EP1218112B1 - Integrated coating method for auto body parts containing plastic parts or for cabins of passenger cars and utility vehicles as well as for their replacement parts and add-on parts, coating obtainable by this method and coated parts - Google Patents

Abstract

A process for painting integrated automobile and commercial vehicle bodies or cabins which comprise plastic parts. The metal parts of the body/cabin are provided with an electrocoat and are integrated with the plastic parts. These plastic parts either already have an electrically conductive aqueous primer coat or an uncured electrically conductive aqueous primer film or are unpainted. Primers are applied to the metal and plastic parts. Atop the primers, a basecoat and a clearcoat are applied.

Description

The present invention relates to a new integrated painting method for Plastics containing bodies or cabins of cars and Commercial vehicles and their spare parts and attachments. In addition, the concerns present invention, the bodies or cabins of cars and Commercial vehicles and their spare parts and attachments, with the help of the new integrated coating process have been coated.

1) Phosphatierung der Stahloberfläche;

2) Beschichtung mit einem kathodischen Elektrotauchlack und Einbrennen der Elektrotauchlackschicht, wodurch die korrosionsschützende Elektrotauchlackierung resultiert;

3) Applikation eines Füllers und Einbrennen der resultierenden Füllerschicht. wodurch der energieabsorbierende Füller oder die Steinschlagschutzgrundierung resultiert;

4) Applikation eines Basislacks, insbesondere eines Wasserbasislacks, wodurch eine Basislackschicht resultiert;

5) Trocknen der Basislackschicht;

6) Applikation eines Klarlacks, wodurch eine Klarlackschicht resultiert; und

7) gemeinsame thermische Härtung der Basislackschicht und der Klarlackschicht, wodurch die farb- und/oder effektgebende Mehrschichtlackierung resultiert (Naß-in-naß-Verfahren).

With a few exceptions, the bodies or cabins of cars and commercial vehicles, in particular lorries and buses, consisting predominantly of galvanized steel, are painted worldwide using the following procedure:

1) phosphating the steel surface;

2) coating with a cathodic electrodeposition paint and baking the electrodeposition paint layer resulting in anti-corrosive electrodeposition coating;

3) Application of a filler and baking of the resulting filler layer. whereby the energy-absorbing filler or the antistonechip primer results;

4) application of a basecoat, in particular a waterborne basecoat, resulting in a basecoat film;

5) drying the basecoat film;

6) application of a clearcoat, resulting in a clearcoat film; and

7) joint thermal curing of the basecoat film and the clearcoat film, whereby the color and / or effect multi-layer coating results (wet-in-wet process).

This process provides multi-layer coatings of excellent chemical Resistance and weather resistance as well as with outstanding Corrosion protection effect and excellent overall appearance.

Currently available for car and commercial vehicle manufacturing Plastics and plastic parts can do this in the automotive industry do not undergo applied painting because they are in this case applied baking or curing temperatures of over 90 ° C deformed become. It is therefore necessary, all later on the bodies or cabins to be mounted plastic parts separately, d. H. Off-line, to paint, using paints must be used in their curing behavior and in their other Properties must be adapted to the plastics. That's why you can too the color of the painting of the plastic parts only with great effort adapted to the color of the paint of the metal parts.

The automotive industry is therefore trying the color shade problem by the so-called Switch off online or inline paint right from the start.

Under the on-line lacquering the lacquering procedure is to be understood, with the plastic parts after the application and the stoving of the filler on the metal parts of the respective car body or commercial vehicle cabin their assembly platform (skid) are added and then joint be painted.

Inline painting is the painting process in which the Plastic parts already after electrocoating the metal parts and before the Application of the filler on the assembly platform of the respective car body or the commercial vehicle cabin are added, after which the entire arrangement uniformly painted.

However, these inherently beneficial approaches often fail because the hitherto commonly used thermosetting coating materials after their curing at Häramgemperaturen below 100 ° C the Customer specifications, in particular with regard to the corrosion schooling effect, the stone chip resistance and condensation resistance, do not meet can.

From US 4,756,975 is a method for coating automobile bodies known. According to this document, by the use of a special "barier coat" layer achieved good results. A process for multi-layer painting is also known from US 5,389,406. Here are good results by a certain selection of different paint layers, so that the burn-in secondly, the paints are higher. From US 5,252,399 are coatings for aluminum substrates known to use a powder coating as the first layer.

Object of the present invention is to provide a new integrated method for Painting of plastic parts containing bodies of cars and Commercial vehicles and their spare parts and attachments to find that the Disadvantages of the prior art no longer has, but Bodies of passenger cars, in particular emergency vehicle cabins, supplies, which have a uniform color and in terms of their optical General impression, its anti-corrosive effect and its rockfall chemicals, Weathering and condensation resistance all requirements of the market. In particular, according to the new integrated Method produced color and / or effect multi-layer coatings a very good resistance in high pressure cleaning test after previous Fatigue resistance and a high resistance to stone chips even at -20 ° C exhibit.

1) die Metallteile der Karosserie oder der Kabine und/oder deren Ersatzteile oder Anbauteile mit einem Elektrotauchlack beschichtet und die resultierende Elektrotauchlackschicht thermisch härtet, wodurch die korrosionshemmende Elektrotauchlackierung resultiert;

2) die elektrotauchlackierten Metallteile der Karosserie oder der Kabine und/oder deren Ersatzteile oder Anbauteile mit den Kunststoffteilen der Karosserie oder der Kabine integriert, wobei die Kunstsstoffteile

2.1) auf ihrer Oberfläche keine Grundierung,

2.2) auf ihrer Oberfläche eine Grundierung aus einer bei Temperaturen ≤100°C thermisch gehärteten elektrisch leitfähigen Hydroprimerlackierung oder

2.3) auf ihrer Oberfläche eine angetrocknete, indes nicht ausgehärtete elektrisch leitfähige Hydroprimerschicht

aufweisen;

3) die integrierte Metall-Kunststoff-Karosserie oder -Kabine sowie deren Ersatzteile und Anbauteile mit einem Hydroprimer beschichtet, wobei

3.1) die integrierte Metall-Kunststoff Karosserie oder -Kabine sowie deren Ersatzteile und Anbauteile, deren Kunstsstoffteile keine Grundierung aufweisen (Variante 2.1), einheitlich mit einem elektrisch leitfähigen Hydroprimer beschichtet wird und die resultierende Hydroprimerschicht bei Temperaturen ≤100°C ausgehärtet wird, wodurch eine zweischichtige Grundierung aus Elektrotauchlackierung und elektrisch leitfähiger Hydroprimerlackierung auf den Metallteilen und eine einschichtige Grundierung aus elektrisch leitfähiger Hydroprimerlackierung auf den Kunstsstoffteilen resultieren;

3.2) die integrierte Metall-Kunststoff-Karosserie oder -Kabine sowie deren Ersatzteile und Anbauteile, deren Kunstsstoffteile eine Grundierung aus einer Hydroprimerlackierung aufweisen (Variante 2.2), einheitlich mit einem hellen Hydroprimer beschichtet wird und die resultierende helle Hydroprimerschicht bei Temperaturen ≤100°C ausgehärtet wird, wodurch auf den Kunstsstoffteilen eine zweischichtige Grundierung aus elektrisch leitfähiger Hydroprimerlackierung und heller Hydroprimerlackierung und auf den Metallteilen eine zweischichtige Grundierung aus Elektrotauchlackierung und heller Hydroprimerlackierung resultieren;
oder

3.3) die integrierte Metall-Kunststoff-Karosserie oder -Kabine sowie deren Ersatzteile und Anbauteile, deren Kunstsstoffteile eine angetrocknete elektrisch leitfähige Hydroprimerschicht aufweisen (Variante 2.3), einheitlich und bezüglich der Kunstsstoffteile naßin-naß mit einem hellen Hydroprimer beschichtet wird, wonach die elektrisch leitfähige Hydroprimerschicht und die helle Hydroprimerschicht gemeinsam bei Temperaturen ≤100°C ausgehärtet werden, wodurch auf den Kunstsstoffteilen eine zweischichtige Grundierung aus elektrisch leitfähiger Hydroprimerlackierung und heller Hydroprimerlackierung und auf den Metallteilen eine zweischichtige Grundierung aus Elektrotauchlackierung und heller Hydroprimerlackierung resultieren;

4) auf die Grundierungen einheitlich einen farb- und/oder effektgebenden Wasserbasislack appliziert und die resultierende Wasserbasislackschicht ohne auszuhärten antrocknet, wonach man

5) auf die angetrocknete Wasserbasislackschicht naß-in-naß mindestens einen Zweikomponentenklarlack appliziert, wodurch mindestens eine Klarlackschicht resultiert; und

6) die angetrocknete Wasserbasislackschicht und mindestens die eine Klarlackschicht gemeinsam bei Temperaturen ≤100°C thermisch oder thermisch und mit aktinischer Strahlung härtet, wodurch die integrierte farb- und/oder effektgebende Mehrschichtlackierung resultiert.

