EP0279813A1

EP0279813A1 - Water soluble coating for the production of the base layer of a multilayered coating

Info

Publication number: EP0279813A1
Application number: EP87900119A
Authority: EP
Inventors: Hans-Dieter Hille; Franz Ebner; Hermann-Josef Drexler
Original assignee: BASF Lacke und Farben AG
Current assignee: BASF Farben und Fasern AG
Priority date: 1985-12-21
Filing date: 1986-12-11
Publication date: 1988-08-31
Also published as: WO1987003829A1; ES2014979T5; AU600254B2; EP0228003B2; JPS63502755A; ATE51633T1; DE3545618A1; ZA869378B; BR8607234A; US4914148A; EP0228003B1; AU6842787A; DE3670089D1; ES2014979B3; EP0228003A1; CA1307611C

Abstract

PCT No. PCT/EP86/00736 Sec. 371 Date Aug. 22, 1988 Sec. 102(e) Date Aug. 22, 1988 PCT Filed Dec. 11, 1986 PCT Pub. No. WO87/03829 PCT Pub. Date Jul. 2, 1987.Basecoating compositions for preparing multilayered protective and/or decorative coatings comprise aqueous dispersions which contain (a) as film-forming material one or more polyurethane resins having an acid number of from 5 to 70, which has been prepared by preparing from (A) liner polyetherdiols and/or polyesterdiols having a molecular weight of from 400 to 3,000 (B) diisocyanates and (C) compounds which contain two groups which are reactive toward isocyanate groups, one or more of the compounds used as component C having one or more groups capable of anion formation which have preferably been neutralized before the reaction with a tertiary amine, an intermediate which as terminal isocyanate groups and whose free isocyanate groups have subsequently been reacted with a polyol which contains three or more hydroxyl groups, preferably a triol, (b) pigments and (c) further customary additives.

Description

0 water-thinnable coating agent for the production of the base layer of a multilayer coating

The invention relates to a base coating composition for the production of multilayer, protective 5 and / or decorative coatings on substrate surfaces consisting of an aqueous dispersion which a) as a film-forming material has at least one polyurethane resin with an acid number of 5 to 70, which has been produced is by using linear polyether and / or polyester diols from ° (A). a molecular weight of 400 to 3000

(B) diisocyanates and

(C) Compounds which contain two groups which are reactive toward isocaynal groups, at least one 5

Part of the compounds used as component (C) has at least one group capable of forming anions, which has preferably been neutralized before the reaction with a tertiary A 0. an intermediate product having terminal isocyanate groups has been prepared, the free isocyanate groups of which are then also present

(D) further compounds 5 which are reactive toward isocyanate groups have been reacted,

(b) pigments and

(c) contains other conventional additives. ¹ Especially in automotive painting but also in other areas where you want coatings with a good decorative effect and at the same time good corrosion protection, substrates are known

5 to be provided with a plurality of coating layers arranged one above the other.

Multicoat paint systems are preferably applied according to the so-called "basecoat-clearcoat" process, i.e. a pigmented basecoat is pre-coated and, after a short flash-off time, without a baking step (wet-on-wet process), overcoated with clearcoat. Then the basecoat and clearcoat are baked together.

15

The "basecoat clearcoat" process has become particularly important in the application of automotive metallic effect paints.

20 Economic and ecological reasons have led to attempts to use aqueous base coating compositions in the production of multilayer coatings.

Coating agents for the production of base layers for multi-layer automotive coatings must be processable according to the rational "wet-on-wet" process that is customary today, i.e. after a predrying time that is as short as possible, they must be able to be overpainted with a (transparent) top coat without showing any annoying signs of dissolving.

When developing coating compositions for base layers of metal effect lacquers, further problems must also be solved. The metal effect depends crucially on the orientation of the metal pigment particles in the paint film. A method ^and processable in the "wet-on-wet metallic effect basecoat must 3 accordingly deliver paint films in which the metal pigments after application in a favorable spatial

Orientation is available and in which this orientation is quickly fixed so that it continues in the course of the

Painting process can not be disturbed.

