EP0881954B1 - Multi-coat painting process - Google Patents

Multi-coat painting process Download PDF

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Publication number
EP0881954B1
EP0881954B1 EP97903326A EP97903326A EP0881954B1 EP 0881954 B1 EP0881954 B1 EP 0881954B1 EP 97903326 A EP97903326 A EP 97903326A EP 97903326 A EP97903326 A EP 97903326A EP 0881954 B1 EP0881954 B1 EP 0881954B1
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EP
European Patent Office
Prior art keywords
lacquer coating
coating composition
base lacquer
resins
aqueous
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.)
Expired - Lifetime
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EP97903326A
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German (de)
French (fr)
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EP0881954A1 (en
Inventor
Detlef Schlaak
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EIDP Inc
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Herberts GmbH
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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

Definitions

  • the invention relates to a method for producing a multilayer painting, especially metallic substrates, the is particularly suitable for automotive painting.
  • Basecoat and clearcoat are preferably wet-on-wet applied, i.e. the basecoat is after a flash-off time, if necessary with heating, and after subsequent application a clear varnish baked together with this.
  • EP-A-0 238 037 is a method to reduce burn-in layers become known in which a filler and an aqueous metallic base coat applied by the wet-on-wet method. The sample part is it can be seen that the filler layer in a usual for filler paints Dry film thickness of 35 microns is applied.
  • the object of the invention is to provide a method for producing Multi-layer paintwork, in particular of automotive paintwork with comparable to the prior art Overall property level, but reduced layer thickness of the To provide overall paint structure, which with as few as possible Burn-in steps can be carried out.
  • the method of multi-layer coating of the invention provided with a burned-in first electrocoat layer Substrate, which is characterized in that on this first Electrocoating layer a second coating layer corresponding to one Dry layer thickness from 10 to less than 30 ⁇ m from a first aqueous, color and / or effect basecoat, the one or contains several polyurethane resins, is applied, whereupon wet-on-wet a third coating layer corresponding to a dry layer thickness of 7 to 15 microns from a second aqueous, color and / or effect Basecoat coating agent applied and on the third coating layer a fourth coating layer from one without baking Clear lacquer coating agent applied and the second, third and fourth Coating layer are baked together, with a first aqueous Basecoat is used, which has a higher content Polyurethane resin has as the second basecoat based on the total weight of the respective aqueous basecoat coating agent, and the solid resin content in the first basecoat coating agent not more than
  • the method according to the invention makes it possible to directly access a burned-in first coating layer created by electrodeposition apply an aqueous basecoat and this layer together with the subsequently applied second Burn in the water-based lacquer layer and clear lacquer layer, using usual Filler layers or other intermediate layers are eliminated.
  • the first layer of coating namely a primer
  • ETL cathodically depositable electrocoat materials
  • aqueous coating agents with a Solids up to 50% by weight, for example 10 to 20% by weight.
  • the Solid is formed from the usual for electrodeposition painting Binders, the ionic groups or in ionic groups convertible groups and, if necessary, for chemical crosslinking capable groups, and any existing crosslinkers, Pigments, fillers and / or additives common in paint.
  • the Ionic or groups which can be converted into ionic groups can be anionic or groups which can be converted into anionic groups, e.g. acidic groups like - COOH groups or cationic or convertible into cationic groups, e.g. basic groups such as amino, ammonium, e.g.
  • Binders with basic groups are preferred. Particularly preferred are nitrogen-containing basic groups. These groups can quaternized or at least partially with one usual neutralizing agent, an acid, e.g. an organic Monocarboxylic acid, e.g. Formic acid or acetic acid, in ionic Groups convicted.
  • an acid e.g. an organic Monocarboxylic acid, e.g. Formic acid or acetic acid, in ionic Groups convicted.
  • the electrodeposition lacquer layer For the production of the first coating layer, the electrodeposition lacquer layer, it is possible, for example, to use the usual anodically depositable electrodeposition lacquer binders and lacquers (ATL) containing anionic groups.
  • ATL lacquers
  • binders based on polyesters, epoxy resins, poly (meth) acrylates, maleate oils or polybutadiene oils with a weight average molecular weight of, for example, 300 to 10,000 and an acid number of 35 to 300 mg KOH / g.
  • the binders carry, for example, -COOH, -SO 3 H and / or -PO 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
  • the binders can be self-crosslinking or externally crosslinking.
  • the lacquers can therefore also contain customary crosslinking agents, for example triazine resins, crosslinking agents which contain groups capable of transesterification or blocked polyisocyanates.
  • customary crosslinking agents for example triazine resins, crosslinking agents which contain groups capable of transesterification or blocked polyisocyanates.
  • Specific examples of such anodically depositable electrodeposition paint binders and paints (ATL) which contain anionic groups and can be used in the process according to the invention are described, for example, in DE-A-28 24 418.
  • cathodic electrodeposition paints are preferred based on cationic or basic binders for the production of first coating layer used.
  • Such basic resins are for example primary, secondary or tertiary amino groups resins containing, the amine numbers e.g. at 20 to 250 mg KOH / g lie.
  • the weight average molecular weight (Mw) of the base resins is preferably from 300 to 10,000.
  • Examples of such base resins are Amino (meth) acrylate resins, amino epoxy resins, amino epoxy resins with terminal double bonds, amino epoxy resins with primary OH groups, Aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products.
  • This Base resins can be self-crosslinking or they are known Crosslinkers used in the mixture.
  • Crosslinkers are Aminoplast resins, blocked polyisocyanates, crosslinkers with terminal Double bonds, polyepoxide compounds or crosslinkers Contain transesterifiable groups.
  • Specific examples of in base resins and cathodic dip lacquer (KTL) baths Crosslinkers are e.g.
  • EP-A-0 082 291 EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 456 270, US 3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199, EP-A-0 476 514.
  • Such resins can be used alone or in a mixture.
  • Prefers so-called “non-yellowing" -KTL systems are used, the one Yellowing or discoloration of the multi-layer coating when baked avoid.
  • it is by means of special selected blocked polyisocyanate crosslinking KTL systems, such as described for example in EP-A-0 265 363.
  • ETL electrocoat
  • pigments and fillers come the usual inorganic and / or organic pigments and Fillers in question. Examples are carbon black, titanium dioxide, Iron oxide pigments, phthalocyanine pigments, quinacridone pigments, kaolin, Talc or silicon dioxide.
  • the pigments can be dispersed into pigment pastes, e.g. under Use of known paste resins. Such resins are known to the person skilled in the art common. Examples of paste resins that can be used in KTL baths are in EP-A-0 183 025 and EP-A-0 469 497.
  • additives are known for ETL coating agents.
  • examples include wetting agents, Neutralizing agents, leveling agents, catalysts, Corrosion inhibitors, anti-foaming agents, solvents, in particular however, light protection agents if necessary in combination with Antioxidants.
  • the second and the third coating layer the usual, familiar to the skilled worker aqueous color and / or effect basecoat used as for the production of basecoat / clearcoat two-coat paint be used and in large numbers be described for example in the patent literature.
  • the waterborne basecoats can be physically drying or under Formation of covalent bonds can be cross-linked. With the under It can form water-based paints that crosslink covalent bonds are self- or third-party networking systems. It can be one or be two-component systems, one-component systems are preferred.
  • the waterborne basecoats which can be used in the process according to the invention contain water-dilutable binders. These contain for Ensuring their water dilutability conferring hydrophilicity non-ionic and / or ionic groups.
  • Suitable non-ionically stabilized binders are such binders, the water dilutability by incorporation of Polyether segments in the resin molecule is reached.
  • Specific Examples of such stabilized polyurethane or Polyurethane acrylate resins are e.g. in EP-A-0 354 261, EP-A-0 422 357 and EP-A-0 424 705.
  • binders containing ionic groups can be cationic or anionic groups Trade binders.
  • Stabilized binders are wholly or partially neutralized cationic (meth) acrylic copolymer, polyester, Polyurethane and / or polyurethane urea resins, especially with one Number average molecular weight (Mn) from 500 to 500000, an OH number of 0 to 450, an amine number from 20 to 200 and one Glass transition temperature from -50 to + 150 ° C.
  • Mn Number average molecular weight
  • Specific examples of these binders familiar to the person skilled in the art, are described in DE-A-40 11 633 described.
  • the waterborne basecoats preferably contain binders which are about anionic groups are stabilized. It is a or several film-forming resins, such as those in aqueous coating compositions, are common, especially in aqueous basecoats.
  • the film-forming Resins can, for example, polyester, (meth) acrylic copolymer or preferably be polyurethane resins. You can self or cross-linking or physically drying. Specific examples for suitable water-dilutable (meth) acrylic copolymers e.g. in EP-A-0 399 427 and EP-A-0 287 144.
  • suitable water-dilutable polyester resins are e.g. in DE-A-29 26 854, DE-A-38 32 142 and EP-A-0 301 300.
  • binders are those in which (meth) acrylic copolymer and Polycondensation resin covalently or in the form of interpenetrating Resin molecules are connected.
  • the combination is (meth) acrylic copolymer and polyester resin.
  • Specific Examples of such a usable combination are, for example in EP-A-0 226 171.
  • Anionically stabilized polyurethane resins are particularly preferred used. Such polyurethane resins are familiar to the person skilled in the art and are described in great variety in the literature. It is about thereby aqueous polyurethane dispersions or solutions or such Binder in which (meth) acrylic copolymer and polyurethane resin covalent or in the form of interpenetrating resin molecules. Examples of suitable polyurethane dispersions are stable, aqueous Dispersions with a solids content of 20 to 50% by weight.
  • the Weight-average molecular weight (Mw) of the resins can vary within wide limits fluctuate, e.g. from 1000 to 500000.
  • the polyurethane resins can functional groups such as Hydroxyl groups or blocked Contain isocyanate groups.
  • polyurethane dispersions are those that are isocyanate-functional by chain extension
  • Prepolymers can be made with polyamine and / or polyol. They are described, for example, in EP-A-0 089 497, EP-A-0 228 003, DE-A-36 28 124 and EP-A-0 512 524.
  • polyurethane dispersions that are made by Chain extension of isocyanate-functional prepolymers with water can be produced, e.g. in DE-A-39 15 459 and DE-A-42 24,617.
  • anionically stabilized usable Polyurethane (PU) dispersions are those that are available through Chain extension of at least one CH-acidic group in the molecule containing polyurethane resins with compounds with at least two CH-acidic groups can react. These are special examples polyurethane resin dispersions described in DE-A-42 28 510.
  • PU dispersions based on siloxane bridges can also be used chain-extended polyurethane resins can be used. Such are e.g. known from DE-A-44 13 562.
  • the waterborne basecoats can be a single aqueous binder contain, but also several aqueous binders in Combination.
  • Aqueous binders based on are preferred contain anionically stabilized polyurethanes. It can be convenient if a part, e.g. up to 50% by weight of the polyurethane binder by resins based on a combination of (meth) acrylic copolymer and Polyester resin is replaced.
  • water-dilutable binders based on cellulose be included.
  • the crosslinking agents familiar to those skilled in the art, such as, for example, formaldehyde condensation resins, such as phenol-formaldehyde condensation resins and amine-formaldehyde condensation resins, as well as free or blocked Polyisocyanates are used.
  • the crosslinkers can be used individually or in Mixture can be used.
  • the mixing ratio crosslinker too Binder resin is preferably 10:90 to 40:60, especially preferably 20:80 to 30:70, in each case based on the Solid weight.
  • the waterborne basecoats used in the process according to the invention contain in addition to the usual physically drying and / or chemical crosslinking binders pigments.
  • the expression used here "Pigments" includes inorganic and / or organic colored pigments and / or effect pigments and any fillers present. All common pigments can be used; examples are Titanium dioxide, iron oxide pigments, carbon black, azo pigments, Phthalocyanine pigments, metal pigments, e.g. made of titanium, aluminum or Copper, interference pigments, e.g. titanium dioxide coated Aluminum, coated mica, graphite effect pigments, platelet-shaped iron oxide, platelet-shaped Copper phthalocyanine pigments, talc, barium sulfate, kaolin, Silicon dioxide.
  • first and second basecoat coating compositions differ in their pigment / volume concentration (PVC) by no more than 30% of the absolute value of the pigment / volume concentration in the second basecoat coating composition.
  • the pigment / volume concentration of the first basecoat coating composition is preferably below that of the second basecoat coating composition.
  • the same is preferred in both basecoat coatings Pigments, particularly preferably the same pigmentations used.
  • the pigmentation is the relative composition of a To understand pigment mixture, d. H. the type of pigments and their respective proportions in the pigment mixture. It is also preferred in the two basecoat coatings pigmentations with similar average specific weight (this results from the relative proportions of the individual pigments) to use.
  • the average specifics preferably differ Weights of the pigmentations in the two basecoat coatings not more than 20% based on the average specific Weight of pigmentation in the second waterborne basecoat.
  • the color-imparting absorption pigments (colored pigments) and, if necessary Fillers are generally found in some of the water-dilutable Binder ground.
  • the rubbing can preferably also be carried out in one special water-thinnable paste resin happen. They can do that Paste resins known to those skilled in the art and suitable for aqueous systems be used. A specific example of a preferred usable paste resin based on an anionically stabilized Polyurethane resin can be found in DE-A-40 00 889. The rubbing takes place in conventional units known to the person skilled in the art. After that with the remaining portion of the aqueous binder or the aqueous Paste resin for the finished pigment pigment grinding completed. Are in paste resins are present in the waterborne basecoat, these add up Binders plus any crosslinker present. Either Binders as well as crosslinkers and paste resins together make up the Solid resin content of the water-based paints.
  • waterborne basecoats can be used as auxiliaries included, such as Catalysts, leveling agents, anti-foaming agents, Anti-cratering agents or, in particular, light stabilizers, if appropriate Connection with antioxidants.
  • the water-based paints for example, have a solids content of 10 to 50% by weight, for example, for effect basecoats preferably 15 - 30 wt .-%, for plain-colored basecoats it is preferably higher, for example at 20-45% by weight.
  • the ratio of Pigment to binder plus crosslinker plus if necessary optionally paste resin in the water-based lacquer is, for example between 0.03: 1 to 3: 1, for effect basecoats it is for example preferably at 0.06: 1 to 0.6: 1, for plain-colored Basecoats are preferably higher, for example 0.06: 1 to 2.5: 1, each based on the solid weight.
  • the one for generation the second water-based paint used in the second coating layer preferably a lower pigment / binder ratio than that for Generation of the third coating layer used second Wet basecoat.
  • binding agent includes the or the Binder as such plus any crosslinker present any paste resins present, the sum of these Constituents represent the solid resin content of the water-based paints.
  • the first to generate the second Coating layer used waterborne basecoat compared to the second waterborne basecoat used to create the third coating layer characterized by a higher proportion by weight of polyurethane resins.
  • the absolute value preferably corresponds to this excess Polyurethane resins in the first water-based paint between 5 and 50%, particularly preferably between 10 and 35% of the absolute value of the Solid resin weight content in the second coating agent.
  • the second basecoat coating agent has a solid resin content from 20% by weight
  • the preferred absolute value for is calculated the polyurethane content in the first basecoat coating composition as a sum the polyurethane content X (% by weight) of the second coating agent plus 5 to 50% of 20% by weight, i.e.
  • the polyurethane content of the first Coating agent is then preferred: X + (1 to 10) wt .-%.
  • the absolute value of the weight content differs Solid resin in the first basecoat by no more than 20% of the absolute value of the weight content of solid resin in the second Basecoat coating compositions; in the example above is Solid resin content of the second basecoat coating composition 20 wt .-%, so accordingly the solid resin content of the first basecoat coating composition total 16 to 24 wt .-%.
  • the solid resin content of the first coating agent particularly preferably equal to or higher than that of the second basecoat coating agent.
  • the first Basecoat coating composition according to a preferred procedure from the second basecoat coating agent by admixing a corresponding one Amount of polyurethane resin can be produced.
  • polyurethane resins that the higher proportion in can make out first waterborne basecoat are the above as Binder suitable for water-based paints Polyurethane resins.
  • the second waterborne basecoat in the first waterborne basecoat of a higher proportion of polyurethane resin can be used for the process according to the invention
  • manufactured second and third coating layers are also in others
  • Water-based paints that differ from one another, preferred however, similar waterborne basecoats can be used.
  • the two water-based paints preferably differ only by the above-mentioned essential to the invention Distinguishing feature. This is explained in more detail below.
  • a clear coat for the generation of the fourth and any additional coating layers are in principle all usual clear coats or transparent colored or colorless pigmented Coating agent suitable. It can be one or act multi-component clear lacquer coating agents. You can be solvent-free (liquid or as a powder clear coat), or it can are systems based on solvents or are are water-thinnable clear coats, whose binder systems in suitably, e.g. anionic, cationic or non-ionic, are stabilized. With the water-borne clear lacquer systems it can are water-soluble or water-dispersed systems, act, for example, emulsion systems or powder slurry systems. The Clear lacquer coating agents harden during baking under training covalent bonds due to chemical cross-linking.
  • the clear lacquers which can be used in the process according to the invention are concerned it is the usual clearcoat coating agent, the expert are common and the one or more common base resins as contain film-forming binders. You can, if the base resins are not self-crosslinking and may also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any restrictions.
  • a film-forming binder can, for example, polyester, polyurethane and / or (Meth) acrylic copolymer resins can be used.
  • Water-clear lacquer systems used as clear lacquer in the process according to the invention can be used can be found in DE-A-39 10 829, DE-A-40 09 931, DE-A-40 09 932, DE-A-41 01 696, DE-A-41 32 430, DE-A-41 34 290, DE-A-42 03 510, EP-A-0 365 098, EP-A-0 365 775, EP-A-0 496 079, EP-A-0 546 640.
  • powder clearcoat systems in the invention Processes that can be used as clear lacquer can be found in EP-A-0 509 392, EP-A-0 509 393, EP-A-0 522 648, EP-A-0 544 206, EP-A-0 555 705, DE-A-42 22 194, DE-A-42 27 580.
  • the transparent coating can be in a single layer or in shape of multiple layers from the same or from several different transparent coating agents can be applied.
  • a substrate for the method according to the invention are electrical conductive materials, such as metals. Particularly suitable are e.g. Automobile bodies or parts of them, them can be made of pretreated or untreated metal, with a electrically conductive layer provided metal or electrically conductive or provided with an electrically conductive layer Plastic.
  • the first one is on these substrates Coating layer, especially in the form of a Corrosion protection primer, electrophoretically in the usual way and in a usual dry layer thickness of ETL primers for example, 15 to 35 microns deposited and baked.
  • a Corrosion protection primer electrophoretically in the usual way and in a usual dry layer thickness of ETL primers for example, 15 to 35 microns deposited and baked.
  • multi-layer coatings are obtained more than the four coating layers produced according to the invention, nevertheless is in the context of the present invention in the invention Process first applied electrocoat layer first Called coating layer.
  • Waterborne basecoat preferably in one spray pass in one of the Opacity of the color-dependent dry layer thickness from 10 to less than 30 ⁇ m, for example 10 to 29 ⁇ m, preferably 10 to 25 ⁇ m, applied particularly preferably from 10 to 20 microns.
  • Suitable spray application methods are compressed air spraying, airless spraying or electrostatic (ESTA) high-rotation spraying, wherein electrostatic spraying for the application of the first waterborne basecoat is the preferred application method.
  • the third Coating layer from the second color and / or effect Waterborne basecoat in one spray pass preferably by compressed air spraying preferably in a smaller dry layer thickness than the second Coating layer, applied from only 7 to 15 ⁇ m and briefly vented, optionally at temperatures up to 80 ° C, for example during 1 to 5 minutes, e.g. by exposure to infrared radiation.
  • the third coating layer is applied and vented the application of the clear lacquer in the wet-on-wet process.
  • the fourth coating layer is made from a common liquid clear coat or powder clearcoat (in this case it is a dry-on-wet application) in a usual for clear lacquer layers Dry layer thickness of for example 30 to 80 microns, preferably 30 to 60 ⁇ m, overpainted and together with the second and third Coated layer.
  • the Baking temperature when baking the three together Coating layers between 80 and 160 ° C, preferably below 140 ° C. If necessary, further layers of clear lacquer from the same or of which various clear lacquer coating agents before or after Branding can be applied.
  • the method according to the invention allows the production of four or even multi-layer paintwork, in particular automotive paintwork with compared to the prior art, the filler layers and / or includes other intermediate layers, reduced total layer thickness and comparable overall property level. There are only two Burn-in steps necessary. It has been shown to be excellent Properties achieved by the procedure according to the invention even though this eliminates the need for conventional filler layers.
  • this waterborne basecoat is 13.8% by weight.
  • Pre-coated body panels are sprayed on Waterborne basecoat (blue metallic) from Example 1 in one Dry layer thickness of 15 ⁇ m applied. After the application flashed off briefly and then a second layer of the same Waterborne basecoat in a dry layer thickness of 10 ⁇ m also through Syringes applied. It is predried at 80 ° C. for 10 minutes. Subsequently, the 2K-HS car series clear coat from Example 1 is used overcoated with a dry film thickness of 40 ⁇ m and at 30 minutes 130 ° C (object temperature) dried.
  • Body panel On a usual phosphated and by cathodic dip painting and pre-coated with a 30 ⁇ m thick filler layer Body panel is made by spraying the one described below Waterborne basecoat (black) in a dry layer thickness of 20 ⁇ m upset. After application, the product is briefly vented and then Predried at 80 ° C for 10 minutes.
  • Waterborne basecoat black
  • This waterborne basecoat has a solid resin content of 21.9% by weight.
  • Pre-coated body panels are sprayed on Water-based paint (black) from example 4 in a dry layer thickness of 15 ⁇ m applied. After application, the product is briefly vented and then a second coat of the same waterborne basecoat in a dry film thickness of 10 ⁇ m also by spraying upset. It is predried at 80 ° C. for 10 minutes. Subsequently is with the 2K-HS car series clear coat from Example 1 in one Dry layer thickness of 40 ⁇ m overcoated and 30 minutes at 130 ° C (Object temperature) dried.
  • the water-based paints 6a), 6b) and 6c) each have one Solid resin content of 23.7% by weight.
  • Table 1 summarizes the results of the stone chip tests carried out. Multi-layer painting 1 2nd 3a 3b 3c 4th 5 6a 6b 6c VDA rockfall 1 3rd 1 1 1 3rd 1 1 Stone chipping using the "split method" 7 12th 3rd 5 6 5 10th 4th 4th 4th 0-1 4-5 0-1 0-1 1 0-1 4-5 0-1 0-1 1 1 0-1 4-5 0-1 0-1 1 1