Accordingly, the new integrated method for painting plastic parts containing bodies or cabins of cars and commercial vehicles and their spare parts and attachments has been found in which one

1) the metal parts of the body or the cabin and / or their spare parts or attachments coated with an electrodeposition paint and the resulting electrodeposition coating layer thermally cured, whereby the corrosion-inhibiting electrodeposition coating results;

2) the electrocoated metal parts of the body or the cabin and / or their spare parts or attachments integrated with the plastic parts of the body or the cabin, wherein the plastic parts

2.1) no primer on its surface,

2.2) on its surface a primer of a thermally cured at temperatures ≤100 ° C electrically conductive hydroprimer or

2.3) on its surface a dried, but not cured electrically conductive Hydroprimerschicht

exhibit;

3) the integrated metal-plastic body or cabin and its spare parts and attachments coated with a hydroprimer, wherein

3.1) the integrated metal-plastic body or cabin and their spare parts and attachments whose plastic parts have no primer (Variant 2.1) is uniformly coated with an electrically conductive hydroprimer and the resulting hydroprimer is cured at temperatures ≤100 ° C, creating a two-layer primer of electrocoating and electrically conductive Hydroprimaler coating on the metal parts and a single-layer primer of electrically conductive Hydroprimaler coating on the plastic parts result;

3.2) the integrated metal-plastic body or cabin and their spare parts and attachments whose plastic parts have a primer of a Hydroprimaler coating (variant 2.2), uniformly coated with a light hydroprimer and the resulting light hydroprimer cured at temperatures ≤100 ° C. which results in a two-layer primer of electrically conductive hydroprimer coating and light hydroprimer coating on the plastic parts and a two-layer primer of electrodeposition coating and light hydroprimer coating on the metal parts;
or

3.3) the integrated metal-plastic body or cabin and their spare parts and attachments whose Kunstsstoffteile have a dried electrically conductive Hydroprimerschicht (variant 2.3), uniformly and wet-wet with respect to the plastic parts coated with a light hydroprimer, after which the electrically conductive Hydroprimerschicht and the light hydroprimer layer are cured together at temperatures ≤100 ° C, resulting in the plastic parts a two-layer primer of electrically conductive hydroprimer and light Hydroprimprimierung and on the metal parts a two-coat primer of electrocoating and bright Hydroprimaler coating;

4) uniformly applied to the primers a color and / or effect waterborne basecoat and the resulting waterborne basecoat dries without curing, after which

5) applying wet-on-wet at least one two-component clearcoat to the dried aqueous basecoat layer, thereby resulting in at least one clearcoat film; and

6) the dried waterborne basecoat layer and at least one clearcoat layer cure together at temperatures ≤100 ° C thermally or thermally and with actinic radiation, whereby the integrated color and / or effect multi-layer coating results.

The following is the new integrated method for painting Plastics containing bodies or cabins of cars and cars Commercial vehicles and their spare parts and attachments for the sake of brevity as "process according to the invention".

1) auf den Metallteilen eine kathodisch oder anodisch, insbesondere kathodisch, abgeschiedene und thermisch gehärtete Elektrotauchlackierung sowie eine elektrisch leitfähige Primerlackierung und/oder eine helle Primerlackierung als Grundierung und

2) auf den Kunststoffteilen eine elektrisch leitfähige Primerlackierung oder eine elektrisch leitfähige Primerlackierung und eine helle Primerlackierung als Grundierung
   mit der Maßgabe, daß die integrierten Karosserien oder Kabinen der PKW und Nutzfahrzeugen sowie deren Ersatzteile und Anbauteile von mindestens einer Primerlackierung über ihre Oberfläche hinweg einheitlich bedeckt sind;
sowie

3) auf der Grundierung der Metallteile und der Kunstsstoffteile eine farbund/oder effektgebende Basislackierung und

4) auf der Basislackierung mindestens eine Klarlackierung.

In addition, the new integrated color and / or effect multi-layer coating for plastic parts containing bodies or cabins of cars and commercial vehicles and their spare parts and attachments has been found, which contains the following layers in the order listed above:

1) on the metal parts a cathodic or anodic, especially cathodic, deposited and thermally cured electrodeposition coating and an electrically conductive primer and / or a light primer paint as a primer and

2) on the plastic parts, an electrically conductive primer coating or an electrically conductive primer coating and a light primer coat as a primer
with the proviso that the integrated bodies or cabins of the passenger cars and commercial vehicles and their spare parts and attachments are uniformly covered by at least one primer paint over its surface;
such as

3) on the primer of the metal parts and the Kunstsstoffteile a color and / or effect basecoat and

4) on the basecoat at least one clearcoat.

The following is the new integrated color and / or effect Multilayer coating for bodies or cabins containing plastic parts of passenger cars and commercial vehicles as well as their spare parts and attachments of brevity half referred to as "multi-layer coating according to the invention".

In view of the state of the art it was surprising and for the The expert unpredictable that the complex task of the present Invention is based, using the method according to the invention and the coating according to the invention could be solved. In particular, surprised that the use of an electrically conductive hydroprimer coating both on the plastic parts as well as on the metal parts very much to the solution contributed. Even more surprising was that the task essentially with the help aqueous coating materials could be solved, which is both the inventive method and the coating according to the invention especially environmentally friendly. Moreover, it was unpredictable that the inventive method and the coating according to the invention in Their energy balance is superior to conventional processes and coatings.

The method according to the invention is used in car bodies, which today consist of metal parts and plastic parts. It also finds Application to cabs of commercial vehicles, in particular of trucks and buses, which today also consist of these components. Of Another method of the invention in the spare parts and the Attachments of the bodies and the cabins applied.

The inventive method is in the process step (1) from the Electrocoating of parts of the body or the cabin or their Spare parts and attachments made of metal. Suitable metals are the conventional and well-known body steels whose surface is galvanized and / or can be phosphated.

For electrocoating all common anodic (ATL) or cathodic (KTL) electrodeposition baths (ETL).

These electrocoating baths are aqueous coating materials (ETL) with a Solids content of in particular 5 to 30 wt .-%.

(A) üblichen und bekannten Bindemitteln, die ionische oder in ionische Gruppen überführbare funktionelle Gruppen (a1) sowie zur chemischen Vernetzung befähigte funktionelle Gruppen (a2) tragen, wobei sie fremdund/oder selbstvemetzend, insbesondere aber fremdvemetzend, sind:

(B) gegebenenfalls Vernetzungsmitteln, die komplementäre funktionelle Gruppen (b1) tragen, die mit den funktionellen Gruppen (a2) chemische Vernetzungsreaktionen eingehen können, und dann obligatorisch angewandt werden, wenn die Bindemittel (A) fremdvernetzend sind; sowie

(C) übliche und bekannte Lackadditive

The solid of the ETL consists of

(A) customary and known binders which carry ionic or functional groups (a1) convertible into ionic groups and functional groups (a2) capable of chemical crosslinking, where they are foreign and / or self-crosslinking, but especially foreign crosslinking,

(B) optionally crosslinking agents bearing complementary functional groups (b1) which can undergo chemical crosslinking reactions with the functional groups (a2) and then compulsorily applied when the binders (A) are externally crosslinking; such as

(C) conventional and known paint additives

Are the crosslinking agents (B) and / or their functional groups (b1) ready built into the binder (A), it is called self-crosslinking.

As complementary functional groups (a2) come the binder (A) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but especially hydroxyl groups, and as complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, Amino, hydroxy and / or beta-hydroxyalkylamide groups, but in particular blocked isocyanate groups into consideration.

(a11) funktionelle Gruppen, die durch Neutralisationsmittel und/oder Quaternisierungsmittel in Kationen überführt werden können, und/oder kationische Gruppen
oder

(a12) funktionelle Gruppen, die durch Neutralisationsmittel in Anionen überführt werden können, und/oder anionische Gruppen.

Examples of suitable ionic or ionic group-transferable functional groups (a1) of the binders (A) are

(a11) functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents and / or cationic groups
or

(a12) functional groups which can be converted by neutralizing agents into anions, and / or anionic groups.

The binders (A) with functional groups (a11) become cathodic depositable electrodeposition paints (KTL), whereas the binders (A) with functional groups (a12) in anodic electrodeposition paints (ATL) be applied.

Examples of suitable functional groups to be used according to the invention (a11) obtained by neutralizing agents and / or quaternizing agents in Cations can be transferred are primary, secondary or tertiary Amino groups, secondary sulfide groups or tertiary phosphines groups, in particular tertiary amino groups or secondary sulfide groups.

Examples of suitable cationic groups to be used according to the invention (a11) are primary, secondary, tertiary or quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or quaternary ammonium groups, tertiary Sulfonium groups, but especially quaternary ammonium groups.

Examples of suitable functional groups to be used according to the invention (a12), which can be converted by neutralizing agents into anions, are Carboxylic acid, sulfonic acid or phosphonic acid groups, in particular Carboxylic acid groups.

Examples of suitable anionic groups to be used according to the invention (a12) are carboxylate, sulfonate or phosphonate groups, in particular Carboxylate groups.

The selection of the groups (a11) or (a12) should be such that no interfering Reactions with the functional groups (a2) with the crosslinking agents (B) can react are possible. The expert can therefore choose in simple way to make his expertise.

Examples of suitable neutralizing agents for cationic convertible functional groups (a11) are inorganic and organic acids such as Sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, Dimethylolpropionic acid or citric acid, in particular formic acid, Acetic acid or lactic acid.

Examples of Suitable Neutralizing Agents for Anion Convertible functional groups (a12) are ammonia, ammonium salts, such as Ammonium carbonate or ammonium bicarbonate, as well as amines, e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.

In general, the amount of neutralizing agent is chosen so that 1 to 100 equivalents, preferably 50 to 90 equivalents of the functional Groups (a11) or (a12) of the binder (b1) are neutralized.

Examples of suitable binders (A) for ATL are from the patent DE-A-28 24 418 known. This is preferably polyester, Epoxy resin esters, poly (meth) acrylates, maleate oils or polybutadiene oils with a weight average molecular weight of 300 to 10,000 daltons and a Acid number from 35 to 300 mg KOH / g.

Examples of suitable KTL are known from the patents EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-333 327, EP-A-0 310 971, EP-A-0 456,270, US-A-3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199 or EP-A-476 514. This is it preferably primary, secondary, tertiary or quaternary amino or Ammonium groups and / or tertiary sulfonium group-containing resins (A) with amine numbers preferably between 20 and 250 mg KOH / g and a weight average molecular weight of 300 to 10,000 daltons. In particular, amino (meth) acrylate resins, amonoepoxide resins, Amine epoxy resins with terminal double bonds, Aminoepoxiharze with primary and / or secondary hydroxyl groups, aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products.

According to the invention, KTL and the corresponding electrocoating baths are used preferably used.

Preferably, the ETL contain crosslinking agents (B).

Examples of suitable crosslinking agents (B) are blocked organic Polyisocyanates, in particular blocked so-called paint polyisocyanates, with aliphatic, cycloaliphatic, araliphatic and / or aromatic bound, blocked isocyanate groups.