In the development of water-thinnable systems which are intended to meet the requirements described above, problems which are difficult to solve due to the special physical properties of the water occur and to date only a few water-thinnable lacquer systems are known which are used as base coating compositions can be used in the sense set out above.

For example, US Pat. No. 4,558,090 discloses coating compositions for the production of the base layer of multilayer coatings, which consist of an aqueous dispersion of a polyurethane resin with an acid number of 5-70. The aqueous polyurethane dispersion, which in addition to the binder can contain pigments and customary additives and, if appropriate, further binder components, is prepared by reaction

(A) a linear polyether and / or polyester diol with terminal hydroxyl groups and a molecular weight of 400 to 3,000, with

(B) a diisocyanate and

(C) a compound which has two groups which are reactive toward isocyanate groups and at least one group capable of forming anions, the group capable of forming anions having been neutralized before the reaction with a tertiary amine to give an intermediate product with terminal isocyanate groups, Conversion of the intermediate product from (A), (B) and (C) into a predominantly aqueous one

Phase and (D) reaction of the isocyanate groups still present with a di- and / or polyamine with primary and / or secondary amino groups.

The coating agents disclosed in US Pat. No. 4,558,090 are well suited for the production of the base layer of multi-layer coatings, but they are unsuitable for practical use, especially in series coating processes, because the quick drying coating agents are used in the application devices used (for example paint spray gun *, automatic, electrostatically supported high-rotation systems, etc.). adhere so well that they can only be removed with great difficulty. As a result, changing the applied coating systems (e.g. changing the color tone), which is very often very quick, especially in automotive serial painting, is not possible.

It was therefore the object of the present invention to develop aqueous dispersions which can be used as base coating compositions for the production of multilayer protective and / or decorative coatings on substrate surfaces and which meet all the requirements set out above for a base coating composition and can also be easily processed in the application devices used.

Surprisingly, this object was achieved by using aqueous dispersions according to the preamble of claim 1, which are characterized in that the polyurethane resin is reacted by reacting the intermediate product obtained from (A) and (B) and (C) with a at least three polyol containing hydroxyl groups, preferably triol, and converting the reaction product thus obtained into the aqueous phase. It is surprising and was not foreseeable that the difficulties attributable to the desired properties (rapid drying of the applied wet film, difficult re-dissolving of the dried film) in the removal of paint residues remaining in the application devices by using the aqueous polyurethane dispersion according to the invention can be solved and that no loss of quality in the finished multi-layer coating must be accepted.

The dispersions according to the invention are obtained by reacting components (A), (B) and (C) to form an intermediate product containing terminal isocyanate groups. Components (A), (B) and (C) are reacted according to the well-known methods of organic chemistry, preferably a step-by-step reaction of the components (eg formation of a first intermediate product from components (A) and (B) , which is then converted to a second intermediate with (C)). However, components (A), (B) and (C) can also be reacted simultaneously.

The reaction is preferably carried out in solvents which are inert to isocyanate groups and are miscible with water. Solvents are advantageously used which, in addition to the properties described above, also have good solvents for those prepared

Polyurethanes are and can be easily separated from aqueous mixtures. Particularly suitable

Solvents are acetone and methyl ethyl ketone.

In principle, all of the components (A) in the

Production of coating agents based on diols commonly used in polyurethane. Suitable polyether diols correspond to the general formula: in which R = hydrogen or a lower alkyl radical, optionally with different substituents, n = 2 to 6 and m = 10 to 50 or even higher. Examples are poly (oxytetramethylene) glycols, poly (oxyethylene) glycols and poly (oxypropylene) glycols.

The preferred polyalkylene ether polyols are poly (oxypropylene) glycols with a molecular weight in the range of 400 to 3,000.

Polyester diols can also be used as the polymeric diol component (component A) in the invention. The polyester diols can be esterified by organic dicarboxylic acids or their. Prepare anhydrides with organic diols. The dicarboxylic acids and the diols can be aliphatic or aromatic dicarboxylic acids and diols.

The diols used to prepare the polyesters include alkylene glycols such as ethylene glycol, butylene glycol, neopenty glycol and other glycols such as dimethylolcyclohexane.

