MXPA96000075A - Procedure to produce decorative coatings of multip layers - Google Patents

Abstract

A method and a coating medium for producing a multilayer decorative coating on a substrate is described, wherein a basecoat coating is applied and is overcoated with a clearcoat coating, where a waterborne lacquer is used. aqueous self-interlacing base, which contains, as a binder vehicle, a dispersion of aqueous polyurethane resin based on a polyurethane resin having a number average molecular weight (Mn) of 2500 to 120,000, a content of 10 to 400 moles of hydroxyl groups and / or R'O side and / or terminals bonded to silicon, where R '= C 1 to C 8 alkyl (O) R' '', and R '' '= C 1 to C 10 alkyl, per 100 g of solid resin, a hydroxyl number of 0 to 150, wherein the hydroxyl groups bound to silicon are not included in the calculation of OH number, and a content of ionic groups, groups convertible to ionic groups and / or Hydrophilic groups of 5 to 200 mEqu per 100 g of res ina sóli

Description

OCEDIMIENTO TO PRODUCE DECORATIVE COATINGS OF MULTIPLE LAYERS DESCRIPTION OF THE INVENTION This invention relates to a process for producing multi-layered decorative coatings of the water-based lacquer / clear lacquer type. A multiplicity of water-based lacquers are known. These lacquers contain aqueous polyurethane dispersions as binding vehicles because of the eubyarada properties of the latter. The chains of the polyurethane resins that form the basis of the polyurethane dispersions can be extended in a wide variety of different ways. Therefore, for example, EP-A-0 0S > 97, EP-A-0 22A 003, DE-A-3Ó 2 & 12 < + and EP-A-0 512 52I- + describe aqueous-based lacquers, which contain, as agglomerating vehicles, aqueous polyurethane dispersions which can be produced by extending the isocyanate functional prepolymer chains with a polyamine and / or a polyol. DE-A-39 15? +59 and DE-A -? + 2 2 617 provide examples of water-based lacquers containing, as binders, aqueous dispersions of polyurethanes which can be produced by extending the chains of functional isokinate prepolymers with Water. Examples of water-based lacquers based on Aqueous polyurethane suspensions that can be produced by spreading, with polyisocyanates, the chains of FU prepolymers that react with polyisocyanates and containing active hydrogen, are presented in DE-A-39 03 &0 and DE-AU 01 ßm. Multi-layer coatings that are produced using water-based lacquers are formulated based on polyurethane formulations produced have the need for an improvement with respect to their resistance to Condensation water. If the known polyurethane dispersions are used as the only binder vehicle in water-based basecoats, the effect is less favorable compared to water-based basecoats containing at least one additional co-binder. EP-A-0 163 21Lt discloses self-penetrating aqueous polyurethane dispersions which preferably contain lateral siliconate groups. The DU dispersions are prepared and stored under conditions such that the reaction of the siliconate groups between them is deliberately avoided. After application, the binder vehicles are entangled by condensation of the siliconate groups with the formation of siloxane bridges. Other aqueous solutions or dispersions of polyurethanes containing reactive siliconate groups which are suitable for crosslinking are known from EP-A-0 315 006. The binder vehicles described in / lysine are synthesized by the reaction of isocyanate groups of isocyanate prepolymers with amino groups, ie, the chain extension is effected by the amino groups. During the preparation of the binder vehicles, a large amount of water is added, so that practically no siloxane bridge is formed, due to the law of mass action. Both EP-A-0 163 2.1W and EP-A-0 315 006 do not mention the fact that the binder vehicles they describe are suitable for the production of water-based lacquers. The object of the present invention is to provide a process for the production of multi-layer decorative coatings of the water-based lacquer / clear lacquer type having an improved resistance to condensation water, where aqueous polyurethane resins are used as binders in aqueous base lacquers. This object is achieved by means of a process for producing a multilayer decorative coating to which the invention relates first, wherein a coating of lacquer imparting a color and / or effect of a water-based lacquer is applied to a substrate optionally pre-coated and overcoated with a clearcoat coating characterized in that a self-interlacing coating medium is used as the water-based lacquer, which contains, as binder vehicle, a dispersion of aqueous polyurethane resin based on a polyurethane resin of linear or branched structure having a number average molecular weight (Mn) of 2500 to 120,000, a content of 10 to 400 mmolar, preferably from 20 to 300 mmolar, most preferably from 4-0 to 200 mmolar of lateral and / or terminal hydroxyl groups and / or R'O bonded to the silicon, wherein R '= C 1-6 alkyl C- & or R "= C to C10 alkyl, per 100 g of solid resin, a hydroxyl number of 0 to 150 mg KOH / g, preferably greater than 1 and less than 100 mg KOH / g, with respect to the solid resins , where the hydroxyl groups bound to silicon are not included in the calculation of the OH number, and a content of ionic groups, groups convertible to ionic groups and / or hydrophilic groups of 5 to 200mFqu per 100 g of solid resin. of aqueous polyurethane used as the binder vehicle in the process according to the invention contains 5 to 200mEqu (milliequivalents) of ionic groups, groups convertible to ionic groups and / or hydrophilic groups per lOOg of solid resin. Ionic groups are acid groups, or if the ionic groups are anionic, they are preferably present in an amount greater than 15 and less than 100 mEqu / 100 g solid resin, most preferably greater than 16 and less than 60 solid resin.