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Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer mehrschichtigen Lackierung, insbesondere metallischer Substrate, das besonders zur Kraftfahrzeuglackierung geeignet ist.The invention relates to a method for producing a multilayer painting, especially metallic substrates, the is particularly suitable for automotive painting.

Heutige Automobilserienlackierungen bestehen meist aus einer Basislack/Klarlack-Decklackierung, die auf eine elektrophoretisch grundierte und mit einer Füllerschicht versehene Karosse aufgebracht wird. Dabei werden Basislack und Klarlack bevorzugt naß-in-naß appliziert, d.h. der Basislack wird nach einer Ablüftzeit, gegebenenfalls unter Erwarmen, und nach anschließender Applikation eines Klarlacks gemeinsam mit diesem eingebrannt. Aus der EP-A-0 238 037 ist ein der Reduzierung von Einbrennschichten dienendes Verfahren bekannt geworden, bei dem ein Füller und ein wäßriger Metallicbasislack nach dem Naß-in-Naß-Verfahren aufgebracht werden. Dem Beispielteil ist zu entnehmen, daß die Füllerschicht in einer für Füllerlacke üblichen Trockenfilmdicke von 35 µm aufgebracht wird.Today's automotive OEM coatings mostly consist of one Basecoat / clearcoat top coat based on an electrophoretic primed body with a filler layer applied becomes. Basecoat and clearcoat are preferably wet-on-wet applied, i.e. the basecoat is after a flash-off time, if necessary with heating, and after subsequent application a clear varnish baked together with this. From EP-A-0 238 037 is a method to reduce burn-in layers become known in which a filler and an aqueous metallic base coat applied by the wet-on-wet method. The sample part is it can be seen that the filler layer in a usual for filler paints Dry film thickness of 35 microns is applied.

Aus der EP-A-0 265 363 ist es bekannt, eine zuvor eingebrannte kataphoretisch aufgebrachte Grundierung mit einer nach dem Naß-in-Naß-Verfahren aufgebrachten zweischichtigen Basislack/Klarlack-Deckschicht zu versehen. Die Füllerschicht wird eingespart. Problematisch ist jedoch, daß Steinschlagschäden an nach diesem Verfahren lackierten Kraftfahrzeugen besonders augenfällig zu Tage treten, da die Grundierungsschicht bei Steinschlag durch Decklackenthaftung freigelegt wird. Der Korrosionsschutz ist dann zwar noch gewährleistet, der optische Eindruck kann jedoch nicht toleriert werden.From EP-A-0 265 363 it is known to use a previously burned-in product Cataphoretically applied primer with a wet-on-wet method applied two-layer basecoat / clearcoat top layer to provide. The filler layer is saved. Is problematic however, that stone chip damage to painted by this process Motor vehicles are particularly striking because the Primer layer exposed in the event of stone chipping through top coat detachment becomes. Corrosion protection is then still guaranteed However, visual impression cannot be tolerated.

Aus Gründen der Rationalisierung und der Materialersparnis besteht bei der Kraftfahrzeuglackierung der Wunsch nach Schichtdickenreduzierung des Lackaufbaus, ohne jedoch wesentliche Einbußen in dessen Gesamteigenschaftsniveau zuzulassen.For reasons of rationalization and material savings there is at automotive painting the desire for reduced thickness of the paint structure, but without significant loss in it Allow overall property level.

Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung von Mehrschichtlackierungen, insbesondere von Kraftfahrzeuglackierungen mit im Vergleich zum Stand der Technik vergleichbarem Gesamteigenschaftsniveau, jedoch verringerter Schichtdicke des Gesamtlackaufbaus bereitzustellen, welches mit möglichst wenigen Einbrennschritten durchführbar ist.The object of the invention is to provide a method for producing Multi-layer paintwork, in particular of automotive paintwork with comparable to the prior art Overall property level, but reduced layer thickness of the To provide overall paint structure, which with as few as possible Burn-in steps can be carried out.