The acid component of the polyester consists primarily of low molecular weight dicarboxylic acids or their anhydrides with 2 to 18 carbon atoms in the molecule.

Suitable acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acids, azelaic acid, sebacic acid, maleic acid, glutaric acid, hexachloro- heptane dicarboxylic acid and tetrachlorophthalic acid. Instead of these acids, their anhydrides can also be used these exist.

Furthermore, polyester diols derived from lactones can also be used as a component in the invention

Use (A). These products are obtained, for example, 5 -. by implementing a. -Caprolactone with one

Diol. Such products are described in U.S. Patent 3,169,945.

The polylactone polyols which are obtained by this reaction 0 are distinguished by the presence of a terminal hydroxyl group and by recurring polyester fractions which are derived from the lactone. These recurring molecular parts can have the formula 5

0

C - (CHR) _n - CH ₂ 0 -, in which n is preferably 4 to 5 and the substituent is hydrogen, an alkyl radical, a cyclogalkyl radical or an alkoxy radical, where no substituent contains more than 12 carbon atoms and the total number of carbon atoms in the substituent in the lactone ring does not exceed 12.

₂ jJ?) As lactone used as starting material may be any desired lactone or any desired combination of lactones, and this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon s and wherein fatome min-

_"J -destens 2 hydrogen at the Kohlenstoff¬ should be available atom on the ring of the group Sauerstoff¬ bound. The lactone used as a raw material can be represented by the following general formula.

in the n and R have the meaning already given. ^{** ■} The lactones preferred in the invention for the preparation of the polyester diols are the caprolactones, in which n has the value 4. The most preferred lactone is the unsubstituted fi capro

^{■ * ■ * ■} lactone, where n is 4 and all R substituents are hydrogen. This lactone is particularly preferred because it is available in large quantities and gives coatings with excellent properties. Various other lactones can also be used individually or in combination.

Examples of aliphatic diols suitable for the reaction with the lactone include ethylene glycol, 1,3-propanediol, 1,4-butanediol, dimethylol-5 cyclohexane.

Any organic diisocyanates can be used as component (B) for the preparation of the polyurethane dispersion. Examples of suitable diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 5 1,4-cyclohexylene diisocyanate , 1,2-cyclohexylene diisocyanate, 1,3-phylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4- Methylene diisocyanate, l-isocyanatomethyl-5-isocyanate-0 nato-1,3,3-trimethylcyclohexane, bis- (4-isocyanatocyclohexyl) methane, bis- (4-isocyanatophenyl) methane, 4,4'-diisocyanatodiphenyl ether and 2 , 3-bis (8-isocyanato-octyl) -4-octyl-5-hexyl-cyclohexene.

5 Compounds are used as component (C) which contain two groups which are reactive toward isocyanate groups, at least some of which as the component (C) compounds used has at least one group capable of forming anions, which has preferably been neutralized before the reaction with a tertiary amine.

The proportion of ionic groups in the polyurethane molecule can be controlled by setting a certain mixing ratio between the groups containing the groups capable of forming anions and the compounds free of these groups.

Suitable groups reacting with isocyanate groups are in particular hydroxyl groups. The use of compounds which contain primary or secondary amino groups can have a negative influence on the processability of the dispersions described above. The type and amount of any compounds containing amino groups to be used are to be determined by the average person skilled in the art by means of routine tests which are simple to carry out.

Carboxyl and sulfonic acid groups are particularly suitable as groups capable of forming anions. These groups can be neutralized with a tertiary amine before the reaction in order to avoid reaction with the isocyanate groups.

DihydroxyDi-ODionic acid, dimethylolpropionic acid, dihydroxysuccinic acid or dihydroxybenzoic acid are suitable as compounds which contain at least two groups reacting with isocyanate groups and at least one group capable of forming anions. Also suitable are the polyhydroxy acids accessible by oxidation of monosaccharides, e.g. Gluconic acid, sugar acid, mucic acid, glucuronic acid and the like.

Compounds containing amino groups are, for example, c. Σ -diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diamino-toluenesulfonic acid (5), 4,4'-diamino-diphenyl ether sulfonic acid and the like.