If the groups which are convertible to ionic groups are basic groups, or if the ionic groups are cationic, they are preferably present in an amount greater than 30 and less than 150 mEqu / 100 solid resin, very preferably greater than 45 and less than 100 mEqu / iOO of solid resin. For hydrophilic groups the 5 to 200 mEqu refers to the lowest molecular weight constituents of such groups, and therefore, for example, to alkylene oxide units in polyalkylene oxide groups, eg, to units of ethylene oxide in polyethylene oxide groups (units of this type are also referred to as repeating units). Examples of ionic groups, groups convertible to ionic groups and hydrophilic groups are presented in the following description, which relates to the production of the aqueous polyurethane resin. The production of aqueous polyurethane resin containing lateral and / or terminal hydroxyl groups and / or R'O bonded to silicon can be carried out, for example: 1. - Preparing, in an organic solvent in the absence of solvents, a PU prepolymer ungelled, linear or branched, which contains ionic groups, groups capable of forming ions and / or hydrophilic groups as well as functional isocyanate groups, 2.- Reacting the free isocyanate groups of the PU prepolymer with 1 or more compounds of the formula general ((HX -) "R)? If (OR ') to (R"), = (I) where X = 0, S, NH or NRXV, preferably NH or NRIV, R = a bifunctional, trifunctional or tetrafunctional, preferably a bi functional organic radical, with a molecular weight of from 13 to 500, preferably an aralkylene containing from 12 carbon atoms, most preferably an alkylene containing from 1 to 12 carbon atoms, R '= alkyl from Cx to C? O C (0) R '' ', preferably an alkyl of CL to C- +, R "equal to R' '' = alkyl of C-, to C10, where R" and R ' '' can be the same or different, RIV = C to Ca alkyl, a = i, 2 or 3, preferably b = 1, 2 or 3, preferably 2 or 3, c = 0, 1 or 2, n = 1 a 3, preferably 1 or 2, most preferably wherein a plurality of radicals R ', R "and R'" may be the same or different and where the sum of a plus b plus c is 4 Optionally in admixture with a or more alkanola inas containing NH.-., and / or NH groups with an OH functionality of at least 1, The quantitative ions of the individual educts are selected so that the final polyurethane resin conforms to the specified ions given above, and 3. - By converting the optionally neutralized reaction product into an aqueous dispersion by the addition of water.

When the optionally neutralized reaction product is converted to an aqueous dispersion, the water can be added to the resin. It is also possible to add the resin to water. It is essential that a quantity of water is added within a short period, which is sufficient to avoid an additional reaction of the HOSi groups formed by hydrolysis. The addition of water is carried out using more than 10 times of an excess of etheric stequeo of the amount of water necessary for the hydrolysis of the R'OSi groups. Preferably, the stequeometric excess is added at least 50 times. The addition of water is most preferably carried out as an amount so that at least half of the amount of water required for the production of the aqueous polyurethane dispersion is added all at once. By adding a sufficient amount of water, the formation of siloxane bridges is substantially prevented by the condensation of the HOSi groups formed by hydrolysis, said condensation proceeding with the separation of the water, that is, an aqueous dispersion of a polyurethane resin is obtained, which is practically free of siloxane bridges and which contains R'OSi and / or HOSi groups in an amount sufficient for entanglement. The solvent, which is optionally present, can be removed optionally by distillation of the aqueous dispersion. During the production of polyurethane resin TO uo5a, the quantitative proportions of the individual educts are selected, and the reaction is conducted, such that the final polyurethane resin contains from 10 to 400 mmoles, preferably from 20 to 300 mmoles, most preferably from 40 to 200 mmoles of groups lateral and / or terminal hydroxyl and / or R'O bonded to silicon, where R '= C to C alkyl? C (0) R '", and R'" = C to C10 alkyl, cor 100 g solid resin, a number average molecular weight (Mn) of 2500 to 120,000, a hydroxyl number of 0 to 150 mg fc 'OH / g, preferably greater than 1 and less than 100 mg KH / g, with respect to the solid resin, wherein the hydroxyl groups bound to silicon are not included in the calculation of the OH number, and a content of ionic groups , groups convertible to ionic groups and / or hydrophilic groups of 5 to 200 Equ per 100 g of solid resin. As an alternative to the process of sequential production via NCO prepolymers described above, the production of the polyurethane resin functionalized with R'OSi can also be carried out by what is known as a one-step process, i.e. steps i and 2 of the process described above can be conducted simultaneously, by reacting the required educts simultaneously among them. With respect to the selection of reagents, it must be ensured that the reactivity of the functional groups -XH is not íañada The production, in stage 1 of the process, for example, of the ungelled, branched polyurethane prepolymer, which contains ionic groups, groups capable of forming ions and / or hydrophilic groups as well as isocyanate functional groups, which is hereinafter also referred to as the PU prepolymer containing NCO groups, may be effected, for example by the reaction of one or more compounds containing at least two groups that react with isocyanate, particularly one or more polyols, preferably diols, with one or more more organic polyisocyanates, preferably diisocyanates, and with one or more compounds containing more than one, preferably two groups which react with isocyanate and which contain at least one ionic group, a group capable of forming ions and / or hydrophilic group. For example, a polyurethane prepolymer containing NCO groups and which can be used as a starting material for the production of the PU dispersion can be produced by the