Überraschenderweise wird die Aufgabe gelöst durch das einen Gegenstand der Erfindung darstellende Verfahren zur Mehrschichtlackierung eines mit einer eingebrannten ersten Elektrotauchlackschicht versehenen Substrats, das dadurch gekennzeichnet ist, daß auf diese erste Elektrotauchlackschicht eine zweite Überzugsschicht entsprechend einer Trockenschichtdicke von 10 bis unter 30 µm aus einem ersten wäßrigen, farb- und/oder effektgebenden Basislacküberzugsmittel, das ein oder mehrere Polyurethanharze enthält, aufgetragen wird, worauf naß-in-naß eine dritte Überzugsschicht entsprechend einer Trockenschichtdicke von 7 bis 15 µm aus einem zweiten wäßrigen, farb- und/oder effektgebenden Basislacküberzugsmittel aufgetragen und auf die dritte Überzugsschicht ohne vorheriges Einbrennen eine vierte Überzugsschicht aus einem Klarlacküberzugsmittel aufgetragen und die zweite, dritte und vierte Überzugsschicht gemeinsam eingebrannt werden, wobei ein erstes wäßriges Basislacküberzugsmittel verwendet wird, das einen höheren Gehalt an Polyurethanharz hat als das zweite Basislacküberzugsmittel, bezogen auf das Gesamtgewicht des jeweiligen wäßrigen Basislacküberzugsmittels, und wobei der Festharzgehalt im ersten Basislacküberzugsmittel um nicht mehr als 20 % von dem absoluten Wert des Gewichtsgehalts an Festharz im zweiten Basislacküberzugsmittel abweicht.Surprisingly, the problem is solved by one object The method of multi-layer coating of the invention provided with a burned-in first electrocoat layer Substrate, which is characterized in that on this first Electrocoating layer a second coating layer corresponding to one Dry layer thickness from 10 to less than 30 µm from a first aqueous, color and / or effect basecoat, the one or contains several polyurethane resins, is applied, whereupon wet-on-wet a third coating layer corresponding to a dry layer thickness of 7 to 15 microns from a second aqueous, color and / or effect Basecoat coating agent applied and on the third coating layer a fourth coating layer from one without baking Clear lacquer coating agent applied and the second, third and fourth Coating layer are baked together, with a first aqueous Basecoat is used, which has a higher content Polyurethane resin has as the second basecoat based on the total weight of the respective aqueous basecoat coating agent, and the solid resin content in the first basecoat coating agent not more than 20% of the absolute value of the weight content of solid resin in the differs from the second basecoat.

Durch das erfindungsgemäße Verfahren wird es möglich, direkt auf eine eingebrannte durch Elektroabscheidung erstellte erste Überzugsschicht ein wäßriges Basislacküberzugsmittel aufzubringen und diese Schicht gemeinsam mit der anschließend aufgebrachten zweiten Wasserbasislackschicht und Klarlackschicht einzubrennen, wobei übliche Füllerschichten oder andere Zwischenschichten entfallen.The method according to the invention makes it possible to directly access a burned-in first coating layer created by electrodeposition apply an aqueous basecoat and this layer together with the subsequently applied second Burn in the water-based lacquer layer and clear lacquer layer, using usual Filler layers or other intermediate layers are eliminated.

Als elektrophoretisch abscheidbare Überzugsmittel zur Erzeugung der ersten Überzugsschicht, nämlich einer Grundierung, können alle an sich bekannten anodisch oder kathodisch abscheidbaren Elektrotauchlacke (ETL), die keiner besonderen Beschränkung unterliegen, verwendet werden.As an electrophoretically depositable coating agent for producing the The first layer of coating, namely a primer, can all be done by itself known anodically or cathodically depositable electrocoat materials (ETL), which are not subject to any particular restriction become.

Dabei handelt es sich z.B. um wäßrige Überzugsmittel mit einem Festkörper bis zu 50 Gew.%, beispielsweise 10 bis 20 Gew.-%. Der Festkörper wird gebildet aus für die Elektrotauchlackierung üblichen Bindemitteln, die ionische Gruppen oder in ionische Gruppen überführbare Gruppen sowie gegebenenfalls zur chemischen Vernetzung fähige Gruppen tragen, sowie gegebenenfalls vorhandenen Vernetzern, Pigmenten, Füllstoffen und/oder lacküblichen Additiven. Die ionischen oder in ionische Gruppen überführbaren Gruppen können anionische oder in anionische Gruppen überführbare Gruppen, z.B. saure Gruppen, wie - COOH-Gruppen oder kationische oder in kationische Gruppen überführbare, z.B. basische Gruppen, wie Amino-, Ammonium-, z.B. quartäre Ammoniumgruppen, Phosphonium- und/oder Sulfonium-Gruppen sein. Bevorzugt sind Bindemittel mit basischen Gruppen. Besonders bevorzugt sind stickstoffhaltige basische Gruppen. Diese Gruppen können quarternisiert vorliegen oder sie werden zumindest teilweise mit einem üblichen Neutralisationsmittel, einer Säure, z.B. einer organischen Monocarbonsäure, wie z.B. Ameisensäure oder Essigsäure, in ionische Gruppen überführt.This is e.g. to aqueous coating agents with a Solids up to 50% by weight, for example 10 to 20% by weight. Of the Solid is formed from the usual for electrodeposition painting Binders, the ionic groups or in ionic groups convertible groups and, if necessary, for chemical crosslinking capable groups, and any existing crosslinkers, Pigments, fillers and / or additives common in paint. The Ionic or groups which can be converted into ionic groups can be anionic or groups which can be converted into anionic groups, e.g. acidic groups like - COOH groups or cationic or convertible into cationic groups, e.g. basic groups such as amino, ammonium, e.g. quaternaries Ammonium groups, phosphonium and / or sulfonium groups. Binders with basic groups are preferred. Particularly preferred are nitrogen-containing basic groups. These groups can quaternized or at least partially with one usual neutralizing agent, an acid, e.g. an organic Monocarboxylic acid, e.g. Formic acid or acetic acid, in ionic Groups convicted.

Zur Herstellung der ersten Überzugsschicht, der Elektrotauchlackschicht, können beispielsweise die üblichen anionische Gruppen enthaltenden anodisch abscheidbaren Elektrotauchlack-Bindemittel und Lacke (ATL) verwendet werden. Es handelt sich beispielsweise um Bindemittel auf Basis von Polyestern, Epoxidharzen, Poly(meth)acrylaten, Maleinatölen oder Polybutadienölen mit einem Gewichtsmittel der Molmasse von beispielsweise 300 bis 10000 und einer Säurezahl von 35 bis 300 mg KOH/g. Die Bindemittel tragen z.B. -COOH, -SO3H und/oder -PO3H2-Gruppen. Die Harze können nach Neutralisation von mindestens einem Teil der sauren Gruppen in die Wasserphase überführt werden. Die Bindemittel können selbstvernetzend oder fremdvernetzend sein. Die Lacke können daher auch übliche Vernetzer enthalten, z.B. Triazinharze, Vernetzer, die umesterungsfähige Gruppen enthalten oder blockierte Polyisocyanate. Spezielle Beispiele für solche im erfindungsgemäßen Verfahren einsetzbare anionische Gruppen enthaltende anodisch abscheidbare Elektrotauchlack-Bindemittel und Lacke (ATL) sind z.B. in der DE-A-28 24 418 beschrieben.For the production of the first coating layer, the electrodeposition lacquer layer, it is possible, for example, to use the usual anodically depositable electrodeposition lacquer binders and lacquers (ATL) containing anionic groups. These are, for example, binders based on polyesters, epoxy resins, poly (meth) acrylates, maleate oils or polybutadiene oils with a weight average molecular weight of, for example, 300 to 10,000 and an acid number of 35 to 300 mg KOH / g. The binders carry, for example, -COOH, -SO 3 H and / or -PO 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase. The binders can be self-crosslinking or externally crosslinking. The lacquers can therefore also contain customary crosslinking agents, for example triazine resins, crosslinking agents which contain groups capable of transesterification or blocked polyisocyanates. Specific examples of such anodically depositable electrodeposition paint binders and paints (ATL) which contain anionic groups and can be used in the process according to the invention are described, for example, in DE-A-28 24 418.

Bevorzugt werden jedoch kathodisch abscheidbare Elektrotauchlacke (KTL) auf Basis kationischer bzw. basischer Bindemittel zur Herstellung der ersten Überzugsschicht eingesetzt. Solche basischen Harze sind beispielsweise primäre, sekundäre oder tertiäre Aminogruppen enthaltende Harze, deren Aminzahlen z.B. bei 20 bis 250 mg KOH/g liegen. Das Gewichtsmittel der Molmasse (Mw) der Basisharze liegt bevorzugt bei 300 bis 10000. Beispiele für solche Basisharze sind Amino(meth)acrylatharze, Aminoepoxidharze, Aminoepoxidharze mit endständigen Doppelbindungen, Aminoepoxidharze mit primären OH-Gruppen, Aminopolyurethanharze, aminogruppenhaltige Polybutadienharze oder modifizierte Epoxidharz-Kohlendioxid-Amin-Umsetzungsprodukte. Diese Basisharze können selbstvernetzend sein oder sie werden mit bekannten Vernetzern im Gemisch eingesetzt. Beispiele für solche Vernetzer sind Aminoplastharze, blockierte Polyisocyanate, Vernetzer mit endständigen Doppelbindungen, Polyepoxidverbindungen oder Vernetzer, die umesterungsfähige Gruppen enthalten. Spezielle Beispiele für in kathodischen Tauchlack (KTL)-Bädern einsetzbare Basisharze und Vernetzer sind z.B. in der EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 456 270, US 3 922 253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199, EP-A-0 476 514 beschrieben.However, cathodic electrodeposition paints (KTL) are preferred based on cationic or basic binders for the production of first coating layer used. Such basic resins are for example primary, secondary or tertiary amino groups resins containing, the amine numbers e.g. at 20 to 250 mg KOH / g lie. The weight average molecular weight (Mw) of the base resins is preferably from 300 to 10,000. Examples of such base resins are Amino (meth) acrylate resins, amino epoxy resins, amino epoxy resins with terminal double bonds, amino epoxy resins with primary OH groups, Aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products. This Base resins can be self-crosslinking or they are known Crosslinkers used in the mixture. Examples of such crosslinkers are Aminoplast resins, blocked polyisocyanates, crosslinkers with terminal Double bonds, polyepoxide compounds or crosslinkers Contain transesterifiable groups. Specific examples of in base resins and cathodic dip lacquer (KTL) baths Crosslinkers are e.g. in EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 456 270, US 3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199, EP-A-0 476 514.

Solche Harze können allein oder im Gemisch eingesetzt werden. Bevorzugt werden sogenannte "non-yellowing"-KTL-Systeme eingesetzt, die eine Vergilbung oder Verfärbung der Mehrschichtlackierung beim Einbrennen vermeiden. Beispielsweise handelt es sich dabei um mittels speziell ausgewählter blockierter Polyisocyanate vernetzende KTL-Systeme, wie beispielsweise in EP-A-0 265 363 beschrieben.Such resins can be used alone or in a mixture. Prefers so-called "non-yellowing" -KTL systems are used, the one Yellowing or discoloration of the multi-layer coating when baked avoid. For example, it is by means of special selected blocked polyisocyanate crosslinking KTL systems, such as described for example in EP-A-0 265 363.

Zusätzlich zu den Basisharzen und gegebenenfalls vorhandenem Vernetzer kann das Elektrotauchlack (ETL)-Überzugsmittel Pigmente, Füllstoffe und/oder lackübliche Additive enthalten. Als Pigmente und Füllstoffe kommen die üblichen anorganischen und/oder organischen Pigmente und Füllstoffe in Frage. Beispiele sind Ruß, Titandioxid, Eisenoxidpigmente, Phthalocyaninpigmente, Chinacridonpigmente, Kaolin, Talkum oder Siliziumdioxid.In addition to the base resins and any crosslinking agents present Can the electrocoat (ETL) coating agent pigments, fillers and / or conventional paint additives. As pigments and fillers come the usual inorganic and / or organic pigments and Fillers in question. Examples are carbon black, titanium dioxide, Iron oxide pigments, phthalocyanine pigments, quinacridone pigments, kaolin, Talc or silicon dioxide.

Die Pigmente können zu Pigmentpasten dispergiert werden, z.B. unter Verwendung von bekannten Pastenharzen. Solche Harze sind dem Fachmann geläufig. Beispiele für in KTL-Bädern verwendbare Pastenharze sind in der EP-A-0 183 025 und in der EP-A-0 469 497 beschrieben.The pigments can be dispersed into pigment pastes, e.g. under Use of known paste resins. Such resins are known to the person skilled in the art common. Examples of paste resins that can be used in KTL baths are in EP-A-0 183 025 and EP-A-0 469 497.