Polyisocyanates with 2 to 5 are preferred for their preparation Isocyanate groups per molecule and with viscosities of 100 to 10,000, preferably 100 to 5000 and especially 100 to 2000 mPas (at 23 ° C) used. In addition, the polyisocyanates in the usual and known manner be hydrophilic or hydrophobic modified.

Examples of suitable polyisocyanates are described, for example, in "Methods of organic chemistry ", Houben-Weyl, volume 14/2, 4, edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Vol. 562, pages 75 to 136.

Further examples of suitable polyisocyanates are isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) -cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) -cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, Dicyclohexylmethane-4,4'-diisocyanate, liquid dicyclohexylmethane-4,4'-diisocyanate a trans / trans content of up to 30% by weight. preferably 25 Wt .-% and in particular 20 wt .-%, which by phosgenation of Isomeric mixtures of bis (4-aminocyclohexyl) methane or by fractionated Crystallization of commercially available bis (4-isocyanatocyclohexyl) methane according to the patents DE-A-44 14 032, GB-A-1220717, DE-A-16 18 795 or DE-A-17 93 785 is available; Trimethylene diisocyanate, tetramethylene diisocyanate, Pentamethylene diisocyanate, hexamethylene diisocyanate, ethylethylene diisocyanate, Trimethylhexane diisocyanate, heptamethylene diisocyanate or diisocyanates, derived from dimer fatty acids, as sold under the trade name DDI 1410 sold by the company Henkel and in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane, 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane, m-tetramethylxylylene diisocyanate (= 1,3-bis (2-isocyanatoprop-2-yl) benzene or tolylene diisocyanate.

Examples of suitable polyisocyanate adducts are isocyanate group-containing Polyurethane prepolymers obtained by reaction of polyols with an excess can be prepared on polyisocyanates and are preferably low in viscosity. It is also possible to use isocyanurate, biuret, allophanate, iminooxadiazinedione, Urethane, urea carbodiimide and / or uretdione groups Polyisocyanates are used. Urethane containing polyisocyanates For example, by reacting a portion of the isocyanate groups with Polyols, e.g. Trimethylolpropane and glycerin.

Very particular preference is given to mixtures of uretdione and / or Isocyanurate groups and / or allophanate groups Polyisocyanate adducts based on hexamethylene diisocyanate, as by catalytic oligomerization of hexamethylene diisocyanate using arise from suitable catalysts used. The polyisocyanate component Incidentally, it can also be made of any mixtures of the free mentioned by way of example Polyisocyanates exist.

i) Phenole wie Phenol, Cresol, Xylenol, Nitrophenol, Chlorophenol, Ethylphenol, t-Butylphenol, Hydroxybenzoesäure, Ester dieser Säure oder 2,5- di-tert.-Butyl-4-hydroxytoluol;

ii) Lactame, wie ε-Caprolactam, δ-Valerolactam, γ-Butyrolactam oder β-Propiolactam;

iii) aktive methylenische Verbindungen, wie Diethylmalonat, Dimethylmalonat, Acetessigsäureethyl- oder -methylester oder Acetylaceton;

iv) Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, n-Amylalkohol, t-Amylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonobutylether, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Propylenglykolmonomethylether, Methoxymethanol, Glykolsäure, Glykolsäureester, Milchsäure, Milchsäureester, Methylolhamstoff, Methylolmelamin, Diacetonalkohol, Ethylenchlorohydrin, Ethylenbromhydrin, 1,3-Dichloro-2-propanol, 1,4-Cyclohexyldimethanol oder Acetocyanhydrin;

v) Mercaptane wie Butylmercaptan, Hexylmercaptan, t-Butylmercaptan, t-Dodecylmercaptan, 2-Mercaptobenzothiazol. Thiophenol, Methylthiophenol oder Ethylthiophenol;

vi) Säureamide wie Acetoanilid, Acetoanisidinamid, Acrylamid, Methacrylamid, Essigsäureamid, Stearinsäureamid oder Benzamid;

vii) Imide wie Succinimid, Phthalimid oder Maleimid;

viii) Amine wie Diphenylamin, Phenylnaphthylamin, Xylidin, N-Phenylxylidin, Carbazol, Anilin, Naphthylamin, Butylamin, Dibutylamin oder Butylphenylamin;

ix) Imidazole wie Imidazol oder 2-Ethylimidazol;

x) Harnstoffe wie Harnstoff, Thioharnstoff, Ethylenharnstoff, Ethylenthioharnstoff oder 1,3-Diphenylharnstoff;

xi) Carbamate wie N-Phenylcarbamidsäurephenylester oder 2-Oxazolidon;

xii) Imine wie Ethylenimin;

xiii) Oxime wie Acetonoxim, Formaldoxim, Acetaldoxim, Acetoxim, Methylethylketoxim, Diisobutylketoxim, Diacerylmonoxim, Benzophenonoxim oder Chlorohexanonoxime;

xiv) Salze der schwefeligen Säure wie Natriumbisulfit oder Kaliumbisulfit;

xv) Hydroxamsäureester wie Benzylmethacrylohydroxamat (BMH) oder Allylmethacrylohydroxamat; oder

xvi) substituierte Pyrazole, Ketoxime, Imidazole oder Triazole; sowie

Examples of suitable blocking agents for the preparation of the blocked polyisocyanates (B) are the blocking agents known from US Pat. No. 4,444,954, such as US Pat

i) phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;

ii) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;

iii) active methylenic compounds, such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;

iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, Glycolic acid esters, lactic acid, lactic acid esters, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or aceto-cyanohydrin;

v) Mercaptans such as butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole. Thiophenol, methylthiophenol or ethylthiophenol;

vi) acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;

vii) imides such as succinimide, phthalimide or maleimide;

viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;

ix) imidazoles such as imidazole or 2-ethylimidazole;

x) ureas such as urea, thiourea, ethyleneurea, ethylene thiourea or 1,3-diphenylurea;

xi) carbamates such as N-phenylcarbamic acid phenyl ester or 2-oxazolidone;

xii) imines such as ethyleneimine;

xiii) oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diaceryl monoxime, benzophenone oxime or chlorohexanone oximes;

xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;

xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or

xvi) substituted pyrazoles, ketoximes, imidazoles or triazoles; such as

Mixtures of these blocking agents, in particular dimethylpyrazole and triazoles, Malonic esters and acetoacetic esters, dimethylpyrazole and succinimide or Butyl diglycol and trimethylolpropane.

Further examples of suitable crosslinking agents (B) are all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F. As polyepoxides for example, those commercially available under the names are also suitable Epikote® from Shell, Denacol® from Nagase Chemicals Ltd., Japan, available polyepoxides, e.g. Denacol EX-411 (Pentaerythritol polyglycidyl ether), Denacol EX-321 (Trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether).

eingesetzt werden.As crosslinking agent (B) can also tris (alkoxycarbonylamino) triazines (TACT) of the general formula

be used.

Examples of suitable tris (alkoxycarbonylamino) triazines (B) are disclosed in U.S. Pat US-A-4,939,213, US-A-5,084,541 or EP-A-0 624 577 described. In particular, the tris (methoxy, tris (butoxy and / or Tris (2-ethylhexoxycarbonylamino) triazines used.

Advantageous are the methyl-butyl mixed esters, the butyl 2-ethylhexyl mixed esters and the butyl esters. These have compared to the pure methyl ester the Advantage of better solubility in polymer melts and also tend less to crystallize.

Further examples of suitable crosslinking agents (B) are aminoplast resins, For example, melamine, guanamine, benzoguanamine or urea resins. In this case, the customary and known amino resins are also suitable, their methylol and / or methoxymethyl groups z. T. by means of carbamate or Allophanate groups are defunctionalized. Crosslinking agent of this kind in US Pat. Nos. 4,710,542 and EP-B-0 245 700 and in the article by B. Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry "in Advanced Organic Coatings Science and Technology Series, 1991, Vol. 13, pages 193 to 207.

Further examples of suitable crosslinking agents (B) are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide.

Further examples of suitable crosslinking agents (B) are compounds with im Means at least two groups capable of transesterification, for example Reaction products of malonic diesters and polyisocyanates or of Esters and partial esters of polyhydric alcohols of malonic acid with Monoisocyanates, as described in European Patent EP-A-0 596 460 to be discribed;

The amount of crosslinking agent (B) in the ETL can vary widely and be directed in particular on the one hand on the functionality of the crosslinking agent (B) and second, according to the number of existing in the binder (A) crosslinking functional groups (a2) and the crosslink density, the you want to achieve. The person skilled in the art can therefore determine the amount of crosslinking agent (B) on the basis of its general expertise, where appropriate with the aid of Determine easier orienting experiments. This is advantageous Crosslinking agent (B) in the ETL in an amount of 5 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 15 to 45% by weight, in each case based on the solids content of the inventive Coating material, included. It is recommended that further, the Amounts of crosslinking agent (B) and binder (A) to be chosen so that in the ETL the ratio of functional groups (b1) in the crosslinking agent (B) and functional groups (a2) in the binder (A) between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, more preferably 1.2: 1 to 1: 1.2 and especially 1.1: 1 to 1: 1.1.