reaction in an anhydrous medium of: a) at least one linear compound or branched containing at least two groups that react with isocyanate and having an average molecular weight of from 60 to 10,000, preferably from 60 to 6,000, b) at least one organic isocyanate, particularly a diisocyanate, c) at least one compound that contains more than one group that reacts with isocyanate and at least one ionic group, group layers of .. • rmar ions and / or hydrophilic group, with a number average molecular weight (mn) of up to 10,000, preferably up to 2,000, in a ratio of NC0 / 0H greater than 1 to 4: 1. The aforementioned linear or branched compound of component A) is preferably at least one polyol based on 1 or more polyesters, polyesters, polyurethanes and / or polycarbonates, which contains at least two OH groups in its molecule and which have a weight molecular weight (n) of 600-10,000, preferably greater than 1000 and less than 5,000, optionally with the use of one or more of at least bifunctional low molecular weight alcohols and / or amines and / or amino alcohols having a molecular weight less than 600, preferably less than 400. All production processes for polyurethane prepolymers containing NCO groups can be conducted as single-stage or multi-stage processes. The PU prepolymer containing isocyanate groups preferably have a content of urethane groups (-NHC00-) and optionally of urea groups (-NHC0NH) of between 10 and 300 milliequivalents per 100g of solid resin. The preparation of the aqueous polyurethane dispersion can be carried out in each stage without organic solvents. The compounds used as component a) for the production of the PU prepolymer containing NCO groups can, for example, be a linear or branched polyol component, v.gr., diols. Examples of such polyols include polyols familiar to those skilled in the art which are used in the field of VU chemistry. Examples are described in DE-A-42 2A 510. If linear biol components are used as the starting material, the proportions of polyols having a functionality of 3 or more can be added in order to effect branching of the polymer. The amount of these must be selected so that no gel formation occurs during the synthesis of the PU prepolymer containing NCO groups. Low molecular weight compounds can optionally be used together with component a. These comprise alcohols and amines in particular. Examples include the known polyurethane chemistry compounds comprising hydroxyl and amine groups which are at least difunctional in the sense of an isocyanate addition reaction and which have a molecular weight of less than 600, preferably less than 300. Suitable compounds include both those which are bifunctional compounds in the sense of an isocinato addition reaction and compounds that are at least tr functional in that sense, or any mixture of compound of this type. Any organic polyisocyanate, such as diisocyanates, can be used as component b) for the production of the polyurethane dispersion, aliphatic, cycloaliphatic, aromatic or isocyanate isocyanates can be used. tralifatics, as well as sterically hindered isocyanates. Polyisocyanates, e.g., diisocyanates, containing ether or ester groups can also be used. Examples of suitable diisocyanates include hexamethylene diisocyanate, i-isocyanatomethyl-5-iso-ianato-1, 3,3, -trimethylcyclohex no, bis- (4-i ocynatocyclohe i 1) -methane, bis (4-iso-iapato- Phenol-methyl, bis- (4-isocyanato-phenyl) -methane and tet ramethyl ether diisocyanate Optionally, small proportions of isocyanates of higher functionality, such as polyisocyanates of the biuret or isocyanurate type, for example, may also be optionally added. or products obtained from the production of an excess of diisocyanate or polyols Compounds which can be used as component c) preferably comprise monomeric compounds of low molecular weight, for example containing more than 1, preferably 2, or at least 2 groups reacting with isocyanate groups and at least 1 ionic group, a group of ion forming complexes and / or a hydrophilic group. Preferred are anionic groups or anion forming groups. Suitable groups which function with isocyanate groups comprise hydroxyl groups and in particular primary and secondary amino groups. Examples of suitable acid groups which are capable of forming anions include carboxyl, phosphoric acid and sulfonic acid groups. Examples of basic groups that can be converted to cations include amino groups Primary, secondary and tertiary or onium groups such as quaternary ammonium, phosphonium and / or tertiary sulfonium groups. The anionic groups that are preferably introduced are carboxyl groups. These can be introduced, for example, by the use of hydroxyalkanecarboxylic acids of the following general formula as component b) (HO), < Q (COOH) v wherein Q represents a linear or branched hydrocarbon radical containing 1 to 12 carbon atoms, and X and Y each represents 1 to 3. Examples thereof include citric acid and tartaric acid. Carboxylic acids such as these are preferred where x = 2 and y = 1. Examples thereof are described in US-A-3 412 054. A preferred group of dihydra-ialkane acid is that which comprises fa-alpha- di et ilolalcano of the general formula CH._5.0H Q '- C - COOH CHa0H wherein Q is hydrogen and an alkyl of C __-C ?. The compounds that are most preferred are alpha, alpha-dimethyl, propionic and alpha, alpha-d-imethyl-butyl alcohol. Other examples of dihydroxyalkane acids that may be used include dihydroxypropionic acid, di-ethylacetatic acid, dihydroxysuccinic acid and Jihydroxybenzoic Examples of acids which contain amine groups and which can be used include alpha-alpha, alpha-diarylaminic acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid- (5) and 4,4-diamyl ester sulfonic acid. -di-fení lico. Acid polyesters such as those described in DE-A-39 03 can also be used as component c) A04 These polyesters preferably have a molecular weight of 300 to 2000, a hydroxyl number of 56 to 374 and an acid number of? A to 1A7. Also c) component c) can be used polyurethane polyols containing ionic groups or groups convertible to ionic groups.

