhibitors, waxes and / or matting agents.

Suitable nanoparticles are in particular those based on silicon dioxide, Aluminum oxide and zirconium oxide with a particle size <50 nm, which none Have a matting effect. Examples of suitable nanoparticles based on Silicon dioxide is pyrogenic silicon dioxide, which is sold under the trade name Aerosil® VP8200, VP721 or R972 from Degussa or the trade name Cab O Sil® TS 610, CT 1110F or CT 1110G from CABOT. in the Generally, these nanoparticles are in the form of dispersions with actinic Radiation-curable monomers, such as the reactive diluents described below, distributed. Examples of suitable monomers which are suitable for the present Are particularly suitable for use, are alkoxylated pentaerythritol tetra or triacrylate, ditrimethylolpropane tetra- or triacrylate, dineopentyl glycol diacrylate, Trimethylolpropane triacrylate, trishydroxyethyl isocyanurate triacrylate, dipentaerythritol penta- or hexaacrylate or hexanediol diacrylate. Generally they contain dispersions the nanoparticles in an amount of 10 to 80% by weight, based on the dispersions, preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight and in particular 25 to 50% by weight. An example of a particularly suitable dispersion  of nanoparticles is the dispersion, which is sold under the trade name High Link® OG 103-31 is distributed by Clariant Hoechst.

Examples of suitable thermally curable reactive diluents are positional isomers Hyperbranched compounds containing diethyloctanediols or hydroxyl groups or Dendrimers, as described, for example, in German patent applications DE 198 05 421 A 1, DE 198 09 643 A1 or DE 198 40 405 A1.

Examples of suitable reactive diluents curable with actinic radiation are those in Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword, "reactive thinner", or in column 7, lines 1 to 26 of DE 198 18 715 A1 or reactive diluents with at least 5, in particular 5 bonds in the molecule which can be activated with actinic radiation, such as for example dipentaerythritol pentaacrylate.

Examples of suitable thermolabile free radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, Peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, Azodinitrile or Benzpinakolsilylether.

Examples of suitable catalysts for the crosslinking are dibutyltin dilaurate, Dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts such as bismuth lactate or - dimethylolpropionate.

Examples of suitable photoinitiators and coinitiators are found in Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446.

Examples of suitable crosslinking agents, such as those used in multicomponent systems and which are usually added to the dispersions (III) subsequently, are polyisocyanates with an average of at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule, such as

• - Diisocyanates such as isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1,3,3- trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethyl cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5- Isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3 - isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1- yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane, 1,2- Diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2- Diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2- Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, tri methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate (HDI), ethyl ethylene diisocyanate, trimethylhexane diisocyanate, heptamethylene diisocyanate or diisocyanates derived from Dimer fatty acids, such as those available under the trade name DDI 1410 from the company Henkel sold and in the patents WO 97/49745 and WO 97/49747 are described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1-pentyl cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1- yl) cyclohexane, 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane or liquid bis (4-isocyanatocyclohexyl) methane with a trans / trans content of up to 30 wt .-%, preferably 25 wt .-% and in particular 20 wt .-%, as in the Patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 is described, preferably isophorone diisocyanate, 5- Isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethylcyclohexane, 5-isocyanato-1- (3- isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1- yl) -1,3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) - cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4- isocyanatobut-1-yl) cyclohexane or HDI, in particular HDI;
• - Isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea Carbodiimide and / or uretdione polyisocyanates, which in Usual and known manner from the diisocyanates described above getting produced; Examples of suitable manufacturing processes and polyisocyanates  are for example from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A, US 4,801,675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A, US 5,290,902 A, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 known; or
• - Dual-cure polyisocyanates made from the polyisocyanates described above and the compounds described above which contain at least one in particular one of the isocyanate-reactive or described above acid-reactive functional groups and at least one, especially one, with contain actinic radiation activatable bond are produced (cf. z. B. the European patent application EP 0 928 800 A1).