Als Additive sind die üblichen Additive möglich, wie sie insbesondere für ETL-Überzugsmittel bekannt sind. Beispiele dafür sind Netzmittel, Neutralisationsmittel, Verlaufsmittel, Katalysatoren, Korrosionsinhibitoren, Antischaummittel, Lösemittel, insbesondere jedoch Lichtschutzmittel gegebenenfalls in Kombination mit Antioxidantien.The usual additives, in particular, are possible as additives are known for ETL coating agents. Examples include wetting agents, Neutralizing agents, leveling agents, catalysts, Corrosion inhibitors, anti-foaming agents, solvents, in particular however, light protection agents if necessary in combination with Antioxidants.

Im erfindungsgemäßen Verfahren werden für die Erzeugung der zweiten und der dritten Überzugsschicht die üblichen, dem Fachmann geläufigen wäßrigen farb- und/oder effektgebenden Basislacküberzugsmittel verwendet, wie sie zur Herstellung von Basislack/KlarlackZweischichtlackierungen eingesetzt werden und in großer Zahl beispielsweise in der Patentliteratur beschrieben werden.In the method according to the invention, the second and the third coating layer the usual, familiar to the skilled worker aqueous color and / or effect basecoat used as for the production of basecoat / clearcoat two-coat paint be used and in large numbers be described for example in the patent literature.

Die Wasserbasislacke können physikalisch trocknend sein oder unter Ausbildung kovalenter Bindungen vernetzbar sein. Bei den unter Ausbildung kovalenter Bindungen vernetzenden Wasserbasislacken kann es sich um selbst- oder fremdvernetzende Systeme handeln. Es können ein- oder zweikomponentige Systeme sein, einkomponentige sind bevorzugt.The waterborne basecoats can be physically drying or under Formation of covalent bonds can be cross-linked. With the under It can form water-based paints that crosslink covalent bonds are self- or third-party networking systems. It can be one or be two-component systems, one-component systems are preferred.

Die im erfindungsgemäßen Verfahren einsetzbaren Wasserbasislacke enthalten wasserverdünnbare Bindemittel. Diese enthalten zur Gewährleistung ihrer Wasserverdünnbarkeit Hydrophilie verleihende nicht-ionische und/oder ionische Gruppen.The waterborne basecoats which can be used in the process according to the invention contain water-dilutable binders. These contain for Ensuring their water dilutability conferring hydrophilicity non-ionic and / or ionic groups.

Beispiele für geeignete nicht-ionisch stabilisierte Bindemittel sind solche Bindemittel, deren Wasserverdünnbarkeit durch Einbau von Polyethersegmenten in das Harzmolekül erreicht wird. Spezielle Beispiele für derartig stabilisierte Polyurethan- bzw. Polyurethanacrylatharze sind z.B. in EP-A-0 354 261, EP-A-0 422 357 und EP-A-0 424 705 beschrieben.Examples of suitable non-ionically stabilized binders are such binders, the water dilutability by incorporation of Polyether segments in the resin molecule is reached. Specific Examples of such stabilized polyurethane or Polyurethane acrylate resins are e.g. in EP-A-0 354 261, EP-A-0 422 357 and EP-A-0 424 705.

Bei den wasserverdünnbaren, ionische Gruppen tragenden Bindemitteln kann es sich um kationische oder um anionische Gruppen tragende Bindemittel handeln.For water-borne binders containing ionic groups can be cationic or anionic groups Trade binders.

Beispiele für die erfindungsgemäß einsetzbaren kationisch stabilisierten Bindemittel sind vollständig oder teilweise neutralisierte kationische (Meth)acrylcopolymer-, Polyester-, Polyurethan- und/oder Polyurethanharnstoffharze, insbesondere mit einem Zahlenmittel der Molmasse (Mn) von 500 bis 500000, einer OH-Zahl von 0 bis 450, einer Aminzahl von 20 bis 200 und einer Glasübergangstemperatur von -50 bis +150°C. Spezielle Beispiele für diese, dem Fachmann geläufigen Bindemittel, sind in der DE-A-40 11 633 beschrieben.Examples of the cationic used according to the invention Stabilized binders are wholly or partially neutralized cationic (meth) acrylic copolymer, polyester, Polyurethane and / or polyurethane urea resins, especially with one Number average molecular weight (Mn) from 500 to 500000, an OH number of 0 to 450, an amine number from 20 to 200 and one Glass transition temperature from -50 to + 150 ° C. Specific examples of these binders, familiar to the person skilled in the art, are described in DE-A-40 11 633 described.

Bevorzugt enthalten die Wasserbasislacke Bindemittel, die über anionische Gruppen stabilisiert sind. Es handelt sich dabei um ein oder mehrere filmbildende Harze, wie sie in wäßrigen Überzugsmitteln, insbesondere in wäßrigen Basislacken, üblich sind. Die filmbildenden Harze können beispielsweise Polyester-, (Meth)acrylcopolymer- oder bevorzugt Polyurethanharze sein. Sie können selbst- oder fremdvernetzend oder physikalisch trocknend sein. Spezielle Beispiele für geeignete wasserverdünnbare (Meth)acrylcopolymere sind z.B. in EP-A-0 399 427 und EP-A-0 287 144 beschrieben.The waterborne basecoats preferably contain binders which are about anionic groups are stabilized. It is a or several film-forming resins, such as those in aqueous coating compositions, are common, especially in aqueous basecoats. The film-forming Resins can, for example, polyester, (meth) acrylic copolymer or preferably be polyurethane resins. You can self or cross-linking or physically drying. Specific examples for suitable water-dilutable (meth) acrylic copolymers e.g. in EP-A-0 399 427 and EP-A-0 287 144.

Spezielle Beispiele für geeignete wasserverdünnbare Polyesterharze sind z.B. in DE-A-29 26 854, DE-A-38 32 142 und EP-A-0 301 300 beschrieben.Specific examples of suitable water-dilutable polyester resins are e.g. in DE-A-29 26 854, DE-A-38 32 142 and EP-A-0 301 300.

Es ist auch möglich Gemische von Bindemitteln einzusetzen. Besonders geeignete Bindemittel sind solche, in denen (Meth)acrylcopolymeres und Polykondensationsharz kovalent oder in Form interpenetrierender Harzmoleküle verbunden vorliegen. Beispiele für eine derartige Kombination sind (Meth)acrylcopolymer und Polyesterharz. Spezielle Beispiele für eine solche verwendbare Kombination sind beispielsweise in der EP-A-0 226 171 beschrieben.It is also possible to use mixtures of binders. Especially suitable binders are those in which (meth) acrylic copolymer and Polycondensation resin covalently or in the form of interpenetrating Resin molecules are connected. Examples of such The combination is (meth) acrylic copolymer and polyester resin. Specific Examples of such a usable combination are, for example in EP-A-0 226 171.

Besonders bevorzugt werden anionisch stabilisierte Polyurethanharze verwendet. Solche Polyurethanharze sind dem Fachmann geläufig und werden in der Literatur in großer Vielfalt beschrieben. Es handelt sich dabei um wäßrige Polyurethandispersionen oder -lösungen oder um solche Bindemittel, in denen (Meth)acrylcopolymer und Polyurethanharz kovalent oder in Form interpenetrierender Harzmoleküle verbunden vorliegen. Beispiele für geeignete Polyurethandispersionen sind stabile, wäßrige Dispersionen mit einem Festkörper von 20 bis 50 Gew.-%. Das Gewichtsmittel der Molmasse (Mw) der Harze kann in weiten Grenzen schwanken, z.B. von 1000 bis 500000. Die Polyurethanharze können funktionelle Gruppen wie z.B. Hydroxylgruppen oder blockierte Isocyanatgruppen enthalten.Anionically stabilized polyurethane resins are particularly preferred used. Such polyurethane resins are familiar to the person skilled in the art and are described in great variety in the literature. It is about thereby aqueous polyurethane dispersions or solutions or such Binder in which (meth) acrylic copolymer and polyurethane resin covalent or in the form of interpenetrating resin molecules. Examples of suitable polyurethane dispersions are stable, aqueous Dispersions with a solids content of 20 to 50% by weight. The Weight-average molecular weight (Mw) of the resins can vary within wide limits fluctuate, e.g. from 1000 to 500000. The polyurethane resins can functional groups such as Hydroxyl groups or blocked Contain isocyanate groups.

Spezielle Beispiele für verwendbare Polyurethandispersionen sind solche, die durch Kettenverlängerung isocyanatfunktioneller Prepolymerer mit Polyamin und/oder Polyol hergestellt werden können. Sie werden beispielsweise in den EP-A-0 089 497, EP-A-0 228 003, DE-A-36 28 124 und EP-A-0 512 524 beschrieben.Specific examples of usable polyurethane dispersions are those that are isocyanate-functional by chain extension Prepolymers can be made with polyamine and / or polyol. They are described, for example, in EP-A-0 089 497, EP-A-0 228 003, DE-A-36 28 124 and EP-A-0 512 524.

Weitere Beispiele sind Polyurethandispersionen, die durch Kettenverlängerung isocyanatfunktioneller Prepolymerer mit Wasser hergestellt werden können, wie z.B. in der DE-A-39 15 459 und der DE-A-42 24 617 beschrieben.Further examples are polyurethane dispersions that are made by Chain extension of isocyanate-functional prepolymers with water can be produced, e.g. in DE-A-39 15 459 and DE-A-42 24,617.

Es können auch Polyurethandispersionen verwendet werden, die durch Kettenverlängerung von gegenüber Polyisocyanaten reaktiven, aktiven Wasserstoff enthaltenden Polyurethanprepolymeren mit Polyisocyanaten hergestellt werden, wie z.B. in DE-A-39 03 804 und DE-A-40 01 841 beschrieben.It is also possible to use polyurethane dispersions which are produced by Chain extension of active, reactive towards polyisocyanates Hydrogen-containing polyurethane prepolymers with polyisocyanates be produced, e.g. in DE-A-39 03 804 and DE-A-40 01 841 described.

Weitere Beispiele für verwendbare anionisch stabilisierte Polyurethan(PU)-Dispersionen sind solche, die erhältlich sind durch Kettenverlängerung von mindestens eine CH-acide Gruppe im Molekül enthaltenden Polyurethanharzen mit Verbindungen, die mit mindestens zwei CH-aciden Gruppen reagieren können. Spezielle Beispiele sind die in der DE-A-42 28 510 beschriebenen Polyurethanharzdispersionen.Further examples of anionically stabilized usable Polyurethane (PU) dispersions are those that are available through Chain extension of at least one CH-acidic group in the molecule containing polyurethane resins with compounds with at least two CH-acidic groups can react. These are special examples polyurethane resin dispersions described in DE-A-42 28 510.

Es können auch PU-Dispersionen auf Basis von über Siloxanbrücken kettenverlängerten Polyurethanharzen verwendet werden. Solche sind z.B. aus der DE-A-44 13 562 bekannt.PU dispersions based on siloxane bridges can also be used chain-extended polyurethane resins can be used. Such are e.g. known from DE-A-44 13 562.

Spezielle Beispiele für anionisch stabilisierte polyurethanbasierende Bindemittel, in denen (Meth)acrylcopolymer und Polyurethanharz kovalent oder in Form interpenetrierender Harzmoleküle verbunden vorliegen, sind z.B. in den EP-A-0 353 797, EP-A-0 297 576, DE-A-41 22 265, DE-A-41 22 266 und WO 95/16004 beschrieben.Special examples of anionically stabilized polyurethane-based Binder in which (meth) acrylic copolymer and polyurethane resin covalent or are present in the form of interpenetrating resin molecules e.g. in EP-A-0 353 797, EP-A-0 297 576, DE-A-41 22 265, DE-A-41 22 266 and WO 95/16004.

Die Wasserbasislacke können ein einziges wäßriges Bindemittel enthalten, es können aber auch mehrere wäßrige Bindemittel in Kombination vorliegen. Bevorzugt sind wäßrige Bindemittel auf Basis anionisch stabilisierter Polyurethane enthalten. Es kann zweckmäßig sein, wenn ein Teil, z.B. bis zu 50 Gew.-%, der Polyurethan-Bindemittel durch Harze auf Basis einer Kombination aus (Meth)acrylcopolymer und Polyesterharz ersetzt wird.The waterborne basecoats can be a single aqueous binder contain, but also several aqueous binders in Combination. Aqueous binders based on are preferred contain anionically stabilized polyurethanes. It can be convenient if a part, e.g. up to 50% by weight of the polyurethane binder by resins based on a combination of (meth) acrylic copolymer and Polyester resin is replaced.

Weiterhin können wasserverdünnbare Bindemittel auf Cellulosebasis enthalten sein.Furthermore, water-dilutable binders based on cellulose be included.

Zur Bereitung der Wasserbasislacke können, insbesondere wenn die eingesetzten Bindemittel nicht selbstvernetzend sind, die üblichen, dem Fachmann geläufigen Vernetzer, wie beispielsweise Formaldehyd-Kondensationsharze, wie Phenol-Formaldehydkondensationsharze und Amin-Formaldehydkondensationsharze, sowie freie oder blockierte Polyisocyanate verwendet werden. Die Vernetzer können einzeln oder im Gemisch eingesetzt werden. Das Mischungsverhältnis Vernetzer zu Bindemittelharz beträgt bevorzugt 10 : 90 bis 40 : 60, besonders bevorzugt 20 : 80 bis 30 : 70, jeweils bezogen auf das Festkörpergewicht.To prepare the water-based paints, especially if the binders used are not self-crosslinking, the usual, the Crosslinking agents familiar to those skilled in the art, such as, for example, formaldehyde condensation resins, such as phenol-formaldehyde condensation resins and amine-formaldehyde condensation resins, as well as free or blocked Polyisocyanates are used. The crosslinkers can be used individually or in Mixture can be used. The mixing ratio crosslinker too Binder resin is preferably 10:90 to 40:60, especially preferably 20:80 to 30:70, in each case based on the Solid weight.