Component c) may also comprise nonionic hydrophilic polyols. Examples of these include compounds containing pallather chains that with incorporated ethylene oxide units. There are compounds which contain 1 or 2 hydrogen atoms which are capable of reacting with isocyanates, and which have polyester chains containing ethylene oxide in their side chain, for example. Examples of these include compounds of the general formulas R: a H0 CH. ,, - N - CHa. -JH- OH (II) ¿o- R - NH - C0 - 0 - X - Y RA HO - X - Y - R * (III) HNR: a - X - Y - R * (IV) wherein R = the radical resulting from an isocyanate component, e.g., of the isocyanates mentioned above, R: a = a H, or a linear, or branched C-Cβ alkyl RA = C-alkyl C 12, preferably an unsubstituted C 1 -C 4 alkyl, X = radical which is obtained by removing the terminal oxygen atom of a polyalkylene oxide chain or containing from 5 to 90, preferably from 20 to 70 chain members, in where at least 40TS, preferably 65 & of the chain members consists of ethylene oxide units, and said chain members, in addition to the ethylene oxide units, may also comprise propylene oxide, butyl ether oxide or styrene oxide units, by example, and Y = -0- or - NRA-, where R * is as defined above. Compounds II or IV can be prepared analogously to Us-A-3 920 59A, US-A-3 905 929 US-A-4 190 566 or US-A-4 237 264, for example. The ammonium, cationic or non-ionic groups of component c) serve to stabilize the aqueous dispersion. The ionic and nonionic groups can be used together. Stabilization by ionic groups is preferred, very preferable by ammonium groups. The dihydroxycarboxylic acids are preferred for The production of an anionic urethane prepolymer. Particularly preferred is di-ethylopropionic acid. Component c) is preferably used in an amount from about 0.4% by weight to about 7.5% by weight, most preferably from about 0.A to 5.0% by weight (calculated as the carboxyl group COOH) with with respect to the pre-polymer urethane (solid resin) used. If the amount of the carboxyl group is less than approximately 0.4 $ by weight, it is difficult to produce a stable emulsion. On the other hand, if the amount exceeds 7.5 $ by weight, this improves the properties of the products, which makes the emulsion highly viscous and reduces the water resistance of the coating. The amounts of a), b) and c) are selected so that a reaction product containing NCO side and / or terminal groups is formed during the reaction, ie, an excess of polyisocyanate is employed. An NCO to OH ratio greater than 1 to 4: 1 may be employed, with the scale of 1.1 to 2: 1 being preferred, and the scale from 1.1 to 1.7: 1 being particularly preferred. The polyurethanes preferably contain less than 2A0 my equivalents of -NHC00-100 per 100 g of solid resin. The reaction product can have a branched structure; in general, however, preferably it has a linear structure with terminal NCO groups. The prepoly was polyurethane containing NCO groups is reacted with one or more compounds of the general formula ((HX-) rlR)? If (OR ') to.R ") ß <I> where X = 0, S, NH or NRIV, preferably NH or NRIV, R = a bifunctional, trifunctional organic radical or tetrafunctional, preferably bifunctional, with a molecular weight of 13 to 500, preferably an aralkylene containing from 1 to 12 carbon atoms, most preferably an alkylene containing from 1 to 12 carbon atoms, R 'is a Cx alkyl a C 0 C (0) R '' ', preferably an alkyl of Cx to Cl +, R "= a R' '' = a alkyl- of C- to C10, R x ^ = a alkyl of C to C ?, a = 1, 2 or 3, preferably 1, b = 1, 2 or 3, preferably 2 or 3, c = 0, 1 or 2, n = lo 3, preferably 1 or 2, most preferably 1, and where the sum of a plus b plus c is four, optionally in admixture with one or more alkanolamines containing NH_j and / or NH groups with an OH functionality of at least 1, to form a polyurethane resin containing ionic groups, groups capable of forming ions and / or hydrophilic groups and lateral R'O groups and / or ends bound to silicon. The compounds of the general formula I are silane derivatives comprising groups of the type (H-X -) -., R containing active hydrogen and which are capable of undergoing addition with respect to isocyanate groups. The amine groups are preferred as the HX functional groups containing active hydrogen; n has the values of 1 to 3, and n preferably assumes the value of 1. The radical R is an organic radical of bifunctional. to tetrafunctional, preferably a bifunctional organic radical, which can chemically contain groups or 16 subst ituyent.es inhertes, and having a molecular weight of 13 to 500. The radical R is preferably a bifunctional aralkylene radical containing from 1 to 12 carbon atoms. The alkylene radical containing from 1 to 12 carbon atoms is particularly preferred as the radical R. Fl derived from silane of the general formula I also contains from 1 to 3, preferably 2 or 3, R'O groups attached to the silicon, in where R 'preferably represents an alkyl of -i to C ?. Some preferred examples of the compounds I include beta-a non-eti ltriethoxysilane, gamma-amino-propyltri-ethoxyieilane, ga ma-amine-propi ltr imethoxysilane, gamma-amino-propyliethe Idiet tin, gamma-a