Suitable tertiary amines for neutralizing the anionic groups are, for example, trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine and the like.

Low molecular weight diols or diamines with primary or secondary amino groups can be used, for example, as compounds which have two groups reactive toward isocyanate groups but are free from groups capable of forming anions.

The isocyanate group-containing intermediate formed from (A), (B) and (C) is reacted with the polyol containing at least three hydroxyl groups, which most likely results in chain extension and possibly also branching of the binder molecule.

During this implementation, care must be taken to ensure that no cross-linked products are obtained.

This can be achieved, for example, by adding an amount of polyol matched to the isocyanate group content of the intermediate product obtained from (A), (B) and (C) and the reaction conditions.

In principle, all polyols containing at least three hydroxyl groups, which can be reacted with the intermediate product obtained from (A), (B) and (C) in such a way that no crosslinked products are formed, are suitable for producing the polyurethane dispersion according to the invention. Examples include trimethylolpropane, glycerin, erythritol, mesoerythritol, arabitol, adonitol, xylitol, mannitol, sorbitol, dulcitol, hexanetriol, (poly) pentaerythritol, etc. Particularly good results can be achieved if trimethylolpropane is used as the polyol.

It is also conceivable that by simultaneously reacting all four components (A), (B), (C) and

Polyol uncrosslinked polyurethanes can be produced, which can be processed to useful base coating compositions.

After the reaction of the intermediate product obtained from (A), (B) and (C) with the polyol component, which is preferably in a solvent which is inert to isocyanate groups and is miscible with water, and which forms a good solvent for the resulting polyurethane and can be easily separated from aqueous mixtures (eg acetone or methyl ethyl ketone) and if necessary neutralization of the groups capable of forming anions is carried out, the reaction product is converted into an aqueous phase. This can be done, for example, by dispersing the reaction mixture in water and distilling off the organic solvent components boiling below 100 ° C.

Under aqueous phase. To understand water, which may also contain organic solvents. Examples of solvents which may be present in water are heterocyclic, aliphatic or aromatic hydrocarbons, mono- or polyvalent alcohols, ethers, esters and ketones, such as N-methylpyrrolidone, toluene, xylene, butanol , Ethyl and butyl glycol and their acetates, butyl diglycol, ethylene glycol dibutyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, acetone, isophorone or mixtures thereof. 87/03829

12th

After the pH of the resulting polyurethane dispersion has been checked and, if appropriate, adjusted to a value between 6 and 9, the dispersion forms the basis of the coating compositions according to the invention, into which the other constituents, such as, for example, additional binders, pigments, organic solvents and auxiliaries can be incorporated homogeneously by dispersion, for example using a stirrer or dissolver. Finally, J_ • _Q is controlled, the pH and, if necessary, preferably adjusted to a value 6-9 7.0 to 8.5 again. Furthermore, the solids content and the viscosity are adjusted to the values adapted to the respective application conditions.

15 The ready-to-use coating agents generally have a solids content of 10 to 30% by weight and their run-out time in the ISO cup 4 is 15 to 30 seconds, preferably 18 to 25 seconds. Their proportion of water is 60 to 90 wt .-%, the

20 of organic solvents 0 to 20 wt .-%, each based on the total coating agent.

The advantageous effects of the coating compositions according to the invention can be attributed to the use of the aqueous polyurethane dispersion described above.

In many cases it is desirable to improve the properties of the coatings obtained by using a further 30 binder systems in the base coating composition.

The base coating compositions according to the invention advantageously contain, as an additional binder component, a water-dilutable melamine resin in a proportion of 1 to 80% by weight, preferably 20 to 60% by weight, based on the solids content of the polyurethane dispersion. Water-soluble melamine resins are known per se and are used on a larger scale. These are etherified melamine-formaldehyde condensate products. Apart from the degree of condensation, which should be as low as possible, their water solubility depends on the etherification component, with only the lowest members of the alkanol or ethylene glycol monoether series giving water-soluble condensates.