Examples of suitable crosslinking agents as used in one-component systems are aminoplast resins such as those found in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., the book "Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff Patents US 4,710,542 A or EP 0 245 700 A1 and in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, Pages 193 to 207; Compounds containing carboxyl groups or Resins such as are described, for example, in patent specification DE 196 52 813 A1; Compounds or resins containing epoxy groups, as described, for example, in US Pat Patent specifications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A or US 3,781,379 A; blocked polyisocyanates as they do for example in the patents US 4,444,954 A, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1 can be described; and or Tris (alkoxycarbonylamino) triazines, as described in the patents US 4,939,213 A, US 5,084,541 A, No. 5,288,865 A or EP 0 604 922 A1.

Examples of suitable deaerating agents are diazadicycloundecane or benzoin.  

Examples of suitable emulsifiers are nonionic emulsifiers, such as alkoxylated ones Alkanols, polyols, phenols and alkylphenols or anionic emulsifiers such as Alkali salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and Sulphonic acids of alkoxylated alkanols, polyols, phenols and alkylphenols.

Examples of suitable wetting agents are siloxanes, fluorine-containing compounds, Carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or Polyurethanes.

An example of a suitable adhesion promoter is tricyclodecanedimethanol.

Examples of suitable film-forming aids are cellulose derivatives such as Cellulose Acetobutyrate (CAB).

Examples of suitable rheology-controlling additives (thickeners) are those from the Patent applications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945 known; crosslinked polymeric microparticles, as described, for example, in EP 0 008 127 A1 are disclosed; inorganic layered silicates such as Aluminum-magnesium silicates, sodium-magnesium and Montmorillonite type sodium magnesium fluorine lithium layered silicates; Silicas such as aerosils; or synthetic polymers with ionic and / or associative active groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, Polyvinylpyrrolidone, styrene-maleic anhydride or Ethylene-maleic anhydride copolymers and their derivatives or polyacrylates; or associative thickeners based on polyurethane, such as those found in Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "thickener", Pages 599 to 600, and in the textbook "Lackadditive" by Johan Bieleman, Wiley- VCH, Weinheim, New York, 1998, pages 51 to 59 and 65; in particular combinations of ionic and nonionic thickeners, such as those in the Patent application DE 198 41 842 A1 for setting a pseudoplastic behavior to be discribed; or the combination of associative thickeners  Polyurethane-based and polyurethane-based wetting agents, as described in German Patent application DE 198 35 296 A1 is described in detail.

Magnesium stearate is an example of a suitable matting agent.

Further examples of the additives listed above and examples of suitable ones UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, Desiccants, skin inhibitors, corrosion inhibitors and waxes (B) are described in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described in detail.

The preparation of the dispersion (III) offers no special methodological features, but rather takes place as described above for the dispersion (I) and (II).

The same applies to the production of the coating material of the invention from the Dispersion (III) and dispersions (I) and (II). It is an advantage if you have the Dispersion (II) before dispersion (I) combined with dispersion (III).

The ratio of dispersion (I) to dispersion (II) can vary very widely depends primarily on the effect pigments present, their Concentration and the optical effect to be adjusted. Preferably lies the ratio (I): (II) at 1:10 to 10: 1, preferably 1: 8 to 8: 1, particularly preferably 1 6 to 6: 1, very particularly preferably 1: 4 to 4: 1 and in particular 1: 2 to 2: 1.

The coating material of the invention is suitable for numerous applications Fields of automotive serial painting, car refinishing, painting of Buildings indoors and outdoors, painting furniture, doors and windows as well as industrial painting, including container coating and coil coating and the Coating of electrical components, suitable. The invention can Coating material as filler, waterborne basecoat or solid-color topcoat, but especially as Waterborne basecoat can be used. It serves as a water-based paint for the production of multi-layer paint systems according to the invention after wet-on-wet Method.  

Suitable substrates consist of metals, plastics, wood, ceramics, stone, textiles, Fiber-bonded, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well Connected these materials.

In the case of electrically conductive substrates, primers can be used which are in are produced in a customary and known manner from electrocoat materials. Come for this both anodic and cathodic electrocoat materials, but especially cathodic ones, into consideration.