Die beim erfindungsgemäßen Verfahren eingesetzten Wasserbasislacke enthalten neben den üblichen physikalisch trocknenden und/oder chemisch vernetzenden Bindemitteln Pigmente. Der hier verwendete Ausdruck "Pigmente" schließt anorganische und/oder organische Buntpigmente und/oder Effektpigmente und gegebenenfalls vorhandene Füllstoffe ein. Es können alle üblichen Pigmente verwendet werden; Beispiele sind Titandioxid, Eisenoxidpigmente, Ruß, Azopigmente, Phthalocyaninpigmente, Metallpigmente, z.B. aus Titan, Aluminium oder Kupfer, Interferenzpigmente, wie z.B. titandioxidbeschichtetes Aluminium, beschichteter Glimmer, Graphiteffektpigmente, plättchenförmiges Eisenoxid, plättchenförmige Kupferphthalocyaninpigmente, Talkum, Bariumsulfat, Kaolin, Siliziumdioxid.The waterborne basecoats used in the process according to the invention contain in addition to the usual physically drying and / or chemical crosslinking binders pigments. The expression used here "Pigments" includes inorganic and / or organic colored pigments and / or effect pigments and any fillers present. All common pigments can be used; examples are Titanium dioxide, iron oxide pigments, carbon black, azo pigments, Phthalocyanine pigments, metal pigments, e.g. made of titanium, aluminum or Copper, interference pigments, e.g. titanium dioxide coated Aluminum, coated mica, graphite effect pigments, platelet-shaped iron oxide, platelet-shaped Copper phthalocyanine pigments, talc, barium sulfate, kaolin, Silicon dioxide.

Es ist bevorzugt, wenn sich das erste und das zweite Basislacküberzugsmittel in ihrer Pigment/Volumen-Konzentration (PVK) um nicht mehr als 30 % des absoluten Wertes der Pigment/Volument-Konzentration im zweiten Basislacküberzugsmittel unterscheidet. Bevorzugt liegt die Pigment/Volumen-Konzentration des ersten Basislacküberzugsmittels unter der des zweiten Basislacküberzugsmittels. Die Pigment/Volumen-Konzentration in einem Überzugsmittel stellt das Verhältnis von Pigmentvolumen zu Pigmentvolumen + Bindemittelvolumen dar und errechnet sich nach folgender Gleichung: PVK = Volument PigmentVolumen Pigment + Volumen Bindemittel · 100 % It is preferred if the first and second basecoat coating compositions differ in their pigment / volume concentration (PVC) by no more than 30% of the absolute value of the pigment / volume concentration in the second basecoat coating composition. The pigment / volume concentration of the first basecoat coating composition is preferably below that of the second basecoat coating composition. The pigment / volume concentration in a coating agent represents the ratio of pigment volume to pigment volume + binder volume and is calculated using the following equation: PVK = Volume pigment Volume of pigment + volume of binder 100%

Bevorzugt werden in beiden Basislacküberzugmitteln die gleichen Pigmente, besonders bevorzugt die gleichen Pigmentierungen verwendet. Dabei ist unter Pigmentierung die relative Zusammensetzung eines Pigmentgemischs zu verstehen, d. h. die Art der Pigmente und deren jeweiliger Mengenanteil in dem Pigmentgemisch. Bevorzugt ist es auch in den beiden Basislacküberzugsmitteln Pigmentierungen mit ähnlichem durchschnittlichem spezifischem Gewicht (dieses ergibt sich aus den relativen Mengenanteilen der einzelnen Pigmente) zu verwenden. Bevorzugt unterscheiden sich die durchschnittlichen spezifischen Gewichte der Pigmentierungen in den beiden Basislacküberzugsmitteln um nicht mehr als 20 %, bezogen auf das durchschnittliche spezifische Gewicht der Pigmentierung im zweiten Wasserbasislack. The same is preferred in both basecoat coatings Pigments, particularly preferably the same pigmentations used. The pigmentation is the relative composition of a To understand pigment mixture, d. H. the type of pigments and their respective proportions in the pigment mixture. It is also preferred in the two basecoat coatings pigmentations with similar average specific weight (this results from the relative proportions of the individual pigments) to use. The average specifics preferably differ Weights of the pigmentations in the two basecoat coatings not more than 20% based on the average specific Weight of pigmentation in the second waterborne basecoat.

Die farbgebenden Absorptionspigmente (Buntpigmente) und gegebenenfalls Füllstoffe werden im allgemeinen in einem Teil der wasserverdünnbaren Bindemittel angerieben. Bevorzugt kann das Anreiben auch in einem speziellen wasserverdünnbaren Pastenharz geschehen. Es können die dem Fachmann geläufigen, für wäßrige Systeme geeigneten Pastenharze verwendet werden. Ein spezielles Beispiel für ein bevorzugt einsetzbares Pastenharz auf Basis eines anionisch stabilisierten Polyurethanharzes findet sich in der DE-A-40 00 889. Das Anreiben geschieht in üblichen dem Fachmann bekannten Aggregaten. Danach wird mit dem restlichen Anteil des wäßrigen Bindemittels oder des wäßrigen Pastenharzes zur fertigen Farbpigmentanreibung komplettiert. Sind in dem Wasserbasislack Pastenharze vorhanden, so addieren sich diese zu Bindemitteln plus gegebenenfalls vorhandenem Vernetzer. Sowohl Bindemittel als auch Vernetzer und Pastenharze ergeben gemeinsam den Festharzgehalt der Wasserbasislacke.The color-imparting absorption pigments (colored pigments) and, if necessary Fillers are generally found in some of the water-dilutable Binder ground. The rubbing can preferably also be carried out in one special water-thinnable paste resin happen. They can do that Paste resins known to those skilled in the art and suitable for aqueous systems be used. A specific example of a preferred usable paste resin based on an anionically stabilized Polyurethane resin can be found in DE-A-40 00 889. The rubbing takes place in conventional units known to the person skilled in the art. After that with the remaining portion of the aqueous binder or the aqueous Paste resin for the finished pigment pigment grinding completed. Are in paste resins are present in the waterborne basecoat, these add up Binders plus any crosslinker present. Either Binders as well as crosslinkers and paste resins together make up the Solid resin content of the water-based paints.

Weiterhin können die Wasserbasislacke lackübliche Hilfsstoffe enthalten, wie z.B. Katalysatoren, Verlaufsmittel, Antischaummittel, Antikratermittel oder insbesondere Lichtschutzmittel gegebenenfalls in Verbindung mit Antioxidantien.Furthermore, the waterborne basecoats can be used as auxiliaries included, such as Catalysts, leveling agents, anti-foaming agents, Anti-cratering agents or, in particular, light stabilizers, if appropriate Connection with antioxidants.

Die Wasserbasislacke besitzen beispielsweise einen Festkörpergehalt von 10 bis 50 Gew.-%, für Effektbasislacke liegt er beispielsweise bevorzugt bei 15 - 30 Gew.-%, für unifarbige Basislacke liegt er bevorzugt höher, beispielsweise bei 20 - 45 Gew.-%. Das Verhältnis von Pigment zu Bindemittel plus gegebenenfalls Vernetzer plus gegebenenfalls Pastenharz im Wasserbasislack beträgt beispielsweise zwischen 0,03 : 1 bis 3 : 1, für Effektbasislacke liegt es beispielsweise bevorzugt bei 0,06 : 1 bis 0,6 : 1, für unifarbige Basislacke liegt es bevorzugt höher, beispielsweise bei 0,06 : 1 bis 2,5 : 1, jeweils bezogen auf das Festkörpergewicht. Der zur Erzeugung der zweiten Überzugsschicht eingesetzte erste Wasserbasislack besitzt bevorzugt ein niedrigeres Pigment/Bindemittel-Verhältnis als der zur Erzeugung der dritten Überzugsschicht eingesetzte zweite Nasserbasislack. Dabei beinhaltet der Ausdruck Bindemittel das oder die Bindemittel als solche plus gegebenenfalls vorhandene Vernetzer plus gegebenenfalls vorhandene Pastenharze, wobei die Summe dieser Bestandteile den Festharzgehalt der Wasserbasislacke repräsentiert.The water-based paints, for example, have a solids content of 10 to 50% by weight, for example, for effect basecoats preferably 15 - 30 wt .-%, for plain-colored basecoats it is preferably higher, for example at 20-45% by weight. The ratio of Pigment to binder plus crosslinker plus if necessary optionally paste resin in the water-based lacquer is, for example between 0.03: 1 to 3: 1, for effect basecoats it is for example preferably at 0.06: 1 to 0.6: 1, for plain-colored Basecoats are preferably higher, for example 0.06: 1 to 2.5: 1, each based on the solid weight. The one for generation the second water-based paint used in the second coating layer preferably a lower pigment / binder ratio than that for Generation of the third coating layer used second Wet basecoat. The term binding agent includes the or the Binder as such plus any crosslinker present any paste resins present, the sum of these Constituents represent the solid resin content of the water-based paints.

Es ist erfindungswesentlich, daß der erste zur Erzeugung der zweiten Überzugsschicht verwendete Wasserbasislack sich gegenüber dem zweiten zur Erzeugung der dritten Überzugsschicht verwendeten Wasserbasislack durch einen höheren Gewichtsanteil an Polyurethanharzen, auszeichnet. Bevorzugt entspricht der absolute Wert dieses Überschusses an Polyurethanharzen im ersten Wasserbasislack zwischen 5 und 50 %, besonders bevorzugt zwischen 10 und 35 % des absoluten Wertes des Gewichtsgehalts an Festharz im zweiten Überzugsmittel. Weist dementsprechend das zweite Basislacküberzugsmittel einen Festharzgehalt von 20 Gew.-% auf, so errechnet sich der bevorzugte absolute Wert für den Polyurethangehalt im ersten Basislacküberzugsmittel als Summe aus dem Polyurethangehalt X (Gew.-%) des zweiten Überzugsmittels plus 5 bis 50 % von 20 Gew,.%, d.h. der Polyurethangehalt des ersten Überzugsmittels ist dann bevorzugt: X + (1 bis 10) Gew.-%. Dabei unterscheidet sich jedoch der absolute Wert des Gewichtsgehaltes an Festharz im ersten Basislacküberzugsmittels um nicht mehr als 20 % von dem absoluten Wert des Gewichtsgehalts an Festharz im zweiten Basislacküberzugsmittel; beträgt also im vorstehenden Beispiel der Festharzgehalt des zweiten Basislacküberzugsmittels 20 Gew.-%, so kann dementsprechend der Festharzgehalt des ersten Basislacküberzugsmittels insgesamt bei 16 bis 24 Gew.-% liegen. Dabei ist der Festharzgehalt des ersten Überzugsmittels besonders bevorzugt gleich oder höher als der des zweiten Basislacküberzugsmittels. Beispielsweise kann das erste Basislacküberzugsmittel gemäß einer bevorzugten Verfahrensweise aus dem zweiten Basislacküberzugmittel durch Zumischen einer entsprechenden Menge an Polyurethanharz hergestellt werden.It is essential to the invention that the first to generate the second Coating layer used waterborne basecoat compared to the second waterborne basecoat used to create the third coating layer characterized by a higher proportion by weight of polyurethane resins. The absolute value preferably corresponds to this excess Polyurethane resins in the first water-based paint between 5 and 50%, particularly preferably between 10 and 35% of the absolute value of the Solid resin weight content in the second coating agent. Know accordingly the second basecoat coating agent has a solid resin content from 20% by weight, the preferred absolute value for is calculated the polyurethane content in the first basecoat coating composition as a sum the polyurethane content X (% by weight) of the second coating agent plus 5 to 50% of 20% by weight, i.e. the polyurethane content of the first Coating agent is then preferred: X + (1 to 10) wt .-%. Here however, the absolute value of the weight content differs Solid resin in the first basecoat by no more than 20% of the absolute value of the weight content of solid resin in the second Basecoat coating compositions; in the example above is Solid resin content of the second basecoat coating composition 20 wt .-%, so accordingly the solid resin content of the first basecoat coating composition total 16 to 24 wt .-%. The solid resin content of the first coating agent particularly preferably equal to or higher than that of the second basecoat coating agent. For example, the first Basecoat coating composition according to a preferred procedure from the second basecoat coating agent by admixing a corresponding one Amount of polyurethane resin can be produced.