The hexamethoxymethylmelamine resins are of the greatest importance. If solubilizers are used, butanol-etherified melamine resins can also be dispersed in the aqueous phase.

It is also possible to insert carboxyl groups in the condensate. Transetherification products of highly etherified formaldehyde condensates with oxycarboxylic acids are water-soluble via their carboxyl group after neutralization and can be used as a crosslinking component in the coating compositions according to the invention.

Instead of the melamine resins described, other water-soluble or water-dispersible amino resins such as e.g. Benzoguanamine resins are used.

In the event that the base coating composition according to the invention contains a melamine resin, it can advantageously additionally contain, as a further binder component, a water-dilutable polyester resin and / or a water-dilutable polyacrylate resin, the weight ratio of melamine resin: polyester / polyacrylate resin being 2: 1 to 1 : 4 and the total proportion of melamine resin, polyester / polyacrylate resin, based on the solids content of the polyurethane dispersion, is 1 to 80% by weight, preferably 20 to 60% by weight.

Water-dilutable polyesters are those with free carboxyl groups, ie polyesters with a high acid number. ' Basically, two methods are known for inserting the required carboxyl groups into the resin system. The first way is to terminate the esterification at the desired acid number. After neutralization with bases, the polyesters thus obtained are soluble in water and form a film when baked. The second possibility is the formation of partial esters of di- or polycarboxylic acids with hydroxyl-rich polyesters with a low acid number. For this reaction, anhydrides of the dicarboxylic acids are usually used, which are reacted with the hydroxyl component under mild conditions to form a free carboxyl group.

Like the polyester resins described above, the water-dilutable polyacrylate resins contain free carboxyl groups. As a rule, these are acrylic or methacrylic copolymers, and the carboxyl groups come from the proportions of acrylic or methacrylic acid.

Blocked polyisocyanates can also be used as crosslinking agents. Any polyisocyanates in which the isocyanate groups have been reacted with a compound can be used in the invention, so that the blocked polyisocyanate formed is resistant to hydroxyl groups at room temperatures, at elevated temperatures, generally in the range from about 90 to 300 C, but reacts. Any organic polyisocyanates suitable for crosslinking can be used in the preparation of the blocked polyisocyanates. Preference is given to the isocyanates which contain about 3 to about 36, in particular about 8 to 15, carbon atoms. Examples of suitable diisocyanates are the above-mentioned diisocyanates (component B). Polyisocyanates with higher isocyanate functionality can also be used. Examples include tris (4-isocyanatophenyl) methane, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 1,3,5-tris (6-iso- cyanatohexyl) biure. Bis- (2,5-diisocyanato-4-methylphenyD-methane and polymeric polyisocyanates, such as dimers and trimers of diisocyanatotoluene. Mixtures of polyisocyanates can also be used.

The organic polyisocyanates which are suitable as crosslinking agents in the invention can also be prepolymers which are derived, for example, from a polyol, including a polyether polyol or a polyester polyol. For this purpose, it is known that polyols are reacted with an excess of polyisocyanates, resulting in prepolymers with terminal isocyanate groups. Examples of polyols that can be used for this are simple polyols such as glycols, e.g. Ethylene glycol and propylene glycol, and others

Polyols such as glycerin, trimethylolpropane, hexanetriol and pentaerythritol; also monoethers, such as diethylene glycol and dipropylene glycol, and polyethers, which are adducts of such polyols and alkylene oxides. Examples of alkylene oxides which are suitable for polyaddition to these polyols to form polyethers are ethylene oxide, propylene oxide, butylene oxide and styrene oxide. These polyaddition products are generally referred to as polyethers with terminal hydroxyl groups. They can be linear or branched. Examples of such polyethers are polyoxyethylene glycol with a molecular weight of 15 ^ 0, polyoxypropylene glycol with a molecular weight of 1,025, polyoxytetraethylene glycol, polyoxyhexamethylene glycol, polyoxynonamethylene glycol, polyoxydecamethylene glycol, polyoxydodecamethylene glycol and mixtures thereof. Other types of polyoxyalkylene glycol ethers can also be used. Particularly suitable polyether polyols are those which are obtained by reacting such polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-eutanediol, 1,6-hexanediol and mixtures thereof; Glycerol trimethylol ethane, trimethylol propane, i 1,2,6-hexanetriol, dipentaerythritol, tripentaerythritol, polypentaerythritol, methyl glucosides and sucrose with alkylene oxides, such as ethylene oxide, propylene oxide or mixtures thereof.