• organische und/oder anorganische Pigmente, Korrosionsschutzpigmente und/oder Füllstoffe wie Calciumsulfat, Bariumsulfat, Silikate wie Talk oder Kaolin, Kieselsäuren, Oxide wie Aluminiumhydroxid oder Magnesiumhydroxid, Nanopartikel, organische Füllstoffe wie Textilfasern, Cellulosefasern, Polyethylenfasern oder Holzmehl, Titandioxid, Ruß, Eisenoxid, Zinkphosphat oder Bleisilikat; diese Additive können auch über Pigmentpasten in die erfindungsgemäße ETL eingearbeitet werden;
• Radikalfänger;
• organische Korrosionsinhibitoren;
• Katalysatoren für die Vernetzung wie anorganische und organische Salze und Komplexe des Zinns, Bleis, Antimons, Wismuts, Eisens oder Mangans, vorzugsweise organische Salze und Komplexe des Wismuts und des Zinns, insbesondere Wismutlactat, -ethylhexanoat oder - dimethylolpropionat, Dibutylzinnoxid oder Dibutylzinndilaurat;
• Slipadditive;
• Polymerisationsinhibitoren;
• Entschäumer,
• Emulgatoren, insbesondere nicht ionische Emulgatoren wie alkoxylierte Alkanole und Polyole, Phenole und Alkylphenole oder anionische Emulgatoren wie Alkalisalze oder Ammoniumsalze von Alkancarbonsäuren, Alkansulfonsäuren. und Sulfosäuren von alkoxylierten Alkanolen und Polyolen, Phenolen und Alkylphenole;
• Netzmittel wie Siloxane, fluorhaltige Verbindungen, Carbonsäurehalbester, Phosphorsäureester, Polyacrylsäuren und deren Copolymere oder Polurethane;
• Haftvermittler;
• Verlaufmittel;
• filmbildende Hilfsmittel wie Cellulose-Derivate;
• Flammschutzmittel;
• organische Lösemittel;
• niedermolekulare, oligomere und hochmolekulare Reaktivverdünner, die an der thermischen Vernetzung teilnehmen können, insbesondere Polyole wie Tricyclodecandimethanol, dendrimere Polyole, hyperverzweigte Polyester, Polyole auf der Basis von Metatheseoligomeren oder verzweigten Alkanen mit mehr als acht Kohlenstoffatomen im Molekül;
• Antikratermittel;

The ETL may contain paint additives (C) in effective amounts. Examples of suitable additives (C) are

• organic and / or inorganic pigments, anticorrosive pigments and / or fillers such as calcium sulfate, barium sulfate, silicates such as talc or kaolin, silicic acids, oxides such as aluminum hydroxide or magnesium hydroxide, nanoparticles, organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour, titanium dioxide, carbon black, iron oxide, Zinc phosphate or lead silicate; these additives can also be incorporated into the inventive ETL via pigment pastes;
• Radical scavengers;
• organic corrosion inhibitors;
• Catalysts for crosslinking, such as inorganic and organic salts and complexes of tin, lead, antimony, bismuth, iron or manganese, preferably organic salts and complexes of bismuth and tin, in particular bismuth lactate, ethylhexanoate or dimethylolpropionate, dibutyltin oxide or dibutyltin dilaurate;
• slip additives;
• polymerization inhibitors;
• defoamers,
• Emulsifiers, in particular nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali metal salts or ammonium salts of alkanecarboxylic acids, alkanesulfonic acids. and sulfo acids of alkoxylated alkanols and polyols, phenols and alkylphenols;
• Wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid monoesters, phosphoric esters, polyacrylic acids and their copolymers or polyurethanes;
• Adhesion promoters;
• Leveling agents;
• film-forming aids such as cellulose derivatives;
• Flame retardants;
• organic solvents;
• low molecular weight, oligomeric and high molecular weight reactive diluents which can participate in thermal crosslinking, in particular polyols such as tricyclodecanedimethanol, dendrimeric polyols, hyperbranched polyesters, polyols based on metathesis oligomers or branched alkanes having more than eight carbon atoms in the molecule;
• Anti-cratering agents;

Further examples of suitable paint additives are in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described.

In accordance with the invention, lead-free cathodic catheters offer particular advantages and are therefore preferably used.

From a methodological point of view, electrocoating has no special features but is carried out as usual by the metal parts to be coated in the electrodeposition bath as a cathode or anode, in particular as a cathode, connected after which the ETL is deposited on the metal surface. After Removal of the metal parts from the electro dip is the Electrocoating after a certain period of rest in the usual and well-known Thermally cured, resulting in the electrodeposition coating.

Thereafter, the electrocoated metal parts in the inventive Process step (2) integrated with the plastic parts, preferably accurately together. Here, the metal parts on a mounting platform (skid) accurately positioned, after which you attach the plastic parts.

Preferably, however, the plastic parts on the assembly platform (skid) accurately positioned and attached the metal parts. After that, it is possible the entire body, that is the integrated body or cabin in one Uniform operation to paint.

As far as the plastic parts are concerned, according to the invention three variants result.

On the one hand, the plastic parts have no primer (variant 2.1).

On the other hand, the plastic parts have a primer on their surface from a thermally hardened at temperatures ≤100 ° C electrically conductive Hydroprimer painting on (variant 2.2).

Third, the plastic parts have on their surface a dried, however, uncured electrically conductive hydroprimer layer on (variant 2.3).

This results in three for the process step (3) according to the invention variants according to the invention:

Variant 3.1):

The integrated metal-plastic body or cabin and its spare parts and attachments whose plastic parts have no primer (variant 2.1), becomes uniform on its surface with an electrically conductive Hydroprimer coated, and the resulting Hydroprimerschicht is at Temperatures ≤100 ° C cured, creating a two-layer primer Electrocoating and electrically conductive hydroprimer coating on the Metal parts and a single-layer primer of electrically conductive Hydroprimer paint on the plastic parts result.

(3.1.1) einheitlich auf die gehärtete elektrisch leitfähige Hydroprimerlackierung einen hellen Hydroprimer applizieren und die resultierende helle Hydroprimerschicht bei Temperaturen ≤100°C thermisch härten
oder

(3.1.2) die elektrisch leitfähige Hydroprimerschicht nach ihrer Applikation ohne auszuhärten antrocknen, auf die angetrocknete elektrisch leitfähige Hydroprimerschicht naß-in-naß einen hellen Hydroprimer applizieren, wonach man die elektrisch leitfähige Hydroprimerschicht und die resultierende helle Hydroprimerschicht gemeinsam bei Temperaturen ≤100°C aushärtet.

With these variants one can still

(3.1.1) uniformly apply to the cured electrically conductive hydroprimer a light hydroprimer and thermally cure the resulting light hydroprimer at temperatures ≤100 ° C.
or

(3.1.2) dry the electrically conductive hydroprimer after application without curing on the dried electrically conductive hydroprimer wet-on-wet apply a light hydroprimer, after which the electrically conductive hydroprimer and the resulting light Hydroprimerschicht together at temperatures ≤100 ° C. cures.

According to both variants (3.1.1) and (3.1.2) result on the metal parts one three-layer primer made of electrocoating, more electrically conductive Hydroprimer painting and light hydroprimer painting and on the Kunstsstoffteilen a two-layer primer of electrically conductive Hydroprimer coating and light hydroprimer coating.

Variant 3.2):

The integrated metal-plastic body or cabin and its spare parts and attachments, whose Kunstsstoffteile a primer of a Hydroprimer paint (variant 2.2), is on its surface uniformly coated with a light hydroprimer and the resulting bright Hydroprimerschicht is cured at temperatures ≤100 ° C, which on the Kunstsstoffteilen a two-layer primer of electrically conductive Hydroprimer painting and light hydroprimer painting and on the Metal parts a two-layer primer of electrocoating and light hydroprimer coating result.

Variant 3.3):

The integrated metal-plastic body or cabin and its spare parts and attachments whose Kunstsstoffteile a dried electrically conductive Hydroprimerschicht have (variant 2.3), on its surface uniform and wet-in-wet with respect to plastic parts with a light color Hydroprimer coated, after which the electrically conductive Hydroprimerschicht and the light hydroprimer layer together at temperatures ≤ 100 ° C be cured, creating a two-layer on the plastic parts Primer made of electrically conductive hydroprimer paint and brighter Hydroprimer painting and on the metal parts a two-layer primer resulting from electrodeposition coating and light hydroprimer coating.

Which variant of the method according to the invention applied in each case becomes, depends on the respective problem statement and after each one existing technical equipment.

According to the invention for all variants of the method according to the invention electrically conductive hydroprimer suitable, as is customary for the Coating of plastics such as ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA. PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short designations according to DIN 7728T1) as well as their Polymer blends and fiber reinforced plastics can be used on this basis and which can be cured at temperatures ≤100 ° C. If necessary the plastic parts for purposes of better adhesion of the hydroprimer in power wash systems or by flaming or by plasma treatment pretreated.

Suitable electrically conductive hydroprimers are so-called Two-component systems.

Component I of the electrically conductive hydroprimer contain conventional and known aqueous polyurethane dispersions, preferably based on Polyester polyurethanes.

• Polyesterpolyolen und
• Verbindungen, durch welche stabilisierende (potentiell) ionische und/oder nichtionische funktionelle Gruppen eingerührt werden, sowie gegebenenfalls
• Polyaminen und
• Aminolakoholen

mit Polyisocyanaten, insbesondere den vorstehend beschriebenen Diisocyanaten.Suitable polyester polyurethanes usually contain the above-described (potentially) cationic functional groups (a11) or the (potentially) anionic functional groups (a12). Instead of or in addition to these functional groups, they may contain nonionic functional groups (a13) based on polyalkylene ethers. You will receive through the implementation of

• Polyesterpolyols and
• Compounds, by which stabilizing (potentially) ionic and / or nonionic functional groups are stirred in, and optionally
• Polyamines and
• Aminolakoholen

with polyisocyanates, especially the diisocyanates described above.

• gegebenenfalls sulfonierten gesättigen und/oder ungesättigten Polycarbonsäuren oder deren veresterungsfähigen Derivaten, gegebenenfalls zusammen mit Monocarbonsäuren, sowie
• gesättigten und/oder ungesättigten Polyolen, gegebenenfalls zusammen mit Monoolen.

The polyester polyols are obtainable by reaction of

• optionally sulphonated, saturated and / or unsaturated polycarboxylic acids or their esterifiable derivatives, optionally together with monocarboxylic acids, and
• saturated and / or unsaturated polyols, optionally together with monools.

Examples of suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. Preference is given to aromatic and / or aliphatic, especially aromatic, polycarboxylic acids used.

Examples of suitable aromatic polycarboxylic acids are phthalic acid, Isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid or Terephthalsäuremonosulfonat, or halophthalic acids, such as tetrachloro or Tetrabromophthalic acid, of which isophthalic acid is advantageous and therefore is preferably used.

Examples of suitable acyclic aliphatic or unsaturated Polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, Undecanedicarboxylic acid, dodecanedicarboxylic acid or dimer fatty acids or Maleic acid, fumaric acid or itaconic acid of which adipic acid, glutaric acid, Azelaic acid, sebacic acid, dimer fatty acids and maleic acid are advantageous and therefore preferably used.