On the electrocoating, there can be one from a common and known Filler paint or stone scarf protection primer.

Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE; UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted. In the case of non-functionalized and / or non-polar Substrate surfaces can be coated in a known manner before coating Pretreatment, such as with a plasma or with flame, subjected to or with a Primer.

Suitable clearcoats for the wet-on-wet process are single or Multi-component clear coats, powder clear coats, powder slurry clear coats, UV-curable Clear varnishes or sealers, such as those found in patent applications, patents and Publications DE 42 04 518 A1, EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A1; US 5,356,669 A1 or US 5,605,965 A1, DE 42 22 194 A1, the product information from BASF Lacke + Farben AG, "Powder Coatings", 1990, the company name of BASF Coatings AG "Powder Coatings, Powder coatings for industrial applications ", January 2000, US 4,268,542 A1, DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE 196 52 813 A1,  DE-A-198 14 471 A1, EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1, EP 0 002 866 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1, DE 20 03 579 B1, WO 97/46549, WO 99/14254, US 5,824,373 A1, US 4,675,234 A1, US 4,634,602 A1, US 4,424,252 A1, US 4,208,313 A1, US 4,163,810 A1, US 4,129,488 A1, US 4,064,161 A. 1, US 3,974,303 A1, EP 0 844 286 A1, DE 43 03 570 A1, DE 43 03 570 A1, DE 34 07 087 A1, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A1, DE 40 20 316 A1 or DE 41 22 743 A1 are known.

The application of the coating materials according to the invention can be carried out by all customary methods Application methods, such as. B. spraying, knife coating, painting, pouring, dipping, watering, Dribbling or rolling take place. The substrate to be coated can be used as such rest, with the application device or system being moved. However, this can also be done substrate to be coated, in particular a coil, are moved, the Application system rests relative to the substrate or is moved in a suitable manner.

Spray application methods, such as, for example, are preferably used Compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), possibly connected with hot spray application such as hot air Hot spraying. The applications can be used at temperatures of max. 70 to 80 ° C be carried out so that suitable application viscosities are achieved without a change in the briefly acting thermal load or Damage to the coating material of the invention and, if appropriate, its reprocessing overspray to be reprocessed. This is how hot spraying can be designed be that the coating material is heated only very briefly in or just before the spray nozzle becomes.

The spray booth used for the application can be used, for example, with a optionally temperature-controlled circulation can be operated with a suitable Absorbent medium for the overspray, e.g. B. the coating material applied in each case itself, is operated.  

The coating material of the invention is thermal and with actinic radiation curable, the application is preferred when illuminated with visible light Wavelength of over 550 nm or in the absence of light. This will a material change or damage to the dual-cure according to the invention Avoid coating material and overspray.

In general, in the production of the effect-giving invention Multicoat paint systems the waterborne basecoat film according to the invention and the Clear coat applied in a wet coat thickness that after curing, layers with the necessary and advantageous layer thicknesses for their functions result; in the In the case of the basecoat, they are 5 to 50, preferably 6 to 40, particularly preferably 7 to 30 and in particular 8 to 25 microns, and in the case of clearcoats they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 µm.

If electrocoat layers and filler layers are used, there are Layer thicknesses in the case of electrocoating at 5 to 50, preferably 6 to 45, particularly preferably 7 to 40 and in particular 8 to 35 microns and in the case of Filler coating at 10 to 150, preferably 15 to 120, particularly preferably 20 to 100 and in particular 25 to 90 µm.

The hardening can take place after a certain rest period. It can last for 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 30 min. The Rest time is used, for example, for the course and for degassing the applied layers or to evaporate volatile components such as solvents or water. The Rest time can be supported and / or by using elevated temperatures up to 80 ° C be shortened, provided there is no damage or changes to the applied Shifts occur, such as early complete networking.

The thermal hardening has no special features in terms of method, but takes place according to the usual and known methods such as heating in a forced air oven or Irradiate with IR lamps. The hardening can also be carried out in stages. she takes place according to the invention at temperatures of 60 to 180 ° C, preferably during a  Time from 1 min to 2 h, particularly preferably 2 min to 1 h and in particular 3 min up to 30 min.