5

Any suitable aliphatic, cycloaliphatic or aromatic alkyl mono alcohols can be used to block the polyisocyanates. Examples include aliphatic alcohols, such as methyl, ethyl,

2_ _Q chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3,5-trimethylhexyl, decyl and lauryl alcohol; aromatic alkyl alcohols, such as phenylcarbinol and methylphenylcarbinol. Small proportions of higher molecular weight and relatively poorly volatile

₁₅ en monoalcohols may also be used, these alcohols, after being split off, acting as plasticizers in the coatings.

Other suitable blocking agents are oximes such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone

^ _n oxime, as well as caprolactams, phenols and hydroxamic acid esters. Preferred blocking agents are malonates, acetoacetic esters and β-diketones.

The blocked polyisocyanates are produced

_ _n ύO_ by reacting a sufficient amount of an alcohol with the organic polyisocyanate so that no free isocyanate groups are present.

The base coating compositions according to the invention can contain all known pigments or dyes which are customary in the paint industry.

Dyes or pigments, which can be inorganic or organic in nature, are, for example, titanium dioxide, graphite, carbon black, zinc chromate, 35

Strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silicochromate, zinc oxide, cadmium sulfide, Chromium oxide, zinc sulfide, nickel titanium yellow, chrome titanium yellow, iron oxide red, iron oxide black, ultramarine blue, phthalocyanine complexes, naphthol red, quinacridones, halogenated thioindigo pigments or the like. As particularly preferred pigments, metal powders are used individually or in a mixture, such as copper, copper alloys, aluminum and steel, preferably aluminum powder, in at least a predominant proportion, in an amount of 0.5 to 25% by weight, based on the total solids content of the coating compositions on binders. Commercially available metal powders which are specially pretreated for aqueous systems are preferred as metallic pigments. The metal powders can also be used together with one or more of the abovementioned non-metallic pigments or dyes. In this case, their proportion is chosen so that the desired metallic effect is not suppressed.

The base coating compositions according to the invention can also contain other customary additives, such as solvents, fillers, plasticizers, stabilizers, wetting agents, dispersing aids, leveling agents, defoamers and catalysts, individually or in a mixture in the customary amounts. These substances can be added to the individual components and / or the overall mixture.

Suitable fillers are, for example, talc, mica, kaolin, chalk, quartz flour, asbestos flour, slate flour, barium sulfate, various silicas, silicates, glass fibers, organic fibers and the like. The coating compositions described above are used according to the invention in processes for the production of multilayer coatings on substrate surfaces, in which (1) an aqueous dispersion is applied as the base coating composition

(2) a polymer film is formed on the substrate surface from the composition applied in step (1)

(3) a suitable transparent cover layer composition is applied to the base layer thus obtained and then

(4) the base layer is baked together with the cover layer.

In principle, all known coating compositions which are not pigmented or only transparent pigmented are suitable as cover layer compositions. These may be conventional ₁ 5 tional solvent-based clear coats, wasserverdünn- bare clear coats or powder clear coats.

Pretreated metal substrates are particularly suitable as substrates to be coated, but they can

_2Q also untreated metals and any other substrates such as wood, plastics, etc. using the inventive base coating compositions with a multilayer protective and / or decorative coating.

₂ 5 can be drawn.

The invention is explained in more detail in the following examples. All information on parts and percentages are given by weight, unless something else is expressly stated.

Preparation of a polyurethane dispersion according to the invention

255 g of a polyester of 1,6-hexanediol and isophthalic acid with an average molecular weight of 614, 35 are heated together with 248 g of a polypropylene glycol with an average molecular weight of 600 and with 100 g of dimethylolpropionic acid to 100 ° C. and Dewatered in a vacuum for 1 hour. At 80 C, 526 g

4,4'-dicyclohexylmethane diisocyanate and 480 g of methyl ethyl ketone were added. The mixture is stirred at 80 ° C. until the free isocyanate group content is 1.69%, based on the total weight.