Examples of suitable cycloaliphatic and cyclic unsaturated Polycarboxylic acids are 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, Hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, tricyclodecanedicarboxylic acid, Tetrahydrophthalic acid or 4-methyltetrahydrophthalic acid. These dicarboxylic acids can be found both in their cis- and in theirs trans form as well as a mixture of both forms.

Also suitable are the esterifiable derivatives of the abovementioned Polycarboxylic acids, e.g. their mono- or polyvalent esters with aliphatic Alcohols with 1 to 4 carbon atoms or hydroxy alcohols with 1 to 4 carbon atoms. In addition, the anhydrides of the above polycarboxylic acids used, if they exist.

Optionally, together with the polycarboxylic acids also Monocarboxylic acids are used, such as benzoic acid, tert-butylbenzoic acid, Lauric acid, isononanoic acid, fatty acids naturally occurring oils, acrylic acid, methacrylic acid, ethacrylic acid or crotonic acid. Isononanoic acid is preferably used as the monocarboxylic acid.

Examples of suitable polyols are diols and triols, in particular diols. Usually, triols in addition to the diols in minor amounts used to introduce branches in the polyester polyols.

Suitable diols are ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol, 1,2-, 1,3-, 1,4-, 1,5- or 1,6-hexanediol, Hydroxypivalic acid neopentyl ester, neopentyl glycol, Diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, Trimethylpentanediol, Ethylbutylpropandiol or the positionally isomeric diethyloctanediols. These diols can also be used as such for the Preparation of the polyurethanes (A) to be used according to the invention become.

in der R¹ und R² jeweils einen gleichen oder verschiedenen Rest darstellen und für einen Alkylrest mit 1 bis 18 C-Atomen, einen Arylrest oder einen cycloaliphatischen Rest stehen, mit der Maßgabe, daß R¹ und/oder R² nicht Methyl sein darf;

in der R³, R⁴, R⁶ und R⁷ jeweils gleiche oder verschiedene Reste darstellen und für einen Alkylrest mit 1 bis 6 C-Atomen, einen Cycloalkylrest oder einen Arylrest stehen und R⁵ einen Alkylrest mit 1 bis 6 C-Atomen, einen Arylrest oder einen ungesättigten Alkylrest mit 1 bis 6 C-Atomen darstellt, und n entweder 0 oder 1 ist.Further examples of suitable diols are diols of the formula I or II:

in which R ¹ and R ² each represent an identical or different radical and are an alkyl radical having 1 to 18 C atoms, an aryl radical or a cycloaliphatic radical, with the proviso that R ¹ and / or R ^{2 may} not be methyl ;

in which R ³ , R ⁴ , R ⁶ and R ⁷ each represent identical or different radicals and are an alkyl radical having 1 to 6 C atoms, a cycloalkyl radical or an aryl radical and R ^{5 is} an alkyl radical having 1 to 6 C atoms, is an aryl radical or an unsaturated alkyl radical having 1 to 6 C atoms, and n is either 0 or 1.

Suitable diols of the general formula I I, all propanediols of the formula are useful, in which either R ¹ or R ² or R ¹ and R ² is not methyl, such as 2-butyl-2-ethylpropanediol-1,3, 2-butyl -2-methylpropanediol-1,3,2-phenyl-2-methylpropanediol-1,3,2-propyl-2-ethylpropanediol-1,3,2-di-tert-butylpropanediol-1,3, 2- Butyl 2-propylpropanediol-1,3,1-dihydroxymethylbicyclo [2.2.1] heptane, 2,2-diethylpropanediol-1,3,2,2-dipropylpropanediol-1,3 or 2-cyclohexyl- 2-methylpropanediol-1,3 and others.

As diols II of the general formula II, for example 2,5-dimethylhexanediol-2,5, 2,5-diethylhexanediol-2,5, 2-ethyl-5-methylhexanediol-2,5, 2,4-Dimethylpentanediol-2,4,3,3-dimethylbutanediol-2,3,4- (2'-hydroxypropyl) benzene and 1,3- (2-hydroxypropyl) benzene.

Of these diols, hexanediol and neopentyl glycol are particularly advantageous and are therefore used with particular preference.

The abovementioned diols can also be used as such for the preparation of Polyester polyurethanes are used with.

Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol, in particular trimethylolpropane.

The abovementioned triols can also be used as such for the preparation of Polyester polyurethanes are used with (see the patent EP-A-0 339 433).

Optionally, minor amounts of monools may be used become. Examples of suitable monools are alcohols or phenols, such as ethanol, Propanol, n-butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, Fatty alcohols, allyl alcohol or phenol.

The preparation of the polyester polyols can in the presence of small amounts of suitable solvent can be carried out as entrainer. As an entrainment agent be z. As aromatic hydrocarbons, in particular xylene and (cyclo) aliphatic hydrocarbons, e.g. B. cyclohexane or Methylcyclohexane used.

Further examples of suitable polyols are polyester diols obtained by reacting a lactone with a diol. They are characterized by the presence of terminal hydroxyl groups and recurring polyester components of the formula - (- CO- (CHR ⁸ ) _m - CH ₂ -O -) -. Here, the index m is preferably 4 to 6 and the substituent R ⁸ = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples thereof are hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.

For the preparation of the polyester diols, the unsubstituted ### caprolactone in which m is 4 and all R ⁸ substituents are hydrogen is preferred. The reaction with lactone is started by low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol or dimethylolcyclohexane. However, other reaction components, such as ethylenediamine, Alkyldialkanolamine or urea can be reacted with caprolactone. Also suitable as relatively high molecular weight diols are polylactam diols which are prepared by reacting, for example, ### -caprolactam with low molecular weight diols.

Polyether polyols, in particular having a number average molecular weight of from 400 to 5000, in particular from 400 to 3000, can be used in addition to the polyester polyols described above. Highly suitable polyether diols are, for example, polyether diols of the general formula H - (- O- (CHR ⁹ ) _o -) _p OH, where the substituent R ⁹ = hydrogen or a lower, optionally substituted alkyl radical, the index o = 2 to 6, preferably 3 to 4, and the index p = 2 to 100, preferably 5 to 50, is. Examples which are particularly suitable are linear or branched polyether diols, such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols.

On the one hand, the polyether diols should not contain excessive amounts of ether groups bring in, because otherwise the resulting polyurethanes swell in water. On the other hand, they can be used in amounts that are non-ionic Stabilization of polyurethanes guaranteed. They then serve as a chain functional nonionic groups (a13).

The introduction of (potential) cationic functional groups (a11) takes place on the incorporation of compounds containing at least one, in particular two, towards isocyanate-reactive and at least one for cation formation containing a competent group in the molecule; the amount to be used can from the desired amine number are calculated.

Suitable isocyanate-reactive groups are in particular Hydroxyl groups and primary and / or secondary amino groups, of which the hydroxyl groups are preferably used.

Examples of suitable compounds of this type are 2,2-dimethylolethyl or - propylamine blocked with a ketone, the resulting Ketoximgruppe before the formation of the cationic group (b1) again is hydrolyzed, or N, N-dimethyl, N, N-diethyl or N-methyl-N-ethyl-2,2-dimethylolethyl or -propylamine.

The introduction of (potentially) anionic groups (a12) in the Polyurethane molecules occur through the incorporation of compounds that are at least a isocyanate-reactive and one capable of anion formation Group contained in the molecule; the amount to be used can from the desired acid value can be calculated.

Examples of suitable compounds of this type are those which contain two isocyanate-reactive groups in the molecule. Suitable isocyanate-reactive groups are in particular hydroxyl groups, as well as primary and / or secondary amino groups. Thus, for example, alkanoic acids having two substituents on the ### - permanent carbon atom can be used. The substituent may be a hydroxyl group, an alkyl group or, preferably, an alkylol group. These alkanoic acids have at least one, generally 1 to 3, carboxyl groups in the molecule. They have 2 to about 25, preferably 3 to 10 carbon atoms. Examples of suitable alkanoic acids are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. A particularly preferred group of alkanoic acids are the ###, ### - dimethylolalkanoic acids of the general formula R ¹⁰ -C (CH ₂ OH) ₂ COOH, where R ^{10 is} a hydrogen atom or an alkyl group having up to about 20 carbon atoms. Examples of particularly suitable alkanoic acids are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanoic acid. The preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid. Examples of amino-containing compounds are ###, ### - diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diaminodiphenyl ether sulfonic acid.

Nonionic stabilizing poly (oxyalkylene) groups (a13) can be introduced into the polyurethane molecules as lateral or terminal groups. For this example, alkoxy poly (oxyalkylene) alcohols having the general formula R ¹¹ O - (- CH ₂ -CH ¹² -O-) _r H in the R ^{11 is} an alkyl radical having 1 to 6 carbon atoms, R ^{12 is} a hydrogen atom or an alkyl radical with 1 to 6 carbon atoms and the index r is a number between 20 and 75, can be used. (see patents EP-A-0 354 261 or EP-A-0 424 705).

The use of polyols, polyamines and amino alcohols leads to Molecular weight increase of the polyurethanes.

Suitable polyols for chain extension are polyols with up to 36 carbon atoms per molecule such as ethylene glycol, diethylene glycol, Triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butylene glycol, 1,6-hexanediol, trimethylolpropane, castor oil or hydrogenated Castor oil, di-trimethylolpropane ether, pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, Bisphenol A, bisphenol F, neopentyl glycol, Hydroxypivalic acid neopentyl glycol ester, hydroxyethylated or hydroxypropylated bisphenol A, hydrogenated bisphenol A or mixtures thereof (see patents EP-A-0 339 433, EP-A-0 436 941, EP-A-0 517 707).

Examples of suitable polyamines have at least two primary and / or secondary On amino groups. Polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that are not reactive with isocyanate groups Have hydrogen atoms. Examples are polyamines with linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.

As diamines hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, Piperazine, 1,4-cyclohexyldimethylamine, hexamethylenediamine-1,6, Trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylenothanolamine. preferred Diamines are hydrazine, alkyl or cycloalkyldiamines such as propylenediamine and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.