non-propyl lfeni Id ietox isi tin, gamma-amino-pro iltrimethoxysilane, delta-a-but-i -trietoxy-silane, delta-amino-buyleldiethoxysilane, N- (2-aminoet-il-3-aminopropyl) - rimetox isi, N- (2-aminoet-il-3-ami-opropyl-tri-2-ei-lhe-oi) si-lino, 6- (aminohe- lal-inopropyl-1) -tt ime or isi-1, and N-aminomet-1-3-aminoprop i 1-ruet i 1-d imetox isi1ano. The reaction of the NCO functional polyurethane prepolymer to form the R'OSi-functionalized polyurethane resin is effected with the complete consumption of the HX group of the compounds I. The isacyanate groups and the HX groups are preferably reacted with each other. etrically in a 1: 1 ratio. However, it is also possible to conduct the reaction with an excess of isocyanate groups. The remaining isocyanate groups can be used for higher synthesis reactions, by reaction with water, hydrazma, carbaxyl acid hydrazides, polyols or amines, for example. The polyurethane ream containing side and / or terminal R'OSi groups bound to silicon may contain hydroxyl groups. If this is desired, the NCO-containing propylene polymer is reacted during the production of the functionalized polyurethane resin << _on R'OSi, with at least one compound of the general formula I and with at least one alkanol ma having an OH functionality of at least 1 and containing at least one NH-B and / or NH group. The reaction is carried out with the complete consumption of the HX groups of the compounds I and the NH groups of the alkanola ima. The isocyanate groups of the functional NCO PU prepolymer are preferably reacted in the stoichiometric ratio with the groups XH of group I and the NH groups of the alkanolamine. In this regard, the alkanola ina and the compound I can be reacted in mixture or successively with the functional polyurethane prepolymer NCO. Alkanalamines having an OH functionality of at least 1 and containing Hja and / or NH groups are compounds which can be tervir as hydroxyl group fauters in the polyurethane resin dispersion. The NH or NH-j groups of the alkanolanes have a reactivity towards the isocyanate groups of the NCO functional PU prepolymer which is considerably greater than its reactivity towards the OH groups The latter, ie the NH groups, reacts preferentially with the isacyanate groups with the formation of urea. Examples of suitable alkanolamines having an OH functionality of at least 1 include monoalkyl alkanolamines and dialkanolanes, eg, diethanolamine, N-methyl ethanolamine, di iso opanala, N-et i 1-isapropanola ina, monoisapropapol- amine, ethanolamine, 2,2-aminoethanol, ethanol, monoethyl ethanolamine, Juthanolamine, cyclohexyl ethanolamine, 3-aminopro-anol, and 2-aminobutanal-1. Instead of alkanola inae containing NHa and / or NH groups, it is also possible to use other monofunctional compounds which react with NCO groups, for example monoamines and / or monoalcohols containing C rad alkyl radicals, to Cao. In this regard, fatty amines and / or fatty alcohols containing more than J 2 carbon atoms are preferred. In this case, polyurethane resins containing R'O groups bound to silicon are obtained, which do not contain any hydroxyl group. Laß monoamines and / or monoalcohals can also be used in a mixture with alkanolamines containing NH »and / or NH groups. In this way, the OH number of the resulting polyurethane resin containing R'O side and / or terminal groups bonded to silicon can be arbitrarily adjusted within the range of 0 to 100. An essential step in the production of the dispersion from polyurethane watery to polyurethane reef baee containing groups R'O lateral and / or terminals linked to the eilicio ee that a quantity of water is added during a short period to the PU prepolymer functionalized with R'OSi, which optionally contains hydroxyl groups, said amount of water is sufficient to avoid a further reaction of the HOSi groups formed by hydrolysis. The water is added using a stoichiometric excess greater than 10 times the amount of water necessary for the hydrolysis of the R'OSi groups. Preferably a stoichiometric excess of at least 50 times is used. The water is most preferably added in an amount such that at least half of the amount of water required for the production of the aqueous polyurethane dispersion is added all at once. By adding a sufficient amount of water subetantially preventing the formation of ßiloxane bridges by the condensation of the HOSi groups formed by hydrolysis, said condensation proceeds with the separation of the water, ie an aqueous dispersion of a polyurethane resin is obtained, which is practically free of siloxane bridges and which contains R'OSi and / or HOSi groups in an amount sufficient for in relacion. The polyurethane resin contains ionic groups, groups capable of forming ions and / or hydroplic groups. The polyurethane resin contains groups capable of forming ions, these are totally or partially converted to corresponding salts with a suitable compound, e.g., an agent eutrizer. This can be done at all stages of the synthesis described above, where it must be ensured that the compounds used for salt formation are selected so that they are shared as chemically-ipherteous entities during