Der höhere Anteil an Polyurethanharz kann, falls im zweiten Wasserbasislack Polyurethanharz enthalten ist, durch das oder die gleichen oder durch davon verschiedene Polyurethanharze ausgemacht werden. Beispiele für Polyurethanharze, die den höheren Anteil im ersten Wasserbasislack ausmachen können, sind die vorstehend als Bindemittel für Wasserbasislacke geeignet beschriebenen Polyurethanharze. The higher proportion of polyurethane resin, if in the second Waterborne basecoat polyurethane resin is contained by the or made out of the same or different polyurethane resins become. Examples of polyurethane resins that the higher proportion in can make out first waterborne basecoat, are the above as Binder suitable for water-based paints Polyurethane resins.

Neben dem erfindungswesentlichen Unterscheidungsmerkmal des gegenüber dem zweiten Wasserbasislack im ersten Wasserbasislack höheren Anteils an Polyurethanharz können für die nach dem erfindungsgemäßen Verfahren hergestellte zweite und dritte Überzugsschicht sich auch in anderen Merkmalen voneinander unterscheidende Wasserbasislacke, bevorzugt jedoch an sich ähnliche Wasserbasislacke eingesetzt werden. Besonders bevorzugt unterscheiden sich die beiden Wasserbasislacke ausschließlich durch das vorstehend genannte erfindungswesentliche Unterscheidungsmerkmal. Dies wird im folgenden näher erläutert.In addition to the essential distinguishing feature of the invention the second waterborne basecoat in the first waterborne basecoat of a higher proportion of polyurethane resin can be used for the process according to the invention manufactured second and third coating layers are also in others Features of water-based paints that differ from one another, preferred however, similar waterborne basecoats can be used. Especially the two water-based paints preferably differ only by the above-mentioned essential to the invention Distinguishing feature. This is explained in more detail below.

Es ist besonders bevorzugt, wenn der erste und der zweite Wasserbasislack, abgesehen von dem Polyurethanüberschuß des ersten Wasserbasislacks qualitativ die gleiche Festharzzusammensetzung aufweisen, d.h., die gleichen Bindemittel und gegebenenfalls Vernetzer und gegebenenfalls Pastenharze vorliegen. Dabei ist es bevorzugt, wenn unter Berücksichtigung der erfindungsgemäßen Spezifikationen die Quantität der jeweiligen Komponenten der Festharzzusammensetzung, abgesehen von dem Polyurethan-Überschuß, lediglich eine Schwankungsbreite von unter 30 %, besonders bevorzugt unter 20 % und insbesondere bevorzugt unter 15 % aufweisen. Insbesondere ist es bevorzugt, wenn beide Wasserbasislacke sich sowohl hinsichtlich ihrer qualitativen als auch quantitativen Festharzzusammensetzung nicht unterscheiden mit Ausnahme des erfindungswesentlichen Unterscheidungskriteriums. Zusätzlich ist es bevorzugt, wenn der zur Erzeugung der zweiten Überzugsschicht verwendete Wasserbasislack einen Farbton aufweist, der dem des zur Erzeugung der dritten Überzugsschicht verwendeten Wasserbasislacks nahekommt oder besonders bevorzugt mit diesem identisch ist. Bevorzugt ist unter einander nahekommenden Farbtönen im Rahmen der vorliegenden Erfindung zu verstehen, daß der sich aus Helligkeitsdifferenz, Bunttondifferenz und Buntheitsdifferenz zusammensetzende Farbabstand zwischen den jeweils bei deckender Lackierung und einer Meßgeometrie von (45/0) bestimmten Farbtönen der zweiten und der dritten Überzugsschicht einen n-fachen ΔE* (CIELAB)-Wert nicht überschreitet. Dabei gilt als ΔE* (CIELAB)-Bezugswert derjenige Wert, der sich in dem dem Fachmann geläufigen CIE-x,y-Diagramm (Chromatizitätsdiagramm) in Anlehnung an DIN 6175 für den Farbton der dritten Überzugsschicht ergibt und wobei folgende Beziehung gilt:

  • n ≤ 90 im mit ΔE* = 0,3 gekennzeichneten Bereich des CIE-x,y-Diagramms,
  • n ≤ 50 im mit ΔE* = 0,5 gekennzeichneten Bereich des CIE-x,y-Diagramms,
  • n ≤ 40 im mit ΔE* = 0,7 gekennzeichneten Bereich des CIE-x,y-Diagramms,
  • n ≤ 30 im mit ΔE* = 0,9 gekennzeichneten Bereich des CIE-x,y-Diagramms.
    • It is particularly preferred if the first and the second water-based lacquer, apart from the excess polyurethane of the first water-based lacquer, have the same solid resin composition, ie the same binders and optionally crosslinking agents and optionally paste resins are present. It is preferred if, taking into account the specifications according to the invention, the quantity of the respective components of the solid resin composition, apart from the excess polyurethane, only have a fluctuation range of less than 30%, particularly preferably less than 20% and particularly preferably less than 15%. In particular, it is preferred if the two waterborne basecoats do not differ in terms of their qualitative or quantitative solid resin composition, with the exception of the distinguishing criterion essential to the invention. In addition, it is preferred if the waterborne basecoat used to produce the second coating layer has a color tone which is close to or particularly preferably is identical to that of the waterborne basecoat used to produce the third coating layer. In the context of the present invention, it is preferred to understand each other as closely as possible color tones that the difference in color, consisting of brightness difference, color tone difference and color difference, between the respective color tones of the second and third coating layers determined with opaque coating and a measurement geometry of (45/0) is an n -fold ΔE * (CIELAB) value. The ΔE * (CIELAB) reference value is the value which results in the CIE x, y diagram (chromaticity diagram) familiar to the person skilled in the art based on DIN 6175 for the color of the third coating layer, and the following relationship applies:
  • n ≤ 90 in the area of the CIE x, y diagram marked with ΔE * = 0.3,
  • n ≤ 50 in the area of the CIE x, y diagram marked with ΔE * = 0.5,
  • n ≤ 40 in the area of the CIE x, y diagram marked with ΔE * = 0.7,
  • n ≤ 30 in the area of the CIE x, y diagram marked ΔE * = 0.9.

    • Als Klarlacküberzugsmittel für die Erzeugung der vierten und gegebenenfalls weiterer Überzugsschichten sind grundsätzlich alle üblichen Klarlacke oder transparent farbig oder farblos pigmentierten Überzugsmittel geeignet. Dabei kann es sich um ein- oder mehrkomponentige Klarlacküberzugsmittel handeln. Sie können lösemittelfrei (flüssig oder als Pulverklarlack) sein, oder es kann sich um Systeme auf der Basis von Lösemitteln handeln oder es handelt sich um wasserverdünnbare Klarlacke, deren Bindemittelsysteme in geeigneter Weise, z.B. anionisch, kationisch oder nicht-ionisch, stabilisiert sind. Bei den wasserverdünnbaren Klarlacksystemen kann es sich um wasserlösliche oder in Wasser dispergierte Systeme, beispielsweise Emulsionssysteme oder Pulverslurry-Systeme handeln. Die Klarlacküberzugsmittel härten beim Einbrennen unter Ausbildung kovalenter Bindungen infolge chemischer Vernetzung aus.As a clear coat for the generation of the fourth and any additional coating layers are in principle all usual clear coats or transparent colored or colorless pigmented Coating agent suitable. It can be one or act multi-component clear lacquer coating agents. You can be solvent-free (liquid or as a powder clear coat), or it can are systems based on solvents or are are water-thinnable clear coats, whose binder systems in suitably, e.g. anionic, cationic or non-ionic, are stabilized. With the water-borne clear lacquer systems it can are water-soluble or water-dispersed systems, act, for example, emulsion systems or powder slurry systems. The Clear lacquer coating agents harden during baking under training covalent bonds due to chemical cross-linking.

    Bei den im erfindungsgemäßen Verfahren verwendbaren Klarlacken handelt es sich um die üblichen Klarlacküberzugsmittel, die dem Fachmann geläufig sind und die ein oder mehrere übliche Basisharze als filmbildende Bindemittel enthalten. Sie können, falls die Basisharze nicht selbstvernetzend sind, gegebenenfalls auch Vernetzer enthalten. Sowohl die Basisharzkomponente als auch die Vernetzerkomponente unterliegen keinerlei Beschränkung. Als filmbildende Bindemittel (Basisharze) können beispielsweise Polyester-, Polyurethan- und/oder (Meth)acryl-Copolymer-Harze verwendet werden.The clear lacquers which can be used in the process according to the invention are concerned it is the usual clearcoat coating agent, the expert are common and the one or more common base resins as contain film-forming binders. You can, if the base resins are not self-crosslinking and may also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any restrictions. As a film-forming binder (Base resins) can, for example, polyester, polyurethane and / or (Meth) acrylic copolymer resins can be used.

    Neben den chemisch vernetzenden Bindemitteln sowie gegebenenfalls Vernetzern können die im erfindungsgemäßen Verfahren einsetzbaren Klarlacke lackübliche Additive, wie z.B. Katalysatoren, Verlaufsmittel, Farbstoffe, insbesondere jedoch Rheologiesteuerer, wie Mikrogele, NAD (= non-aqueous-dispersions), disubstituierte Harnstoffe ("sagging control agents"), sowie Lichtschutzmittel gegebenenfalls in Kombination mit Antioxidantien enthalten.In addition to the chemically crosslinking binders and, if appropriate Crosslinkers can be used in the process according to the invention Clear varnish additives, such as Catalysts, leveling agents, Dyes, but especially rheology control agents such as microgels, NAD (= non-aqueous dispersions), disubstituted ureas ("sagging control agents "), and light protection agents, if necessary in combination contain with antioxidants.

    Spezielle Beispiele für ein- (1K) und zweikomponentige (2K) nichtwäßrige Klarlacksysteme, die im erfindungsgemäßen Verfahren als Klarlack eingesetzt werden können, findet man in DE-A-38 26 693, DE-A-40 17 075, DE-A-41 24 167, DE-A-41 33 704, DE-A-42 04 518, DE-A-42 04 611, EP-A-0 257 513, EP-A-0 408 858, EP-A-0 523 267, EP-A-0 557 822, WO-92 11 327.Specific examples of one (1K) and two component (2K) non-aqueous Clear lacquer systems that in the process according to the invention as Clear varnish can be used can be found in DE-A-38 26 693, DE-A-40 17 075, DE-A-41 24 167, DE-A-41 33 704, DE-A-42 04 518, DE-A-42 04 611, EP-A-0 257 513, EP-A-0 408 858, EP-A-0 523 267, EP-A-0 557 822, WO 92 11 327.

    Spezielle Beispiele für ein- (1K) oder zweikomponentige (2K) Wasserklarlacksysteme, die im erfindungsgemäßen Verfahren als Klarlack eingesetzt werden können, findet man in DE-A-39 10 829, DE-A-40 09 931, DE-A-40 09 932, DE-A-41 01 696, DE-A-41 32 430, DE-A-41 34 290, DE-A-42 03 510, EP-A-0 365 098, EP-A-0 365 775, EP-A-0 496 079, EP-A-0 546 640.Special examples for one (1K) or two-component (2K) Water-clear lacquer systems used as clear lacquer in the process according to the invention can be used can be found in DE-A-39 10 829, DE-A-40 09 931, DE-A-40 09 932, DE-A-41 01 696, DE-A-41 32 430, DE-A-41 34 290, DE-A-42 03 510, EP-A-0 365 098, EP-A-0 365 775, EP-A-0 496 079, EP-A-0 546 640.

    Spezielle Beispiele für Pulverklarlacksysteme, die im erfindungsgemäßen Verfahren als Klarlack eingesetzt werden können, findet man in EP-A-0 509 392, EP-A-0 509 393, EP-A-0 522 648, EP-A-0 544 206, EP-A-0 555 705, DE-A-42 22 194, DE-A-42 27 580.Specific examples of powder clearcoat systems in the invention Processes that can be used as clear lacquer can be found in EP-A-0 509 392, EP-A-0 509 393, EP-A-0 522 648, EP-A-0 544 206, EP-A-0 555 705, DE-A-42 22 194, DE-A-42 27 580.

    Der transparente Überzug kann in einer einzigen Schicht oder in Form von mehreren Schichten aus dem gleichen oder aus mehreren verschiedenen transparenten Überzugsmitteln aufgebracht werden. Zweckmäßig wird die transparente Überzugsschicht jedoch als vierte Schicht aus nur einem Klarlacküberzugsmittel aufgebracht.The transparent coating can be in a single layer or in shape of multiple layers from the same or from several different transparent coating agents can be applied. The is expedient transparent coating layer, however, as the fourth layer of only one Clear coating agent applied.