It is also possible to use polyamines which have more than two amino groups contained in the molecule. However, in these cases - e.g. through the co-use of Monoamines - take care that no crosslinked polyurethane resins are obtained become. Such useful polyamines are diethylenetriamine, triethylenetetramine, Dipropylenediamine and dibutylenetriamine. As an example of one Monoamine is ethylhexylamine mentioned (see the patent EP-A-0 089 497).

Examples of suitable amino alcohols are ethanolamine or diethanolamine.

The polyurethanes may be terminal and / or lateral olefinically unsaturated Contain groups. Groups of this kind can, for example, with the help of Compounds are introduced which contain at least one isocyanate-reactive Group, in particular hydroxyl group, and at least one vinyl group exhibit. Examples of suitable compounds of this type are Trimethylolpropane monoallyl ether or trimethylolpropane mono (meth) acrylate.

The polyurethanes can be grafted with ethylenically unsaturated compounds become. Examples of suitable polyurethanes to be used according to the invention (A), which are present as Pfropfmischpolymerisate, are from the patents EP-A-0 521 928, EP-A-0 522 420, EP-A-0 522 419 or EP-A-0 730 613 known.

The production of the polyurethanes has no special features, but takes place according to the usual and known methods of Polyurethane chemistry.

The polyurethanes are used to prepare the electrically conductive hydroprimer neutralized with the neutralizing agents described above and in Dispersed water so that a dispersion having a solids content of preferably 10 to 70, preferably 20 to 60, particularly preferably 25 to 50 and in particular 30 to 45 wt .-%, each based on the dispersion results.

The further essential constituent of component I of the invention using electrically conductive hydroprimer is at least one electrical conductive pigment. Examples of suitable electrically conductive pigments are Metal pigments, conductivity blacks, doped pearlescent pigments or conductive Barium sulfate. Particularly suitable electrically conductive pigments are the Conductivity soot In addition, on Römpp Lexikon varnishes and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Metallpigmente", p. 381, and "Conductive Pigments," p. 354.

The content of the electrically conductive hydroprimer to electrically conductive Pigments can vary very widely and is preferably from 0.01 to 10, preferably 0.1 to 8, more preferably 0.5 to 7, most preferably 0.5 to 6 and in particular 0.5 to 5 wt .-%, each based on the total amount of the electrically conductive hydroprimer.

• wassermischbare organische Lösemittel und/oder
• rheologiesteuernde Additive, wie die aus den Patentschriften WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 oder WO 97/12945 bekannten; vernetzte polymere Mikroteilchen, wie sie beispielsweise in der EP-A-0 008 127 offenbart sind; anorganische Schichtsilikate, vorzugsweise Smektite, insbesondere Montmorillonite und Hectorite, wie Aluminium-Magnesium-Silikate, Natrium-Magnesium- und Natrium-Magnesium-Fluor-Lithium-Schichtsilikate des Montmorillonit-Typs oder anorganische Schichtsilikate wie Aluminium-Magnesium-Silikate, Natrium-Magnesium- und Natrium-Magnesium-Fluor-Lithium-Schichtsilikate des Montmorillonit-Typs (ergänzend wird auf das Buch von Johan Bielemann »Lackadditive«, Wiley-VCH, Weinheim, New York, 1998, Seiten 17 bis 30, verwiesen); Kieselsäuren wie Aerosile; oder synthetische Polymere mit ionischen und/oder assoziativ wirkenden Gruppen wie Polyvinylalkohol, Poly(meth)acrylamid, Poly(meth)acrylsäure, Polyvinylpyrrolidon, Styrol-Maleinsäureanhydrid- oder Ethylen-Maleinsäureanhydrid-Copolymere und ihre Derivate oder hydrophob modifizierte Polyacrylate; oder assoziative Verdickungsmittel auf Polyurethanbasis, wie sie in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Verdickungsmittel«, Seiten 599 bis 600, und in dem Lehrbuch »Lackadditive« von Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, Seiten 51 bis 59 und 65, beschrieben werden;

enthalten.In addition, the electrically conductive hydroprimer, the conventional paint additives described above (C) in conventional and known effective amounts and also

• water-miscible organic solvents and / or
• rheology control additives, such as those known from the patents WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945; crosslinked polymeric microparticles such as disclosed in EP-A-0081227; inorganic phyllosilicates, preferably smectites, in particular montmorillonites and hectorites, such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium fluorine-lithium phyllosilicates of the montmorillonite type or inorganic phyllosilicates, such as aluminum-magnesium silicates, sodium-magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type (see also the book by Johan Bielemann "Lackadditive", Wiley-VCH, Weinheim, New York, 1998, pages 17 to 30); Silicas such as aerosils; or synthetic polymers having ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified polyacrylates; or associative thickeners based on polyurethane, as described in Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Thickeners", pages 599 to 600, and in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pp. 51-59 and 65;

contain.

Component II of the invention to be used electrically conductive Hydroprimer contains at least one polyisocyanate, which advantageously as such is liquid. In addition, component II may also be conventional and known organic solvents, compared to polyisocyanates are inert.

Until use of the electrically conductive hydroprimer in the According to the invention, its components I and II are separated stored from each other

The weight ratio of component I and component II can vary very broadly and is determined by the one Crosslinking density, which is the cured electrically conductive Hydroprimer painting should, and the other according to the number of isocyanate-reactive groups in the component I and the functionality and the Concentration of the polyisocyanates in the component II. Advantageously the weight ratio I: II at 100: 50, preferably 100: 40, preferably 100: 30, more preferably 100: 20, most preferably 100: 15 and especially 100: 10.

After its application in a conventional manner, the hydroprimer becomes in the process step (3) according to the invention at temperatures <100 ° C thermally hardened, whereby the electrically conductive hydroprimer coating results.

Examples of suitable light hydroprimers to be used according to the invention are also two-component systems. Your component I contains at least one in Water dissolved or dispersed hydroxyl group-containing binder and at least one light pigment, and its component II contains at least one Polyisocyanate.

Suitable hydroxyl-containing binders are polyesters, polyacrylates, Polyurethanes, acrylated polyesters and / or acrylated polyurethanes, in particular Polyurethanes, into consideration. Examples of suitable polyurethanes are the above . described

Examples of suitable light pigments are those above and below pigments described, provided that they are light and opaque.

As components II, the above-described components II in Consideration.

The bright hydroprimers are used with advantage if one Alignment between the hue of preferably dark, electrically conductive hydroprimer coating and, in particular, bright, Waterborne coating is necessary.

According to the invention, the primer resulting in process step (3) the integrated body or cabin or their spare parts and attachments applied color and / or effect water-based paint.

Suitable aqueous basecoats contain at least one dissolved in water or dispersed hydroxyl-containing binder and at least one color and / or effect pigment. In addition, they can be the above described paint customary additives and at least one of the above contain described crosslinking agents in the known effective amounts.

Examples of suitable hydroxyl-containing binders are polyurethanes and / or acrylated polyurethanes.

In addition, the water-based paint can still at least one hydroxyl-containing polyacrylate, a hydroxyl-containing polyester and / or a hydroxylated acrylated polyester as an additional (s) Binder included.

Examples of suitable color and / or effect pigments can be inorganic or organic compounds are produced. Of the Therefore, waterborne basecoat to be used according to the present invention is guaranteed This variety of suitable pigments a universal use and allows the realization of a variety of color tones and optical effects.

As effect pigments, metal flake pigments such as commercially available Aluminum bronzes, chromated aluminum bronzes according to DE-A-36 36 183, commercially available stainless steel bronzes and non-metallic effect pigments, such as Example pearlescent or interference pigments used. In addition will on Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 176, »Effect pigments« and pages 380 and 381 »Metal oxide mica pigments« to "metal pigments", referenced.

Examples of suitable inorganic color pigments are titanium dioxide, Iron oxides, sicotrans yellow and carbon black. Examples of suitable organic coloring pigments are thioindigo pigments indanthrene blue, cromophthal red, Irgazine orange and Heliogen green. In addition, on Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, 1998, pages 180 and 181, »Iron Blue Pigments« to »Iron Oxide Black«, pages 451 to 453 »Pigments« to »Pigment Volume Concentration«, page 563 »Thioindigo Pigments« and page 567 "Titanium Dioxide Pigments".

The proportion of pigments in the aqueous basecoat can be extremely wide vary and depends mainly on the opacity of the pigments, the desired hue and the desired optical effect. Preferably the pigments in the aqueous basecoat according to the invention in an amount of 0.5 to 50, preferably 0.5 to 45, particularly preferably 0.5 to 40, very particularly preferably 0.5 to 35 and in particular 0.5 to 30 wt .-%, each based on the total weight of the water-based paint. This can also be Pigment / binder ratio, d. H. the ratio of the pigments to the Polyurethanes and other optional binders, vary widely. Preferably, this ratio is 6.0: 1.0 to 1.0: 50, preferably 5: 1.0 to 1.0: 50, more preferably 4.5: 1.0 to 1.0: 40, more preferably 4: 1.0 to 1.0: 30 and especially 3.5: 1.0 to 1.0 : 25.

These pigments can also pigment pastes in the inventive Waterborne basecoats are incorporated, wherein as a friction resins u.a. the polyurethanes be considered.

For the preparation of the polyurethanes, the above in the production the hydroprimer described starting compounds into consideration.

Examples of suitable water-based paints and the corresponding Lacquers are known from the patents EP-A-0 089 497, EP-A-0 256 540, EP-A-0 260 447, EP-A-0 297 576, WO 96/12747, EP-A-0 523 610, EP-A-0 228 003, EP-A-0 397 806, EP-A-0 574 417, EP-A-0 531 510, EP-A-0 581 211, EP-A-0 708 788, EP-A-0 593 454, DE-A-43 28 092, EP-A-0 299 148, EP-A-0 394 737, EP-A-0 590,484, EP-A-0 234 362, EP-A-0 234 361, EP-A-0 543 817, WO 95/14721, EP-A-0 521 928, EP-A-0 522 420, EP-A-0 522 419, EP-A-0 649 865, EP-A-0 536 712, EP-A-0 596 460, EP-A-0 596 461, EP-A-0 584 818, EP-A-0 669 356, EP-A-0 634,431, EP-A-0 678 536, EP-A-0 354 261, EP-A-0 424 705, WO 97/49745, WO 97/49747, EP-A-0 401 565, EP-B-0 730 613 or WO 95/14721.