the synthesis. The compounds used for the formation of eal, such as neutralizing agents, for example, are preferably added in conjunction with water. Preferred groups that are capable of forming ions are those that are capable of forming anions. Examples of talee groups such as these have been described above in relation to the synthesis of the PU prepolymer containing NCO groups. A base, e.g., an amine, preferably a tertiary amine, is then employed for the conversion to anions. Examples of suitable tertiary amines include trialkylamines such as trimethylamine, triethylamine, t-isopropylamine, tri-n-propylamine and tri-n-bu-lamin; N-alkylmorph nae such as N-methylmorpholine and N-ethyl orfolin; N-dialkylalkanala inas such as N-dimet iletanola ina, N-diethylethanolane and N-dimeti-1 isopropanolamine, and mixtures of at least doe of these compounds. If the polyurethane resin contains cation-forming groups, one or more acids for the formation of ions are preferably used. Examples of suitable acids include phosphoric acid or esters of acid phosphoric acid, or carboxylic acids organice as acid formic acid, acetic acid, propionic acid or acrylic acid, hydroxycarboxylic acids such as lactic acid, dimethylolpropiopic acid or citric acid, or dicarboxylic acids such as a manic acid, glutaric acid or oxalic acid. Mixtures of estoß acids can also be used. However, a quaternization reaction with alkylating agents is also possible, such as a reaction with alkyl halides or epoxides, for example. The reaction of the compounds is used for the synthesis of the NCO functional PU prepolymer, and also the subsequent reaction to form the polyurethane resin functionalized with R'OSi, are conducted in an anhydrous media, for example at temperatures between 20 and 140 ° C, preferably between 40 and 100 ° C. The reactions can be conducted free of solvents, or suitable organic solvents that are familiar to one skilled in the art for polyurethane synthesis can be employed. Solvents miscible in water or not miscible in water can be used as solvents. It is generally advantageous to use those solvents which are removed at any stage of the production of the PU dispersion (for example after the final production of the latter), by distillation, optionally under reduced pressure, for example. Examples of suitable solvents include ketones eg, acetone, methyl ethyl ketone or methyl isobutyl ketone; N-alkylpyrrolidine, taike as N-met i J pyrrolidone, for example; "Iteres, such as diethylene glycol dimethyl ether or dipropylene glycol dimethyl ether, for example, and also cyclic urea urea derivative such as 1, 3-di- and i 1-3,4, 5,6-tetra idro-2 (lH ) -pyrimidinone. The polyurethane resin that is free of solvent or that is present in organic solution is converted to an aqueous phase by adding sufficient amounts of water. A finely divided polyurethane dispersion is obtained, with an average particle size greater than 10 nm and less than 2000 nm, preferably greater than 50 n and less than 500 nm. The particle size distribution can be onomodal or imodal, preferably monomodal. In general, it is not necessary to use together emulsifiers in order to convert the polyurethane resins used to aqueous dispersions. However, the possible use of ionic and non-ionic types of emulsifiers is not a rule in order to facilitate emulsification and optionally reduce the number of ionizable groups. During the production of the polyurethane dispersion, the educts are reacted with others in amounts such that binder vehicle qualities are obtained which are desirable to any person skilled in the art, e.g., dispersibility in water, viscosity behavior. , film forming properties, storage stability. For example, the properties such as the hardness and resistance to interperism of coatings obtained from the dispersions, can also be influenced by the choice of the type and quantity of the components. The amount of the type and the amount of the components can easily be determined by one skilled in the art with the help of the teaching given here, optionally with the aid of routine tests. In general, the quantitative proportions of the individual outputs are preferably selected and the reaction is preferably conducted so that the polyurethane resin forming the base of the polyurethane dispersion has a number average molecular weight (Mn) of 2500. at J 20000, a content of 10 to 400 mmoles, preferably of 20 to 300 mmoles, most preferably of 40 to 200 mmoles of lateral and / or terminal hydroxyl groups and / or R'O bonded to silicon, where R '= alkyl from C to C? or C (0) R "', and R' '' = Cx to C10 alkyl, per 100 g of solid reein, a hydroxyl number of 0 to 150 mg KH / g, preferably greater than 1 and less than 100 mg KOH / g, with respect to the solid resin, in which the hydroxyl groups bound to silicon are not included in the calculation of the OH number, and a content of ionic groups, groups convertible to ionic groups and / or hydrophobic groups. from 5 to 200 mFq per 100 g of solid resin Production of aqueous PU dispersion based on polyurethane resin containing hydroxyl groups and / or R'O side and / or terminal bonded to silicon can be effected