Even curing with actinic radiation has no special methodological features, but takes place with the help of electromagnetic radiation such as near infrared, visible Light, UV radiation or X-rays, in particular UV radiation, and / or Corpuscular radiation like electron radiation. UV radiation is preferred applied.

In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be done directly by adding carbon dioxide and / or nitrogen, for example the surface of the applied layers can be guaranteed. Even in the case of Curing with UV radiation can, in order to avoid the formation of ozone, under inert gas be worked.

For curing with actinic radiation, the usual and well-known Radiation sources and optical auxiliary measures applied. Examples of more suitable Radiation sources are high or low pressure mercury vapor lamps, which optionally doped with lead to open a radiation window up to 405 nm, or Electron beam sources. Further examples of suitable radiation sources are given in the German patent application DE 198 18 735 A1, column 10, lines 31 to 61. Their arrangement is known in principle and can take into account the conditions of the workpiece and the process parameters are adjusted. For complicated shaped workpieces like Automobile bodies can be the areas not accessible to direct radiation (Shadow areas) such as cavities, folds and other design-related Undercuts with spot, small area or all-round emitters connected with one automatic moving device for the irradiation of cavities or edges, be cured.

The facilities and conditions of these hardening methods are also described in R. Holmes, U. V. and E. B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom, 1984.  

The hardening can take place in stages, i. H. by multiple exposure or Irradiation with actinic radiation. This can also take place alternately, i. that is for example, alternately cured with UV radiation and electron radiation.

Thermal curing and curing with actinic radiation can be carried out simultaneously or can be used alternately. The two hardening methods will alternate used, for example, can begin with actinic radiation and end with thermal curing. In other cases, it can prove to be beneficial prove to start and end with curing with actinic radiation. The person skilled in the art can determine the hardening method which is appropriate for the individual case The most advantageous is due to his general specialist knowledge if necessary under Determine simple preliminary tests.

The single-layer and multi-layer effect coatings according to the invention produced from the coating materials according to the invention, in particular the effect multi-layer coatings according to the invention, have the overall quality required for use in automotive series coating. So are yours
optical properties (appearance) such as

• - Shine,
• - Mapping Distinctness (DOI),
• - opacity,
• - striking dichroic optical effects,

their mechanical properties like

• - hardness,
• - scratch resistance,
• - abrasion resistance and
• - impact strength,

their adhesive properties like

• - interlayer adhesion and
• - Adhesion to the substrate

as well as their chemical properties like

• - weather resistance,
• - UV resistance,
• - resistance to tarnishing,
• - Etch resistance and
• - Resistance to chemicals (especially acids and bases), solvents, Resin, bird droppings and petrol

at such a high level that they can also be used for painting particularly high quality Luxury automobiles come into consideration.

But above all, they are characterized by an excellent uniformity of color in the area and show no or very few and hardly visible light-dark Shades or clouds.

Examples and comparative tests Production Example 1 The preparation of an aqueous polyurethane dispersion

716.6 parts by weight of a condensation product (number average molecular weight: 1410) from 1.81 mol of a polymeric fatty acid (dimer content at least 98% by weight, Trimer content at most 2.0% by weight, monomer content at most traces), 0.82 mol Isophthalic acid, 0.61 mol of hexanediol and 0.61 mol of neopentyl glycol, 61 parts by weight Dimethylolpropionic acid, 10.6 parts by weight of neopentyl glycol, 365 parts by weight Methyl ethyl ketone and 308.3 parts by weight of m-tetramethylxylylidene diisocyanate were in a suitable reaction vessel with stirring under a nitrogen atmosphere to 80 ° C  heated. The reaction was up to an isocyanate content of 1.1 wt .-%, based on the Total amount of the reaction mixture continued. Then 52.6 Parts by weight of trimethylolpropane are added, after which the resulting Reaction mixture was stirred at 80 ° C until no free isocyanate groups were more detectable. Then 33 parts by weight of dimethylethanolamine, 255 parts by weight of butyl glycol and then 2153 parts by weight of deionized water stirred. The methyl ethyl ketone was distilled off under vacuum. The result was one finely divided dispersion, the pH of which with dimethylethanolamine to 7.4 and not volatile content were adjusted to 31% by weight with deionized water.