Now 28.5 g of trimethylolpropane and then

0.4 g of dibutyltin dilaurate was added and stirring was continued at 80 ° C. for 2 hours. After addition of 1590 g of methyl ethyl ketone, the mixture is kept at 80 ° C. until the viscosity, measured in a DIN beaker, is 65 s (sample dissolved in N: methylpyrrolidone in a ratio of 2: 3).

After adding a mixture of 22.4 g of dimethylethanolamine and 2650 g of deionized water, the methyl ethyl ketone is distilled off in vacuo, and a finely divided dispersion with a solids content of 30%, a pH of 7.4 and a viscosity of 48 is obtained s, measured in a DIN cup.

Production of two-layer coatings according to the base coat / clear coat method using the polyurethane dispersion according to the invention prepared according to the above instructions

The two-layer coating was produced according to the experimental data given in US Pat. No. 4,558,090.

A metallic effect basecoat produced using the polyurethane dispersion according to the invention could be processed into a high-quality two-layer metallic effect coating with an excellent metallic effect. The removability of paint residues remaining in the application devices is demonstrated by means of the following comparative tests: a metal effect basecoat according to US Pat. No. 4,558,090 and a metal effect basecoat according to the present invention were coated on a glass plate in a wet film thickness of 100 μm using a Applied.

After drying for 2 hours at room temperature, a mixture of 50 parts of water and 50 parts of n-propanol was used to try to remove the dried lacquer film from the glass plate. For this purpose, a brush soaked with this cleaning mixture was passed over the dried paint film in a circular motion with light pressure. The paint film formed from the metallic effect basecoat produced according to the invention dissolved homogeneously after the first circular movements. The lacquer film produced using the dispersion disclosed in US Pat. No. 4,558,090, on the other hand, initially swelled and only detached from the substrate after numerous circular movements in larger coherent flat sheets.

This experiment was repeated with a large number of different solvents or solvent mixtures. Similar results were obtained in all cases.

Claims

HPate claims:

1. Base coating composition for the production of multilayer, protective and / or decorative coatings consisting of an aqueous dispersion which

(a) as film-forming material at least one polyurethane resin with an acid number of 5 to 70, which has been produced by

(A) linear polyether and / or polyester diols with a molecular weight of 400 to 3000

(B) diisocyanates and

(C) Compounds which contain two groups reactive toward isocyanate groups, at least some of the compounds used as component (C) having at least one group capable of forming anions, which has preferably been neutralized before the reaction with a tertiary amine, a terminal Intermediate product having isocyanate groups has been prepared, the free isocyanate groups of which are then also present

(D) further, reactive towards isocyanate groups

Compounds containing groups have been implemented

(b) pigments and

(c.) contains further conventional additives, characterized in that the aqueous polyurethane dispersion by reacting the intermediate product obtained from (A), (B) and (C) with a polyol containing at least three hydroxyl groups, preferably triol, and converting the reaction product thus obtained into an aqueous phase has been prepared. 2Z

2. A process for producing a multilayer, protective and / or decorative coating on a substrate surface, in which (1) an aqueous dispersion is applied as the base coating composition, which (a) as film-forming material has at least one polyurethane resin with an acid number of 5 to 70 , which has been prepared by using linear polyether and / or polyester diols with a molecular weight of 400 to 3000 from 0 (A)

(B) diisocyanates and

(C) Compounds which contain two groups reactive toward isocyanate groups, at least some of the compounds used as component (C) having at least one group capable of forming anions, preferably before the reaction with a tertiary amine An intermediate product containing terminal isocyanate groups has been neutralized, the free isocyanate groups of which are then also included

(D) further compounds _Q which are reactive toward isocyanate groups have been reacted,

(b) pigments and

(c) contains other conventional additives.