by known methods. For example, it is possible to place the neutralized resins in a container and mix them with water with good dispersion. The aqueous bases containing opc. Finally, neutralizing agents can also be placed in a container and the resin can be incorporated with stirring. A continuous mode of operation is also possible, eg, the resin, the water and the neutralizing agent can be homogeneously mixed together simultaneously in known processing units, eg, a rotor-stator mixer. The pH of the resulting polyurethane dispersion can be adjusted to a value between 5 and 10, for example. From the components, a turbid aqueous dispersion is obtained, from opaque to milky, finely divided. The anionic PU dispersions which are preferably used have an acid number of 50 to 90 (with respect to solids), preferably greater than 10 and less than 50. The solids content is between 25 and 65 by weight, preferably greater than 35 and less than 60 $ in weight. The number average molecular weight (Mn) of the polyurethane resins contained in the PU dispersions is from 2500 to 120,000 for example, with the lower limit being 4000, most preferably 10000 and the upper limit up to 50000. Rotate the solvents that are optionally contained in the polyurethane dispersions, if Be desired, by distillation. This can be done under reduced pressure. The water-based lacquers produced from PU dispersions are self-interlacing. The PU resins which form the bases of the PU diespereiones have hydroxyl numbers of between 0 and 100, preferably between 0 and 60 mg KOH / g, where the hydroxyl groups bound to silicon are not included in the calculation of the number from OH. If the water-based interlacing lacquers used in the process according to the invention are to be open to external interlacing further, the hydraxyl number of the polyurethane resins is preferable within the upper scale of values. Pigments, additional binders, additives and optionally small amounts of solvents can be added to the dispersion of FU for the production of the interlacing water-based lacquers. In addition to the dispersion of the crosslinking polyurethane resin, the water-based lacquers may contain one or more of the different, additional binding vehicles. This may be advantageous in order to obtain synergistic effects, for example. Examples of additional binder vehicles include customary film-forming, water-soluble or water-thinnable reeins familiar to those skilled in the art, such as water-thinnable polyester resins, polyacrylate resins. 26 Can be thinned with water and / or another type of polyurethane resins that can be thinned with water. These can be reactive resins or na functional. The amount of resins added may be from 0 to 75% by weight, preferably from 0 to 50% by weight of the total resin solids. With from 0 to 30% by weight being particularly preferred. In this regard, the term "resin solids" represents the sum of all binding vehicles, excluding the content of entanglement agent that is optionally present for external entanglement, which is possibly also desired. The specifications and quantitative proportions of additional binder vehicles are selected so that a mixture is obtained which, on average, has a content of ionic groups, groups convertible to ionic groups and / or hydrofine groups of 5 to 200 mEqu per 100 g. of polyurethane resin. Anion groups are preferred. Examples of water-thinnable polyesters that may be used include those containing free carboxyl groups, polyesters with a high acid number. In principle, there are two known methods to incorporate the carboxyl groups requirements to the resin seventh. The first route is to terminate the ification when the desired number of acid has been reached. When this method is employed, the incorporation of hindered carboxyl groups is preferred, for example by condensation with di-ethyl-J-propionic acid. After neutralization with In contrast, the polyesters that are obtained from this form are soluble in water. The second possibility consists in forming partial ethers of di or polycarboxylic acids with palyesters which are rich in hydroxy groups and which have a low acid number. Dicarboxylic acid anhydrides are usually used for this reaction; these react with the hydcox component under the moderate ionee condition by the formation of a free carboxyl group. Water-thinnable polyacrylate resins which can be used can also contain free carboxyl groups, just like the polyether resins described above. Examples of polyacrylate resins include polyacrylate or acrylic copolymers, and carboxyl groups originated from the content of acrylic or methacrylic acid. The additional polyurethane dispersions should be understood to represent those described in, for example, DE-A-36 2A 125. They are anionically stabilized PU dispersions which can be produced by the reaction of polyols, di-dianates, ionic compounds and chain extenders with amines. In addition, the dispersions of PU stabilized by nonionic, hydrophilic groups can also be added to the self-quenching aqueous bake lacquers used in the process according to the invention. The polyesters can be thinned with water or water-based resins.