Preparation example 2 The preparation of an aqueous polyester resin solution

In a reactor equipped with stirrer, thermometer and packed column 729 parts by weight of neopentyl glycol, 768 parts by weight of hexanediol, 462 parts by weight Hexahydrophthalic anhydride and 1710 parts by weight of a polymeric fatty acid (Dimer content at least 98% by weight, trimere content at most 2% by weight, Monomer content at most traces) weighed and melted. The resulting melt was heated with stirring so that the Column head temperature did not exceed 100 degrees Celsius. It was at maximum with Esterified 220 ° C until an acid number of 9 was reached. After cooling down 1808 ° C., 768 parts by weight of trimellitic anhydride were added and further esterified, until an acid number of 32 was reached. The reaction mixture was then brought up to 120 Cooled degrees Celsius and dissolved with 1392 parts by weight of butyl glycol. After this Cooling to 90 ° C were slowly 158 parts by weight of dimethylethanolamine and then stirred in 1150 parts by weight of deionized water. The resulting one Polyester resin solution was adjusted to pH 7.6 with dimethylethanolamine and with deionized water adjusted to a non-volatile content of 60 wt .-%.

Preparation example 3 The production of a polyurethane modified polyacrylate resin

500 parts by weight of a condensation product (number average molecular weight: 1423) from 1.0 mol of a polymeric fatty acid (dimer content at least 98% by weight, Dimer content not more than 2.0% by weight, monomer content highest traces), 1.5 mol Isophthalic acid, 1.6 moles of neopentyl glycol and 1.7 moles of hexanediol, 31.2 parts by weight Neopentyl glycol, 185 parts by weight methyl ethyl ketone, 201.7 parts by weight m- Tetramethylxylylidene diisocyanate and 0.7 part by weight of dibutyltin dilaurate were added Stirring heated to 80 ° C under a nitrogen atmosphere. The reaction was up to an isocyanate content of 1.3 wt .-%, based on the total amount of Reaction mixture continued. Thereafter, 30 parts by weight of diethanolamine added, and the resulting reaction mixture was stirred at 80 ° C until no more isocyanate groups were detectable. Then 466 parts by weight Butyl glycol stirred in, after which the methyl ethyl ketone was distilled off in vacuo. The the resulting polyurethane solution was then applied to a butyl glycol non-volatile content of 60 wt .-% set.

In a steel boiler, equipped with monomer feed, initiator feed, thermometer, Oil heating and reflux condenser were 28.44 parts by weight of butyl glycol and 24, 24 Parts by weight of the above-mentioned polyurethane solution and heated to 110 ° C. Then a solution of 5.1 parts by weight of t-butyl perethylhexanoate in 6.0 Parts by weight of butyl glycol evenly added at such a rate that the addition was completed after 5.5 hours. With the start of the addition of initiator was also with the addition of a mixture of 18.36 parts by weight of n-butyl methacrylate, 17 parts by weight of methyl methacrylate, 17 parts by weight of lauryl methacrylate, 17.34 Parts by weight of hydroxypropyl acrylate and 12.75 parts by weight of styrene started. The Monomer mixture was added evenly at such a rate that the addition was completed in five hours. After the initiator solution was completely added, the reaction temperature remained for an hour Kept at 110 ° C.