After its application in a conventional manner, the Water-based paint not thermally cured, but only dried.

In the process according to the invention, in process step (5), reference is made to dried waterborne basecoat wet-on-wet at least one, preferably one. Two-component clearcoat applied, whereby the clearcoat results.

As is known, the two-component clearcoats comprise a component I. with at least one hydroxyl-containing binder and a Component II with at least one polyisocyanate. Components I and II are stored separately until their common use.

Examples of suitable polyisocyanates are those described above.

Examples of suitable hydroxyl-containing binders are oligomeric or polymeric, random, alternating and / or block-like constructed linear and / or branched and / or comb-like (co) polymers of ethylenic unsaturated monomers, or polyaddition resins and / or Polycondensation. These terms are supplemented by Römpp lexicon Paints and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyaddition Resins (Polyadducts)", as well as pages 463 and 464, "polycondensates", "polycondensation" and "polycondensation resins" directed.

Examples of suitable (co) polymers are poly (meth) acrylates and partially saponified polyvinyl esters.

Examples of suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, Epoxy-amine adducts, polyureas, polyamides or polyimides.

The present invention to be used containing hydroxyl groups Binders or resins are oligomers and polymers. As part of the The present invention is understood to mean oligomers resins which at least 2 to 15 repeating monomer units in its molecule contain. In the context of the present invention, polymers are used Resins understood that have at least 10 repeating monomer units in their Contain molecule. In addition to these terms on Römpp lexicon Paints and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomers«, page 425, referenced.

The invention to be used hydroxyl-containing resins contain primary and / or secondary hydroxyl groups. It is a whole significant advantage of the method and the Resins of the invention using both types of hydroxyl groups can be. This allows the reactivity of the resins of the invention to control the steric effects.

The OH number of the hydroxyl groups to be used according to the invention containing resins can vary very widely and is preferably from 10 to 500, preferably 20 to 400 and in particular 30 to 350 mg KOH / g.

The resin may further contain at least one functional group which when irradiated with actinic radiation with a group of their kind or one reacts to another functional group. These functional groups can already in the invention to be used hydroxyl-containing Resins may be present or subsequently in the resins by polymer analogues Reactions, be introduced.

Examples of suitable functional groups of this type are allyl, vinyl acrylate or Methacrylate groups, in particular acrylate groups. At the actinic Radiation can be electromagnetic radiation such as X-rays, UV radiation, visible light or near IR light (NIR) or vice versa Corpuscular radiation act like electron beams.

Of the above-described hydroxyl-containing binders For example, poly (meth) acrylates, polyesters, and polyurethanes are preferred used. Particular advantages result from the joint use of the Poly (meth) acrylates and the polyester.

• Katalysatoren für die Vernetzung wie Dibutylzinndilaurat, Lithiumdecanoat oder Zinkoctoat;
• transparente Füllstoffe auf der Basis von Siliziumdioxid, Aluminiumoxid oder Zirkoniumoxid; ergänzend wird noch auf das Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, Seiten 250 bis 252, verwiesen;
• Sag control agents wie Harnstoffe, modifizierte Harnstoffe und/oder Kieselsäuren, wie sie beispielsweise in den Literaturstellen EP-A-192 304, DE-A-23 59 923, DE-A-18 05 693, WO 94/22968, DE-C-27 51 761, WO 97/12945 oder "farbe + lack", 11/1992, Seiten 829 ff., beschrieben werden; und/oder
• Mattierungsmittel wie Magnesiumstearat.

In addition to the binder and the polyisocyanates, the two-component clearcoats to be used according to the invention may also contain the customary lacquer additives described above in the known effective amounts. It goes without saying that in this case only those additives are used which do not affect the transparency of the clearcoat. Further examples of suitable additives for clearcoats are

• Catalysts for crosslinking such as dibutyltin dilaurate, lithium decanoate or zinc octoate;
• transparent fillers based on silica, alumina or zirconia; in addition, reference is made to the Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252;
• Sag control agents such as ureas, modified ureas and / or silicas, as described, for example, in the publications EP-A-192 304, DE-A-23 59 923, DE-A-18 05 693, WO 94/22968, DE-C 27 51 761, WO 97/12945 or "paint + varnish", 11/1992, pages 829 et seq .; and or
• Matting agents such as magnesium stearate.

After application, the waterborne basecoat and the clearcoat are added in process step (6) according to the invention together at temperatures ≤100 ° C thermally or thermally and cured with actinic radiation, wherein especially the two-component clearcoat thermally or thermally and with actinic radiation (dual cure) is cured. This results in the Basecoat and clearcoat.

In a further process step (7), the clearcoat can with a high scratch resistant clearcoat are overcoated. Examples of suitable Clearcoats for the production of such highly scratch-resistant clearcoats are organically modified ceramic materials, which are also under the brand ORMOCER®.

Except for the application of electrocoating (ETL), the application of the Coating materials described above by all conventional Application methods, such as Spraying, doctoring, painting, casting, diving, Soaking, trickling or rolling done. It can be coated Substrate (the integrated body or cabin as well as the spare part or Anbauteil) as such, with the application device or system is moved. However, the substrate to be coated can also be moved, wherein the application equipment rests relative to the substrate or in a suitable manner is moved. Which method is used depends primarily on the size of the substrate. So you become as big a substrate as a cabin for Commercial vehicles primarily with the help of mobile application facilities coat.

Preferably, spray application methods are used, such as Compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as Hot air - hot spraying. The application can be carried out at temperatures of max. 70 to 80 ° C are performed so that reaches appropriate application viscosities be, without that in the momentarily acting thermal load a Change or damage of the coating material and its if necessary, reprocessing overspray. That's how it works Hot spraying be designed so that the coating material only very briefly in the or just before the spray nozzle is heated.

The spray booth used for the application, for example, with a optionally be operated temperature-controlled circulation, with a suitable absorption medium for the overspray, z. B. the coating material itself, is operated.

If the coating material contains components that are actinic radiation can be networked, the application is under illumination with visible light of a Wavelength of about 550 nm or performed with exclusion of light. hereby be a material change or damage to the coating material and of the overspray avoided.

In general, the electrically conductive hydroprimer layer and the light hydroprimer layer, the basecoat layer and the clearcoat layer in one Wet layer thickness applied, that after their curing layers with the for their Functions necessary and advantageous layer thicknesses result. In case of electrically conductive hydroprimer coating and the light hydroprimer coating this layer thickness is 10 to 150, preferably 15 to 120, especially preferably 20 to 100 and in particular 25 to 90 microns, in the case of Basecoat it is 5 to 50, preferably 10 to 40, especially preferably 12 to 30 and in particular 15 to 25 microns, and in the case of Clearcoating is 10 to 100, preferably 15 to 80, especially preferably from 20 to 70 and in particular from 25 to 60 μm.

The thermal curing can take place after a certain rest period. she can a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 minute to have 45 minutes. The rest period is used for example for the course and the Degassing of the paint layers or for evaporation of volatile components like solvents. The rest period can be increased by the application of elevated temperatures up to 90 ° C and / or reduced air humidity <10g water / kg air, In particular, <5g / kg of air, supported and / or shortened, provided that no damage or changes in the paint layers occur, such as one premature full networking.

The thermal curing has no special features, but takes place by the usual and known methods such as heating in one Convection oven or irradiation with IR lamps. Here, the thermal Curing also be done gradually. Advantageously, the thermal Curing at a temperature of 50 to 100 ° C, more preferably 80 to 100 ° C and in particular 90 to 100 ° C for a period of 1 min to 2 h, more preferably 2 minutes to 1 hour and especially 3 minutes to 30 minutes.

The thermal curing can, with appropriate material composition of the coating material is supplemented by curing with actinic radiation in particular UV radiation and / or electron beams can be used. Optionally, it can with actinic radiation of other sources of radiation. In case of Electron beams are preferably carried out under an inert gas atmosphere. This For example, by supplying carbon dioxide and / or nitrogen directly be ensured to the surface of the paint layer.

Even in the case of curing with ultraviolet radiation may be to increase the formation of ozone avoid working under inert gas.

For curing with actinic radiation, the usual and known Radiation sources and optical aids applied. Examples of suitable Radiation sources are high or low pressure mercury vapor lamps, which optionally doped with lead to a beam window up to 405 nm open, or electron beam sources. Their arrangement is known in principle and can the circumstances of the workpiece and the process parameters be adjusted. For complicated shaped workpieces such as Automotive bodies can use the areas that are not directly accessible to radiation (Shadow areas) such as cavities, folds and other design-related Undercuts connected with point, small area or round radiators with an automatic movement device for the irradiation of Cavities or edges are cured.

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

Here, the curing can be done in stages, d. H. by multiple Exposure or irradiation with actinic radiation. This can too alternately, d. h., that alternating with UV radiation and Electron radiation is cured.

Are the thermal curing and curing together with actinic radiation Applied (Dual Cure), these methods can be simultaneous or alternating be used. If the two curing methods are used alternately, can be started, for example, with the thermal curing and with the hardening be terminated with actinic radiation. In other cases, it may turn out to be prove advantageous to begin with the curing with actinic radiation and to end herewith. The person skilled in the art can choose the curing method for each Individual case is particularly well suited due to its general expertise if necessary, determine with the aid of simple preliminary tests.

1) auf den Metallteilen eine kathodisch oder anodisch, insbesondere kathodisch, abgeschiedene und thermisch gehärtete Elektrotauchlackierung sowie eine elektrisch leitfähige Hydroprimerlackierung und/oder eine helle Primerlackierung als Grundierung und

2) auf den Kunststoffteilen eine elektrisch leitfähige Hydroprimerlackierung oder eine elektrisch leitfähige Hydroprimerlackierung und eine helle Hydroprimerlackierung als Grundierung
mit der Maßgabe, daß die integrierten Karosserien oder Kabinen der PKW und Nutzfahrzeugen sowie deren Ersatzteile und Anbauteile von mindestens einer Hydroprimerlackierung über ihre gesamte Oberfläche hinweg einheitlich bedeckt sind;
sowie

3) auf der Grundierung der Metallteile und der Kunstsstoffteile eine farbund/oder effektgebende Basislackierung und

4) auf der Basislackierung mindestens eine Klarlackierung.