    Als Substrat für das erfindungsgemäße Verfahren sind elektrisch leitfähige Materialien, wie beispielsweise Metalle geeignet. Insbesondere geeignet sind z.B. Automobilkarossen oder Teile davon, sie können aus vorbehandeltem oder unvorbehandeltem Metall, aus mit einer elektrisch leitfähigen Schicht versehenem Metall oder elektrisch leitendem oder mit einer elektrisch leitfähigen Schicht versehenen Kunststoff bestehen. Auf diese Substrate wird die erste Überzugsschicht, insbesondere in Form einer Korrosionsschutzgrundierung, elektrophoretisch in üblicher Weise und in einer für ETL-Grundierungen üblichen Trockenschichtdicke von beispielsweise 15 bis 35 µm abgeschieden und eingebrannt. Im besonderen Fall vorbeschichteter Substrate erhält man Mehrschichtlackierungen mit mehr als den erfindungsgemäß erzeugten vier Überzugsschichten, dennoch wird im Rahmen der vorliegenden Erfindung die beim erfindungsgemäßen Verfahren zuerst aufgebrachte Elektrotauchlackschicht als erste Überzugsschicht bezeichnet.As a substrate for the method according to the invention are electrical conductive materials, such as metals. Particularly suitable are e.g. Automobile bodies or parts of them, them can be made of pretreated or untreated metal, with a electrically conductive layer provided metal or electrically conductive or provided with an electrically conductive layer Plastic. The first one is on these substrates Coating layer, especially in the form of a Corrosion protection primer, electrophoretically in the usual way and in a usual dry layer thickness of ETL primers for example, 15 to 35 microns deposited and baked. In particular In the case of pre-coated substrates, multi-layer coatings are obtained more than the four coating layers produced according to the invention, nevertheless is in the context of the present invention in the invention Process first applied electrocoat layer first Called coating layer.

    Auf das mit der eingebrannten ETL-Schicht versehene Substrat wird die zweite Überzugsschicht aus dem ersten farb- und/oder effektgebenden Wasserbasislack bevorzugt in einem Spritzgang in einer von der Deckfähigkeit des Farbtons abhängigen Trockenschichtdicke von 10 bis unter 30 µm, beispielsweise 10 bis 29 µm, bevorzugt von 10 bis 25 µm, besonders bevorzugt von 10 bis 20 µm aufgetragen. Beispiele für geeignete Spritzauftragsverfahren sind Druckluftspritzen, Airless-Spritzen oder elektrostatisches (ESTA)-Hochrotationsspritzen, wobei elektrostatisches Spritzen für den Auftrag des ersten Wasserbasislacks das bevorzugte Auftragsverfahren darstellt. Nach einer kurzen Ablüftzeit, gegebenenfalls bei erhöhten Temperaturen bis 80°C, bevorzugt jedoch bei Umgebungstemperatur, wird die dritte Überzugsschicht aus dem zweiten farb- und/oder effektgebenden Wasserbasislack in einem Spritzgang bevorzugt durch Druckluftspritzen bevorzugt in einer geringeren Trockenschichtdicke als die zweite Überzugsschicht, von nur 7 bis 15 µm aufgetragen und kurz abgelüftet, gegebenenfalls bei Temperaturen bis 80°C, beispielsweise während 1 bis 5 Minuten, z.B. durch Einwirkung von Infrarotstrahlung. Im Anschluß an die Applikation und das Ablüften der dritten Überzugsschicht erfolgt der Auftrag des Klarlacks im Naß-in-Naß-Verfahren.On the substrate provided with the burned-in ETL layer second coating layer from the first color and / or effect Waterborne basecoat preferably in one spray pass in one of the Opacity of the color-dependent dry layer thickness from 10 to less than 30 µm, for example 10 to 29 µm, preferably 10 to 25 µm, applied particularly preferably from 10 to 20 microns. examples for Suitable spray application methods are compressed air spraying, airless spraying or electrostatic (ESTA) high-rotation spraying, wherein electrostatic spraying for the application of the first waterborne basecoat is the preferred application method. After a short Flash-off time, if necessary at elevated temperatures up to 80 ° C, preferred, however, at ambient temperature, the third Coating layer from the second color and / or effect Waterborne basecoat in one spray pass, preferably by compressed air spraying preferably in a smaller dry layer thickness than the second Coating layer, applied from only 7 to 15 µm and briefly vented, optionally at temperatures up to 80 ° C, for example during 1 to 5 minutes, e.g. by exposure to infrared radiation. In connection to the third coating layer is applied and vented the application of the clear lacquer in the wet-on-wet process.

    Die vierte Überzugsschicht wird aus einem üblichen flüssigen Klarlack oder Pulverklarlack (in diesem Fall handelt es sich um eine Trocken-in-Naß-Applikation) in einer für Klarlackschichten üblichen Trockenschichtdicke von beispielsweise 30 bis 80 µm, bevorzugt 30 bis 60 µm, überlackiert und gemeinsam mit der zweiten und dritten Überzugsschicht eingebrannt. Beispielsweise liegt die Einbrenntemperatur beim gemeinsamen Einbrennen der drei Überzugsschichten zwischen 80 und 160°C, bevorzugt unter 140°C. Gegebenenfalls können weitere Klarlackschichten aus dem gleichen oder davon verschiedenen Klarlacküberzugsmitteln vor oder nach dem Einbrennen aufgebracht werden.The fourth coating layer is made from a common liquid clear coat or powder clearcoat (in this case it is a dry-on-wet application) in a usual for clear lacquer layers Dry layer thickness of for example 30 to 80 microns, preferably 30 to 60 µm, overpainted and together with the second and third Coated layer. For example, the Baking temperature when baking the three together Coating layers between 80 and 160 ° C, preferably below 140 ° C. If necessary, further layers of clear lacquer from the same or of which various clear lacquer coating agents before or after Branding can be applied.

    Das erfindungsgemäße Verfahren erlaubt die Herstellung vier- oder auch mehrschichtiger Lackierungen, insbesondere Kraftfahrzeuglackierungen mit im Vergleich zum Stand der Technik, der Füllerschichten und/oder andere Zwischenschichten einschließt, verringerter Gesamtschichtdicke und vergleichbarem Gesamteigenschaftsniveau. Es sind nur zwei Einbrennschritte notwendig. Es hat sich gezeigt, daß hervorragende Eigenschaften durch die erfindungsgemäße Verfahrensweise erzielt werden, obwohl diese den Wegfall üblicher Füllerschichten ermöglicht.The method according to the invention allows the production of four or even multi-layer paintwork, in particular automotive paintwork with compared to the prior art, the filler layers and / or includes other intermediate layers, reduced total layer thickness and comparable overall property level. There are only two Burn-in steps necessary. It has been shown to be excellent Properties achieved by the procedure according to the invention even though this eliminates the need for conventional filler layers.

    Beispiel 1 (Stand der Technik, Lackierung mit Füllerschicht) Example 1 (state of the art, painting with filler layer)

    Auf ein übliches phosphatiertes und durch kathodische Tauchlackierung und mit einer 30 µm dicken Füllerschicht vorbeschichtetes Karosserieblech wird durch Spritzen ein Wasserbasislack (Blau-Metallic) in einer Trockenschichtdicke von 15 µm aufgebracht. Nach der Applikation wird kurz abgelüftet und anschließend 10 Minuten bei 80°C vorgetrocknet. Anschließend wird mit einem handelsüblichen 2K-HS-Autoserienklarlack (Zweikomponenten-High-Solid-Klarlack auf Acrylharz/Polyisocyanat-Basis) in einer Trockenschichtdicke von 40 µm überlackiert und 30 Minuten bei 130°C (Objekttemperatur) getrocknet. Der Wasserbasislack (Blau-Metallic) bestand aus folgenden Komponenten:

    17,00 Teile
    wäßrige Polymerisatdispersion aus DE-A-36 28 124, Herstellungsbeispiel 1
    9,20 Teile
    wäßrige Polyurethandispersion aus DE-A-42 24 617, Herstellungsbeispiel 2
    3,10 Teile
    wäßriges Polyurethanharz gemäß Beispiel aus DE-A-40 00 889
    2,70 Teile
    Hexamethoxymethylmelamin
    1,00 Teile
    Aluminiumbronze
    1,60 Teile
    Cu-Phthalocyaninpigment
    0,90 Teile
    Talkum
    0,50 Teile
    lacküblicher Entschäumer
    0,50 Teile
    lackübliches Netzmittel
    7,00 Teile
    Butoxyethanol
    2,50 Teile
    2-Propanol
    2,50 Teile
    2-Butanol
    51,50 Teile
    deionisiertes Wasser
    A water-based paint (blue metallic) with a dry layer thickness of 15 µm is applied by spraying to a customary, phosphated body panel pre-coated by cathodic dip painting and with a 30 µm thick filler layer. After application, the product is briefly flashed off and then predried at 80 ° C. for 10 minutes. It is then overpainted with a commercially available 2K-HS automotive series clear coat (two-component high-solid clear coat based on acrylic resin / polyisocyanate) in a dry layer thickness of 40 µm and dried for 30 minutes at 130 ° C (object temperature). The water-based paint (blue metallic) consisted of the following components:
    17.00 parts
    aqueous polymer dispersion from DE-A-36 28 124, preparation example 1
    9.20 parts
    aqueous polyurethane dispersion from DE-A-42 24 617, preparation example 2
    3.10 parts
    aqueous polyurethane resin according to the example from DE-A-40 00 889
    2.70 parts
    Hexamethoxymethylmelamine
    1.00 parts
    Aluminum bronze
    1.60 parts
    Cu phthalocyanine pigment
    0.90 parts
    talc
    0.50 parts
    customary defoamer
    0.50 parts
    customary paint wetting agent
    7.00 parts
    Butoxyethanol
    2.50 parts
    2-propanol
    2.50 parts
    2-butanol
    51.50 parts
    deionized water

    Der Festharzgehalt (absoluter Wert des Gewichtsgehalts an Festharz) dieses Wasserbasislacks beträgt 13,8 Gew.-%.The solid resin content (absolute value of the weight content of solid resin) this waterborne basecoat is 13.8% by weight.

    Beispiel 2 (Vergleich, Lackierung ohne Füllerschicht) Example 2 (comparison, painting without filler layer)

    Auf ein übliches phosphatiertes und durch kathodische Tauchlackierung vorbeschichtetes Karosserieblech wird durch Spritzen der Wasserbasislack (Blau-Metallic) aus Beispiel 1 in einer Trockenschichtdicke von 15 µm aufgebracht. Nach der Applikation wird kurz abgelüftet und anschließend eine zweite Schicht aus dem gleichen Wasserbasislack in einer Trockenschichtdicke von 10 µm ebenfalls durch Spritzen aufgebracht. Es wird 10 Minuten bei 80°C vorgetrocknet. Anschließend wird mit dem 2K-HS-Autoserienklarlack aus Beispiel 1 in einer Trockenschichtdicke von 40 µm überlackiert und 30 Minuten bei 130°C (Objekttemperatur) getrocknet.On a usual phosphated and by cathodic dip painting Pre-coated body panels are sprayed on Waterborne basecoat (blue metallic) from Example 1 in one Dry layer thickness of 15 µm applied. After the application flashed off briefly and then a second layer of the same Waterborne basecoat in a dry layer thickness of 10 µm also through Syringes applied. It is predried at 80 ° C. for 10 minutes. Subsequently, the 2K-HS car series clear coat from Example 1 is used overcoated with a dry film thickness of 40 µm and at 30 minutes 130 ° C (object temperature) dried.

    Beispiel 3 a-c (erfindungsgemäß) Example 3 ac (according to the invention)

    Beispiel 2 wird wiederholt mit dem Unterschied, daß die 15 µm dicke auf die KTL-Schicht aufgebrachte Lackschicht nicht aus dem Wasserbasislack (Blau-Metallic) aus Beispiel 1 aufgebracht wird, sondern aus einem modifizierten Wasserbasislack (Blau-Metallic), während die anschließend in 10 µm Trockenschichtdicke aufgebrachte Lackschicht wie in Beispiel 2 aus dem Wasserbasislack (Blau-Metallic) aus Beispiel 1 erzeugt wird. Der modifizierte Wasserbasislack (Blau-Metallic) wird hergestellt durch Vermischen von 87 Teilen des Wasserbasislacks (Blau-Metallic) aus Beispiel 1 mit 13 Teilen eines auf einen Festkörpergehalt von 34 Gew.-% eingestellten wäßrigen Polyurethanharzes. Als wäßrige Polyurethanharze dienen:

  • a) wäßrige Polyurethandispersion aus DE-A-42 24 617, Herstellungsbeispiel 2
  • b) wäßriges Polyurethanharz gemäß Beispiel aus DE-A-40 00 889
  • c) wäßrige Polyurethandispersion aus WO 95/28 249, Herstellungsbeispiel 1
    • Example 2 is repeated with the difference that the 15 μm thick lacquer layer applied to the KTL layer is not applied from the water-based lacquer (blue-metallic) from example 1, but from a modified water-based lacquer (blue-metallic), while the subsequently in 10 μm dry layer thickness applied lacquer layer as in example 2 is produced from the water-based lacquer (blue metallic) from example 1. The modified waterborne basecoat (blue metallic) is produced by mixing 87 parts of the waterborne basecoat (blue metallic) from Example 1 with 13 parts of an aqueous polyurethane resin adjusted to a solids content of 34% by weight. The following are used as aqueous polyurethane resins:
  • a) aqueous polyurethane dispersion from DE-A-42 24 617, preparation example 2
  • b) aqueous polyurethane resin according to the example from DE-A-40 00 889
  • c) aqueous polyurethane dispersion from WO 95/28 249, preparation example 1

    • Der Festharzgehalt (absoluter Wert des Gewichtsgehalts an Festharz) der Wasserbasislacke 3a), 3b) und 3c) beträgt jeweils 16,4 Gew.-%. Es liegt also ein Überschuß von (16,4-13,8) x 100/13,8 = 18.9 Gew.-% Festharz und damit auch Polyurethanharz, im Vergleich mit dem Wasserbasislack von Beispiel 1 vor.The solid resin content (absolute value of the weight content of solid resin) of the Water-based paints 3a), 3b) and 3c) are each 16.4% by weight. It lies thus an excess of (16.4-13.8) x 100 / 13.8 = 18.9% by weight solid resin and thus also polyurethane resin, in comparison with the water-based paint of Example 1 before.