Subsequently, a solution of 1.17 parts by weight of t-butyl perethylhexanoate in 3.5 parts by weight of butyl glycol evenly added at such a rate that the addition was complete after 1.5 hours. With the start of adding the  Initiator solution was also added with a mixture of 5.85 parts by weight Acrylic acid and 4.65 parts by weight of n-butyl methacrylate, 2.94 parts by weight Methyl methacrylate, 5.90 parts by weight lauryl methacrylate, 1.25 parts by weight Hydroxypropyl acrylate and 2.94 parts by weight of styrene started. The monomer mixture was added evenly at such a rate that the addition was completed within an hour. After that the temperature of the Reaction mixture kept at 110 ° C for 1.5 hours. The resulting one Resin solution was distilled under vacuum to a solids content of 80% by weight concentrated and with dimethylethanolamine at this temperature within 30 Minutes neutralized to a degree of neutralization of 80%. The resin solution was cooled to 60 ° C, after which the heating was turned off. Then slowly Water was added until the solids content of the dispersion was 40% by weight. The The dispersion had an acid number of 36.7 mg KOH / g and a pH of 7.6.

Preparation example 4 The production of a dispersion containing effect pigments (I)

The dispersion (I) was prepared by mixing 3.0 parts by weight of the commercially available Aluminum effect pigments Alu-Stapa Hydrolux® VP 51284 / G6, 1.8 parts by weight of the commercially available aluminum effect pigment Alu-Stapa Hydrolux® 2154 (both from the Eckart), 4.8 parts by weight of butyl glycol, 1.0 part by weight of 1-propoxy-2-propanol and 2.4 parts by weight of the polyester resin solution prepared in Preparation Example 2.

Preparation example 5 The production of a further dispersion containing effect pigments (I)

The dispersion (I) was prepared by mixing 0.6 part by weight of the commercially available Aluminum effect pigments Alu-Stapa Hydrolux® VP 51284 / G6, 1.8 parts by weight of the commercially available aluminum effect pigment Alu-Stapa Hydrolux® 2154 (both from the Eckart), 2.9 parts by weight of butyl glycol and 2.4 parts by weight of Polyester resin solution prepared according to preparation example 2.  

Preparation example 6 The preparation of a dispersion containing effect pigments (II)

The dispersion (II) was prepared by mixing 2.4 parts by weight of the commercially available Aluminum effect pigments Alu-Stapa Hydrolux® VP 51284 / G6, 1.9 parts by weight Butylglycol, 1.0 part by weight of 1-propoxy-2-propanol and 0.5 part by weight of 2-ethyl-1- hexanol produced.

Example 1 and comparative experiment V1 The preparation of one according to the invention (Example 1) and one not inventive (comparative experiment V1) waterborne basecoat

The water-based lacquer according to the invention and the water-based lacquer not according to the invention were obtained by Mix the starting products specified in Table 1 in the specified Order established.

Table 1

The material composition of the water-based lacquer according to the invention (example 1) and that not according to the invention (comparative experiment V1)

The water-based paints were adjusted to a viscosity of 70 to 90 mPas in a shear field of 1,000 s ^-1 .

Example 2 and comparative experiment V2 The preparation of one according to the invention (Example 2) and one not multi-layer coating according to the invention (comparative experiment V2)

For example 2, the waterborne basecoat of example 1 was used.

For the comparative test V2, the waterborne basecoat of the comparative test V1 used.

For testing the application properties of waterborne basecoats Test boards measuring 30 × 70 cm are produced in a customary and known manner. For this purpose, steel panels (body panels), which are used with a customary and known cathodically deposited and baked electrodeposition coating were coated with a commercially available filler from BASF Coatings AG, after which the resulting filler layer for five minutes at 20 ° C and a relative Air humidity of 65% and vented in a forced air oven for 30 minutes 140 ° C was baked.

After the test panels had cooled to 20 ° C, the waterborne basecoats were applied in two Spray coats applied. The first order is made using ESTA (bell speed: 45,000 rpm. Steering air: 120 Nl / min. Voltage: 65 KV; Distance: 0.25 m; Outflow amount of paint: 170 ml / min), corresponding to a dry film thickness of 8 to 2 µm. The second job was carried out pneumatically (distance: 0.32 m; paint flow rate: 540 ml / min; atomizing air Quantity: 300 Nl / min. Atomizing air pressure: 4.8 bar; Horn air pressure: 5.2 bar; Hornluft- Quantity: 395 Nl / min), corresponding to a dry film thickness of 4 to 6 µm. The Waterborne basecoats were applied after the first and second coats, respectively flashed off for two minutes.