The color and / or effect multicoat system according to the invention, obtained in particular by the process according to the invention, comprises the layers superimposed in the following order:

1) on the metal parts a cathodic or anodic, in particular cathodic, deposited and thermally cured electrodeposition coating and an electrically conductive Hydroprimaler coating and / or a bright primer coating as primer and

2) on the plastic parts, an electrically conductive hydroprimer coating or an electrically conductive hydroprimer coating and a light hydroprimer coating as a primer
with the proviso that the integrated bodies or cabins of the cars and commercial vehicles and their spare parts and attachments are uniformly covered by at least one Hydroprimer paint over its entire surface;
such as

3) on the primer of the metal parts and the Kunstsstoffteile a color and / or effect basecoat and

4) on the basecoat at least one clearcoat.

The color and / or effect multicoat system can still with a highly scratch-resistant clearcoat (6) be provided.

The color and / or effect multicoat systems according to the invention have an excellent property profile, which in terms of mechanics, Optics, corrosion resistance and adhesion even at very low temperatures and / or very well balanced after condensation. So have the Multicoat paint systems of the invention required by the market high optical quality and interlayer adhesion and throw no problems like lack of condensation resistance, cracking (mud cracking) in the Basecoats or flow defects or surface structures in the Clearcoats on.

In particular, the multicoat system of the invention has a excellent metallic effect. an excellent D.O.I. (distinctiveness of the reflected image) and excellent surface smoothness. she is weather resistant, resistant to chemicals and bird droppings and scratch resistant and shows a very good reflow behavior.

Another important advantage is the excellent recoatability of the according to the invention even without sanding. This can they easily with conventional and well-known high scratch resistant coating materials the base of organically modified ceramic materials are coated.

It should be emphasized that these benefits are obtained regardless of whether the each considered parts of the integrated bodies of the invention Passenger cars or cabins of commercial vehicles and their spare parts and attachments are overpainted metal parts or plastic parts. In other words: the complex substrates have a multi-layer coating, which over the entire surface of the same high quality.

Last but not least, it proves to be a very special advantage that with the help of inventive method, a multi-layer coating can be realized can, which is based predominantly on aqueous coating materials.

Accordingly, the inventive integrated bodies of Passenger cars or cabins of commercial vehicles and their spare parts and attachments also a longer service life, a better aesthetic impression when Viewers and better technological usability on what they do economically attractive.

Claims (18)

1. An integrated process for painting automobile and commercial vehicle bodies and cabins and their replacement parts and add-on parts which comprise plastic parts, wherein

   1) the metal parts of the body or cabin and/or their replacement parts or add-on parts are coated with an electrocoat material and the resulting electrocoat film is cured thermally to give the corrosion-inhibiting electrocoat;

   2) the electrocoated metal parts of the body or cabin and/or of their replacement parts or add-on parts are integrated with the plastic parts of the body or cabin, said plastic parts having

   2.1) no priming on their surface,

   2.2) on their surface, priming consisting of an electrically conductive aqueous primer coating which is cured thermally at temperatures ≤100°C, or

   2.3) on their surface, a partially dried but not fully cured electrically conductive aqueous primer film;

   3) the integrated metal-plastic body or cabin are coated with an aqueous primer, where

   3.1) the integrated metal-plastic body or cabin and its replacement parts and add-on parts whose plastic parts have no primer (variant 2.1) are uniformly coated with an electrically conductive aqueous primer and the resulting aqueous primer film is cured at temperatures ≤100°C to give a two-coat primer system comprising electrocoat and electrically conductive aqueous primer coat on the metal parts and a single-coat primer system comprising electrically conductive aqueous primer coat on the plastic parts;

   3.2) the integrated metal-plastic body or cabin and its replacement parts and add-on parts whose plastic parts have priming consisting of an aqueous primer coating (variant 2.2) are uniformly coated with a pale aqueous primer and the resulting pale aqueous primer film is cured at temperatures ≤100°C to give a two-coat primer system comprising electrically conductive aqueous primer coat and pale aqueous primer coat on the plastic parts and a two-coat primer system comprising electrocoat and pale aqueous primer coat on the metal parts;
   or

   3.3) the integrated metal-plastic body or cabin and its replacement parts and add-on parts whose plastic parts have a partially dried electrically conductive aqueous primer film (variant 2.3) are uniformly coated, wet-on-wet in terms of the plastic parts, with a pale aqueous primer, after which the electrically conductive aqueous primer film and the pale aqueous primer film are jointly cured at temperatures ≤100°C to give a two-coat primer system comprising electrically conductive aqueous primer coat and pale aqueous primer coat on the plastic parts and a two-coat primer system comprising electrocoat and pale aqueous primer coat on the metal parts;

   4) an aqueous color and/or effect basecoat material is applied uniformly to the primer systems and the resulting aqueous basecoat film is partially dried without curing, after which

   5) at least one two-component clearcoat material is applied wet-on-wet to the partially dried aqueous basecoat film to give at least one clearcoat film; and

   6) the partially dried aqueous basecoat film and the at least one clearcoat film are jointly cured at temperatures ≤100°C, thermally or both thermally and with actinic radiation, to give the integrated multicoat color and/or effect paint system.
2. The process as claimed in claim 1, characterized in that in step (2) of the process the electrocoated metal parts of the body or of the cabin and/or the replacement parts or add-on parts are placed on an assembly stage on which the plastic parts of the body or cabin have already been precisely positioned.
3. The process as claimed in claim 1 or 2, characterized in that in step (3.1) of the process the procedure adopted is to

   (3.1.1) apply a pale aqueous primer uniformly to the cured electrically conductive aqueous primer coat and to cure the resulting pale aqueous primer coat thermally at temperatures ≤100°C
   or

   (3.1.2) partially dry the electrically conductive aqueous primer film following its application, without full curing, to apply a pale aqueous primer wet-on-wet to the partially dried electrically conductive aqueous primer film, and then to cure the electrically conductive aqueous primer film and the resulting pale aqueous primer film jointly at temperatures ≤100°C,

   so as to result, in accordance with both variants, in a three-coat primer system comprising electrocoat, electrically conductive aqueous primer coat and pale aqueous primer coat on the metal parts and a two-coat primer system comprising electrically conductive aqueous primer coat and pale aqueous primer coat on the plastic parts.
4. The process as claimed in one of claims 1 to 3, characterized in that a lead-free cathodically depositable electrocoat material based on at least one epoxy-amine adduct is used.
5. The process as claimed in one of claims 1 to 4, characterized in that the electrically conductive aqueous primer comprises a component I comprising at least one aqueous polyurethane dispersion and at least one electrically conductive pigment, and at least one component II comprising at least one polyisocyanate.
6. The process as claimed in claim 5, characterized in that carbon black is used as electrically conductive pigment.
7. The process as claimed in one of claims 1 to 6, characterized in that the pale aqueous primer comprises a component I comprising at least one hydroxyl-containing binder in dispersion or solution in water and at least one pale pigment, and a component II comprising at least one polyisocyanate:
8. The process as claimed in claim 7, characterized in that at least one polyester, polyacrylate, polyurethane, acrylated polyester and/or acrylated. polyurethane, especially a polyurethane, is used as hydroxyl-containing binders.
9. The process as claimed in one of claims 1 to 8, characterized in that the aqueous basecoat material comprises at least one hydroxyl-containing binder in dispersion or solution in water and at least one color and/or effect pigment.
10. The process as claimed in claim 9, characterized in that the aqueous basecoat material comprises at least one polyurethane and/or at least one acrylated polyurethane as hydroxyl-containing binders.
11. The process as claimed in claim 9 or 10, characterized in that the aqueous basecoat material further comprises at least one hydroxyl-containing polyacrylate, one hydroxyl-containing polyester and/or one hydroxyl-containing acrylated polyester as additional binder(s).
12. The process as claimed in one of claims 1 to 11, characterized in that the aqueous basecoat material comprises at least one crosslinking agent.
13. The process as claimed in one of claims 1 to 12, characterized in that the two-component clearcoat material comprises a component I having at least one hydroxyl-containing binder and a component II having at least one polyisocyanate.
14. The process as claimed in one of claims 1 to 13, characterized in that the two-component clearcoat material is curable thermally or both thermally and with actinic radiation.
15. The process as claimed in one of claims 1 to 14, characterized in that the cured two-component clearcoat material is overcoated with a highly scratch-resistant clearcoat.
16. An integrated multicoat color and/or effect paint system for integrated automobile and commercial vehicle bodies or cabins and their replacement parts and add-on parts which comprise plastic parts, comprising the following coats lying atop one another in the stated sequence:

    1) on the metal parts, a cathodically or anodically, especially cathodically, deposited and thermally cured electrocoat and also an electrically conductive primer coat and/or a pale aqueous primer coat as the primer system, and

    2) on the plastic parts, an electrically conductive aqueous primer coat or an electrically conductive aqueous primer coat and a pale aqueous primer coat as the primer system,
    with the proviso that the integrated automobile and commercial vehicle bodies or cabins and their replacement parts and add-on parts are uniformly covered over their entire surface by at least one aqueous primer coat;
    and

    3) on the primer system of the metal parts and of the plastic parts, a color and/or effect basecoat, and

    4) on the basecoat, at least one clearcoat.
17. The integrated multicoat color and/or effect paint system as claimed in claim 16, characterized in that it has been provided with a highly scratch-resistant clearcoat (6).
18. Automobile and commercial vehicle bodies or cabins and their replacement parts and add-on parts which comprise plastic parts, comprising at least one multicoat color and/or effect paint system producible as claimed in one of claims 1 to 15 and/or at least one multicoat color and/or effect paint system as claimed in claim 16 or 17.