(2). A polymer film is formed on the surface from the composition applied in step (1), (3) a suitable, suitable cover layer composition is formed on the base layer thus obtained 13

applied and then the base layer is baked together with the cover layer, characterized in that the polyurethane dispersion forming the base coating composition by reacting the intermediate product obtained from (A), (B) and (C) with a polyol containing at least three hydroxyl groups, preferably triol, and transfer of the reaction product thus obtained into the aqueous phase.

3. Base coating composition or method according to claims 1 or 2, characterized in that the reaction of the intermediate product obtained from (A), (B) and (C) with the polyol in a water-miscible, boiling below 100 C against inert isocyanate groups and from aqueous mixtures of easily separable organic solvents, preferably acetone.

4. Base coating composition or method according to one of claims 1 to 3, characterized in that the intermediate product obtained from (A), (B) and (C) has been reacted with trimethylolpropane.

5. base coating composition or method according to any one of claims 1 to 4, characterized in that Z4

the base coating composition contains, as an additional binder component, a water-dilutable melamine resin in a proportion of 1 to 80% by weight, preferably 20 to 60% by weight, based on the solids content of the polyurethane dispersion.

6. Base coating composition or method according to one of claims 1 to 5, characterized in that the base coating composition contains, as a further binder component, a water-dilutable polyester resin and / or a water-dilutable polyacrylate resin, the weight ratio of melamine resin to polyester resin and / or

Polyacrylate resin is 2: 1 to 1: 4 and the total proportion of melamine resin, polyester and polyacrylate resin, based on the solids content of the polyurethane dispersion, is 1 to 80% by weight, preferably 0 to 60% by weight.

7. Base coating composition or method according to one of claims 1 to 6, characterized in that the base coating composition as an additional binder component is a blocked polyisocyanate, together with a water-dilutable. Contains polyester resin and / or a water-dilutable polyacrylate resin, the proportion of polyisocyanate, polyester resin and / or polyacrylate resin as a whole

1 to 80 wt .-%, based on the solids content of the polyurethane dispersion.

8. base coating composition or method according to any one of claims 1 to .7, characterized in that the base coating composition 0.5 to Contains 25% by weight of metal pigments, based on the total solids content of the polyurethane dispersion.

* ^■ 9. Use of aqueous dispersions that

(a) as film-forming material at least one polyurethane resin with an acid number of 5 to 70, which has been prepared by using 0

(B) diisocyanates and 5

(C) Compounds which contain two groups which are reactive toward isocyanate groups, at least some of the compounds _Q used as component (C) having at least one group capable of forming anions, preferably before the reaction with a tertiary amine has been neutralized, an intermediate product having terminal isocyanate groups has been prepared, the free isocyanate groups of which have subsequently been reacted with a polyol containing at least three hydroxyl groups, preferably triol, 0

(b) pigments and

(c) contain other conventional additives as base coating compositions

5 for the production of multilayer, protective and / or decorative coatings on substrate surfaces. 10. Substrate coated with a multilayer, protective and / or decorative coating which has been obtained by

(1) An aqueous dispersion has been applied as the base coating composition

(a) as a film-forming material at least one polyurethane resin with an acid number of 5 to 70, which has been produced by

(A) linear polyethers and / or polyester diols with a molecular weight of 400 to 3000

(B) diisocyanates and

(C) Compounds which contain two groups which are reactive towards isocyanate groups, at least some of the compounds used as component (C) having at least one group capable of forming anions, which is preferably used before the reaction with a tertiary one

Amine has been neutralized, an intermediate product containing terminal isocyanate groups has been produced, the free isocyanate groups of which are then also used

(D) other compounds containing groups reactive toward isocyanate groups have been reacted

(b) pigments and

(c) contains other conventional additives.

(2) a polymer film has been formed on the surface from the composition applied in step (1), 1

(3) a suitable transparent cover layer composition has been applied to the base layer thus obtained and then

(4) the base layer has been baked together with the cover layer, characterized in that the aqueous polyurethane dispersion forming the base coating composition, preferably by reacting the intermediate product obtained from (A), (B) and (C) with a polyol containing at least three hydroxyl groups Triol, and conversion of the reaction product thus obtained into an aqueous phase.