After application, the waterborne basecoats were left at 80 ° C for 15 minutes dried, cooled and with a commercially available two-component clear varnish from the company BASF Coatings AG overlays. After that, the waterborne basecoats and the Clear coat layers baked at 130 ° C for 30 minutes, which makes the Multi-layer coating according to the invention of Example 2 and that not according to the invention Multi-layer painting of comparative test V2 resulted.  

The test panels were monitored under diffuse light from a distance of 2 to 3 m (80 °) and obliquely (40 °) visually with regard to the light-dark shading (clouds) assessed and graded (grade 1: no clouds visible; up to grade 5: clouds very clear visible).

The following results were obtained:

Example 2

Clouds (supervision): 2; Clouds (oblique view) 3

Comparative experiment V1

Clouds (supervision) 3; Clouds (oblique view) 5

Thus, the waterborne basecoat of Example 2 showed significantly less light-dark Shades as the waterborne basecoat of Comparative Experiment V2.

Claims (12)

1. Aqueous, effect-imparting coating material, comprising at least one water-soluble or dispersible binder and at least one effect pigment, can be prepared by:

• A) a first part of the effect pigment or at least a first effect pigment in a mixture
  at least one water-miscible organic solvent and
  an aqueous solution or dispersion of at least one water-soluble or dispersible binder
  dispersed and
• B) a second part of the effect pigment or at least a second effect pigment in a mixture
  at least one water-miscible organic solvent and
  at least one solvent that is immiscible or only slightly miscible with water
  dispersed, after which
• C) the dispersions (I) and (1I) combined with the aqueous solution or dispersion of at least one water-soluble or dispersible binder.

2. Coating material according to claim 1, characterized in that the Dispersion (II) before dispersion (I) combined with dispersion (III). 3. Coating material according to claim 1 or 2, characterized in that the in Water does not or only to a small extent miscible organic solvents 20 ° C less than 10 wt .-%, based on water and solvent, of water can record. 4. Coating material according to one of claims 1 to 3, characterized in that Water at 20 ° C less than 6 wt .-%, based on water and solvent the organic which is immiscible or only miscible to a small extent in water Can absorb solvents. 5. Coating material according to one of claims 1 to 3, characterized in that one uses 2-ethyl-1-hexanol (isooctanol) as organic solvent. 6. Coating material according to one of claims 1 to 5, characterized in that one uses metallic effect pigments as effect pigments. 7. Coating material according to claim 7, characterized in that as Metallic effect pigments Aluminum effect pigments used. 8. Coating material according to claim 7, characterized in that as Aluminum effect pigments leafing and / or non-leafing pigments used. 9. Coating material according to claim 7 or 8, characterized in that Aluminum effect pigments are used, which has an essentially round shape and / or have a substantially elongated shape. 10. Coating material according to one of claims 1 to 9, characterized in that one as water-soluble or dispersible binders polyurethane, polyester and / or polyurethane-modified (meth) acrylate copolymers used.   11. A method for producing a coating material according to one of claims 1 to 10, characterized in that

• A) a first part of the effect pigment or at least a first effect pigment in a mixture
  at least one water-miscible organic solvent and
  an aqueous solution or dispersion of at least one water-soluble or dispersible binder
  dispersed and
• B) a second part of the effect pigment or at least a second effect pigment in a mixture
  at least one water-miscible organic solvent and
  at least one solvent which is immiscible or only slightly miscible with water
  dispersed, after which
• C) the dispersions (I) and (II) are combined with the aqueous solution or dispersion of at least one water-soluble or dispersible binder.

12. Use of the coating materials according to one of claims 1 to 10 and / or the coating materials prepared according to claim 11 in the Automobile series painting, car refinishing, the painting of Buildings indoors and outdoors, painting doors, windows and Furniture as well as industrial painting, including coil coating, containers Coating and coating of electrical components.