    Beispiel 4 (Stand der Technik, Lackierung mit Füllerschicht) Example 4 (state of the art, painting with filler layer)

    Auf ein übliches phosphatiertes und durch kathodische Tauchlackierung und mit einer 30 µm dicken Füllerschicht vorbeschichtetes Karosserieblech wird durch Spritzen der nachstehend beschriebene Wasserbasislack (Schwarz) in einer Trockenschichtdicke von 20 µm aufgebracht. Nach der Applikation wird kurz abgelüftet und anschließend 10 Minuten bei 80°C vorgetrocknet.On a usual phosphated and by cathodic dip painting and pre-coated with a 30 µm thick filler layer Body panel is made by spraying the one described below Waterborne basecoat (black) in a dry layer thickness of 20 µm upset. After application, the product is briefly vented and then Predried at 80 ° C for 10 minutes.

    Anschließend wird mit dem 2K-HS-Autoserienklarlack aus Beispiel 1 in einer Trockenschichtdicke von 40 µm überlackiert und 30 Minuten bei 130°C (Objekttemperatur) getrocknet. Der Wasserbasislack (Schwarz) bestand aus folgenden Komponenten:

    11,00 Teile
    des 60 gew.-%igen Bindemittels aus WO 95/16004, Punkt 2, Beispiel 4
    19,90 Teile
    wäßrige Polyurethandispersion aus DE-A-42 24 617, Herstellungsbeispiel 2
    12,90 Teile
    wäßriges Polyurethanharz gemäß Beispiel aus DE-A-40 00 889
    3,80 Teile
    Hexamethoxymethylmelamin
    3,00 Teile
    Ruß
    2,00 Teile
    Talkum
    0,70 Teile
    lacküblicher Entschäumer
    1,20 Teile
    lackübliches Netzmittel
    0,70 Teile
    Haftvermittler
    5,70 Teile
    Butoxyethanol
    4,50 Teile
    Diethylenglykol-monobutylether
    3,00 Teile
    N-Methylpyrroldion
    0,30 Teile
    Dimethylethanolamin
    31,30 Teile
    deionisiertes Wasser
    Then the 2K-HS automotive series clearcoat from example 1 is overpainted in a dry layer thickness of 40 μm and dried for 30 minutes at 130 ° C. (object temperature). The water-based paint (black) consisted of the following components:
    11.00 parts
    of the 60% by weight binder from WO 95/16004, point 2, example 4
    19.90 parts
    aqueous polyurethane dispersion from DE-A-42 24 617, preparation example 2
    12.90 parts
    aqueous polyurethane resin according to the example from DE-A-40 00 889
    3.80 parts
    Hexamethoxymethylmelamine
    3.00 parts
    soot
    2.00 parts
    talc
    0.70 parts
    customary defoamer
    1.20 parts
    customary paint wetting agent
    0.70 parts
    Adhesion promoter
    5.70 parts
    Butoxyethanol
    4.50 parts
    Diethylene glycol monobutyl ether
    3.00 parts
    N-methylpyrroldione
    0.30 parts
    Dimethylethanolamine
    31.30 parts
    deionized water

    Dieser Wasserbasislack hat einen Festharzgehalt von 21,9 Gew.-%.This waterborne basecoat has a solid resin content of 21.9% by weight.

    Beispiel 5 (Vergleich, Lackierung ohne Füllerschicht) Example 5 (comparison, painting without filler layer)

    Auf ein übliches phosphatiertes und durch kathodische Tauchlackierung vorbeschichtetes Karosserieblech wird durch Spritzen der Wasserbasislack (Schwarz) aus Beispiel 4 in einer Trockenschichtdicke von 15 µm aufgebracht. Nach der Applikation wird kurz abgelüftet und anschließend eine zweite Schicht aus dem gleichen Wasserbasislack in einer Trockenschichtdicke von 10 µm ebenfalls durch Spritzen aufgebracht. Es wird 10 Minuten bei 80°C vorgetrocknet. Anschließend wird mit dem 2K-HS-Autoserienklarlack aus Beispiel 1 in einer Trockenschichtdicke von 40 µm überlackiert und 30 Minuten bei 130°C (Objekttemperatur) getrocknet.On a usual phosphated and by cathodic dip painting Pre-coated body panels are sprayed on Water-based paint (black) from example 4 in a dry layer thickness of 15 µm applied. After application, the product is briefly vented and then a second coat of the same waterborne basecoat in a dry film thickness of 10 µm also by spraying upset. It is predried at 80 ° C. for 10 minutes. Subsequently is with the 2K-HS car series clear coat from Example 1 in one Dry layer thickness of 40 µm overcoated and 30 minutes at 130 ° C (Object temperature) dried.

    Beispiel 6 a-c erfindungsgemäß Example 6 ac according to the invention

    Beispiel 5 wird wiederholt mit dem Unterschied, daß die 15 µm dicke auf die KTL-Schicht aufgebrachte Lackschicht nicht aus dem Wasserbasislack (Schwarz) aus Beispiel 4 aufgebracht wird, sondern aus einem modifizierten Wasserbasislack (Schwarz), während die anschließend in 10 µm Trockenschichtdicke aufgebrachte Lackschicht wie in Beispiel 5 aus dem Wasserbasislack (Schwarz) aus Beispiel 4 erzeugt wird. Der modifizierte Wasserbasislack (Schwarz) wird hergestellt durch Vermischen von 85 Teilen des Wasserbasislacks (Schwarz) aus Beispiel 4 mit 15 Teilen eines auf einen Festkörpergehalt von 34 Gew.-% eingestellten wäßrigen Polyurethanharzes.
    Als wäßrige Polyurethanharze dienen:

  • a) wäßrige Polyurethandispersion aus DE-A-42 24 617, Herstellungsbeispiel 2
  • b) wäßriges Polyurethanharz gemäß Beispiel aus DE-A-40 00 889
  • c) wäßrige Polyurethandispersion aus WO 95/28 249, Herstellungsbeispiel 1
    • Example 5 is repeated with the difference that the 15 μm thick lacquer layer applied to the KTL layer is not applied from the water-based lacquer (black) from example 4, but from a modified water-based lacquer (black), while the one subsequently applied in 10 μm dry layer thickness Lacquer layer as in Example 5 is produced from the water-based lacquer (black) from Example 4. The modified waterborne basecoat (black) is prepared by mixing 85 parts of the waterborne basecoat (black) from Example 4 with 15 parts of an aqueous polyurethane resin adjusted to a solids content of 34% by weight.
    The following are used as aqueous polyurethane resins:
  • a) aqueous polyurethane dispersion from DE-A-42 24 617, preparation example 2
  • b) aqueous polyurethane resin according to the example from DE-A-40 00 889
  • c) aqueous polyurethane dispersion from WO 95/28 249, preparation example 1

    • Die Wasserbasislacke 6a), 6b) und 6c) haben jeweils einen Festharzgehalt von 23,7 Gew.-%. Der Überschuß an Festharz und im vorliegenden Falle auch an Polyurethanharz zum Wasserbasislack von Beispiel 4 beträgt daher (23,7-21,9) x 100/21,9 = 8,3 Gew.-%.The water-based paints 6a), 6b) and 6c) each have one Solid resin content of 23.7% by weight. The excess of solid resin and in in the present case also on polyurethane resin for waterborne basecoat Example 4 is therefore (23.7-21.9) x 100 / 21.9 = 8.3% by weight.

    Sowohl die Mehrschichtlackierung aus den Beispielen 1, 2 3a - c als auch aus den Beispielen 4, 5, 6a - c unterscheiden sich jeweils weder in der Haftung noch in der Schwitzwasserbeständigkeit, die Ergebnisse entsprechen heute üblichen technologischen Anforderungen.Both the multi-layer coating from Examples 1, 2 3a - c as neither do examples differ from examples 4, 5, 6a-c either in the liability still in the condensation resistance, the results meet today's technological requirements.

    Tabelle 1 stellt die Ergebnisse der durchgeführten Steinschlagtests zusammen. Mehrschichtlackierung 1 2 3a 3b 3c 4 5 6a 6b 6c VDA-Steinschlag 1 3 1 1 1 3 1 1 Steinschlag nach "Splitt-Methode" 7 12 3 5 6 5 10 4 4 4 0-1 4-5 0-1 0-1 1 0-1 4-5 0-1 0-1 1 Table 1 summarizes the results of the stone chip tests carried out. Multi-layer painting 1 2nd 3a 3b 3c 4th 5 6a 6b 6c VDA rockfall 1 3rd 1 1 1 3rd 1 1 Stone chipping using the "split method" 7 12th 3rd 5 6 5 10th 4th 4th 4th 0-1 4-5 0-1 0-1 1 0-1 4-5 0-1 0-1 1

    Bewertung: Angabe der kreisrunden Schadenfläche in mm2 und der an der Schadenfläche durch 10minütige Einwirkung von 1 %iger Kupfersulfatlösung bestimmte Rostgrad, Rostgrad 0 = bester Wert, Rostgrad 5 = schlechtester Wert.Evaluation: Specification of the circular damage area in mm 2 and the degree of rust determined on the damaged area by the action of 1% copper sulfate solution for 10 minutes, degree of rust 0 = best value, degree of rust 5 = worst value.

    Claims (8)

    1. Process for the production of a multilayer lacquer coating on a substrate provided with a stoved, first electrodeposition coating layer, characterised in that a second coating layer, corresponding to a dry film thickness of 10 to below 30 µm, of a first, aqueous coloured and/or effect base lacquer coating composition containing one or more polyurethane resins is applied onto the first electrodeposition coating layer, whereupon a third coating layer corresponding to a lesser dry film thickness of 7 to 15 µm of a second, aqueous coloured and/or effect base lacquer coating composition is applied wet-on-wet and a fourth coating layer of a clear lacquer coating composition is applied without prior stoving onto the third coating layer and the second, third and fourth coating layers are stoved together, wherein the first and the second aqueous base lacquer coating compositions contain identical or different polyurethane resins, and the first base lacquer coating composition has a higher polyurethane resin content than the second base lacquer coating composition, relative to the total weight of the particular aqueous base lacquer coating composition, and wherein the solids content in the first base lacquer coating composition deviates by no more than 20% from the absolute value of the weight of the solid resin content in the second base lacquer coating composition.
    2. Process according to claim 1, characterised in that the first aqueous base lacquer coating composition was produced by mixing polyurethane resin into the second base lacquer coating composition.
    3. Process according to claim 1 or 2, characterised in that the excess of polyurethane resin in the first aqueous base lacquer coating composition amounts to 5 to 50% of the absolute value of the content by weight of solid resin in the second base lacquer coating composition.
    4. Process according to claim 1, 2 or 3, characterised in that the first base lacquer coating composition has a pigment volume concentration which varies by no more than 30% from the absolute value of the pigment volume concentration of the second base lacquer coating composition.
    5. Process according to one of claims 1 to 4, characterised in that, apart from the excess polyurethane resin content of the second base lacquer coating composition, the resins which form the solid resin content of the first and second base lacquer coating composition have the same qualitative and quantitative composition.
    6. Process according to one of claims 1 to 5, characterised in that identical pigment formulations are present in both the base lacquer coating compositions or that the pigment formulations in both base lacquer coating compositions have, on average, similar specific weights.
    7. Process according to one of claims 1 to 6, characterised in that the pigment content relative to the solids content is higher in the second base lacquer coating composition than in the first base lacquer coating composition.
    8. Process according to one of claims 1 to 7, characterised in that it is performed for lacquer coating motor vehicles or components thereof.
    EP97903326A 1996-02-23 1997-02-19 Multi-coat painting process Expired - Lifetime EP0881954B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19606716 1996-02-23
    DE19606716A DE19606716C1 (en) 1996-02-23 1996-02-23 Process for multi-layer painting
    PCT/EP1997/000784 WO1997030795A1 (en) 1996-02-23 1997-02-19 Multi-coat painting process

    Publications (2)

    Publication Number Publication Date
    EP0881954A1 EP0881954A1 (en) 1998-12-09
    EP0881954B1 true EP0881954B1 (en) 1999-08-11

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    EP (1) EP0881954B1 (en)
    JP (1) JP4096069B2 (en)
    AU (1) AU1792497A (en)
    BR (1) BR9707608A (en)
    DE (2) DE19606716C1 (en)
    ES (1) ES2140962T3 (en)
    WO (1) WO1997030795A1 (en)

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    EP0881954A1 (en) 1998-12-09
    WO1997030795A1 (en) 1997-08-28
    BR9707608A (en) 1999-07-27
    AU1792497A (en) 1997-09-10
    US5976343A (en) 1999-11-02
    DE19606716C1 (en) 1997-08-14
    JP2000505352A (en) 2000-05-09
    ES2140962T3 (en) 2000-03-01
    JP4096069B2 (en) 2008-06-04
    DE59700330D1 (en) 1999-09-16

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