Polyurethane can also be acrylated or ingested in dispersions by suitable polymerization processes. Examples of acrylated polyurethane dispersions which can be used are described in DE-A-41 22 265. Another group of aqueous dispersions which can be added to the aqueous-based lacquers used in the process according to the invention are the dispersions described in DE-A-36 26 J24, which are based on condensation polymers containing ionic epoxide groups, and which are reacted with na saturated, copolymerizable monomers. When additional binders are added, it is self-evident that additional ionically stabilized resins and dispersions can only be used together with ionic dispersions with the same type of filler, in order not to have a negative effect on stability. If additional external entanglement is desired, various crosslinking agents, eg, condensation resins of aldehydes such as condensation resins of fenalformaldehyde and amine-phamalmaldehyde condensation resins, for example, and also blocked polyisocyanates, can to be used to produce water-based lacquers intrinsically self-interlacing which can be used in the process according to the invention. The crosslinking agents can be used individually or in a mixture. The mixing ratio of crosslinking agent to polyurethane resin is preferable ?! e 10:90 to 40:60, most preferably from 20:60 to 30:70, with respect to the weight of solids in each case. If additional binders are used in addition to the dispersion of the polyurethane resin according to the invention, the above mixing ratios are preferably bathed in the total resin eolide. Examples of amine resins which are suitable as entanglement agents include alkylated resins which are produced by the reaction of α-inotylazines and amidat iakines with aldehyde. Amines or compounds containing groups such as melamine, guano ina, acetoguana ina, benzoguanamine, dicyandiamide or urea are condensed with aldehydes, particularly formaldehyde, by known industrial methods in the presence of alcohols such as methanol, ethanol, propanol, butanol or hexanol. The reactivity of the amine resins of this type is determined by the degree of condensation, the ratio of the amine or amide components to formaldehyde and by the type of alcohol used for etherification. Examples of resins of this type and their production are described in "Hauben-Weyl, Methoden dec organischen Chemie C" Methods of Organic Chemistry "3 1963, page 357. These products are of commercial use. they can use blocked polyisocyanates Any polyisocyanate can be used for the invention wherein the isocyanate groups are reacted with a compound such that the blocked polyisocyanate formed ee resistant to hydroxyl groups and to water at room temperature, but react at elevated temperatures, on the scale of about 90 about 250 ° C, for example. Any organic polyisocyanates which are suitable for crosslinking can be used for the production of the blocked polyisocyanates. The isocyanates are preferred to contain approximately from 3 to approximately 36 carbon atoms, particularly from about A to 15 carbon atoms. The diisocyanates mentioned above as component b) are examples of suitable diisocyanates. Polyisocyanates of a higher isocyanate functionality are preferred, as mentioned above under b). Examples of the same include tris- (4-ißocianatofeni 1) -methane, 1, 3, 5-tiieocianatobenzene, 2,4,6-tri isocyanata toluene, 1, 3, 5-tris (6-isoci n tohe no) - biuret, polymeric bie- (2, 5-di isocyanato-4-methyl-1-pheny1) -methane and polyisocyanate, such as dimers and trimers of diisocyanatotoluene. Mixtures of polyisocyanates can also be used. The argonic polyisocyanates which can be used as crosslinking agents in aqueous phase lacquers can also be prepolymers, which can be derived from a polyol, for example. For this purpose, the polyols are reacted in a usual manner with an excess of polyisocyanates, so that they form prepolymer which they contain terminal isocyanate groups. The blocked polyisocyanates which can be used as crosslinking agents can be blocked with the usual volatile monovalent blocking agents which are used in lacquer chemistry. Examples of eßtoß include various alcohols, oximes, phenols, nitrogen heterocyclic fune ionalee, -NH such as sunflower derivatives or triassal derivatives, amines, beta-ketone compounds and ophthalmide. The polyisocyanates can be blocked with the same or different blocking agents in a molecule. It is also possible to use mixtures of different blocked polyisocyanates as crosslinking agents, as well as polyisocyanates which have been blocked in different forms intra-olecularly. In addition, the self-entangling aqueous base lacquer may contain polymer microparticles conocidas known to one skilled in the art. Interlaced or non-interlaced microparticles can be used. Examples of polymer microparticles such as these are described in EP-A-0 036 127 and EP-A-0 234 362. The aqueous self-linking baεe laεes used in the process according to the invention may also contain industrial lacquer additives. , for example, means that affect the rheology, such as highly dispersed hydrated silica, inorganic layer silicate or polymeric urea compounds. Examples of substances that act as thickeners also include cellulose ethereal water soluble such as hydroxyethyl cellulose, methyl cellulose or carba i eti cellulose, as well as synthetic polymers that contain ionic groups or groups with an associating action such as polyvinyl alcohol, polymethacrylamide, poly ethacrylic acid, polyvinylpirralidone, styrene copol eroß - maleic anhydride or maleic anhydride and derivatives thereof, and also hydrofluorically modified polyurethane or paliacri lates. In addition, anti-sedimentation agents, flow improvers, light stabilizers, anti-foam agents such as silicate-containing compounds, for example, surfactants and binding agents can also be used. The term "surfactants" should also be understood to mean known paste resin which can be used to promote better dispersion and division of the pigments. Catalysts can optionally be used to accelerate hardening; however, it is also possible to use thermal energy to harden ßin the use of a catalyst. Industrial solvent solvents are suitable as solvents present in small quantities. Fetuses can originate from the production of the binder vehicle or can be added separately. Examples of solvents such as these include mono- or polyhydric alcohols, e.g., propanol, butanol or hexanal; glycol ethers or esters, e.g. dialkyl ethers of diethylene glycol, dialkyl ethers of dipropylene glycol, each ; > not containing an alkyl of C ^ -C ^, ethoxy propanol or diglycol; glycols v.gr., ethylene glycol, propylene glycol and oligomers thereof; n-met i Ipirral idona, as well as ketones such as ethyle-l-ketone, acetone or cyclohexanone; aromatic or aliphatic hydrocarbons, e.g., toluene or xylene, or aliphatic hydrocarbons linealee or branched from C ^ -Cxa ». The self-lacing water-based lacquers may contain one or more inorganic and / or organic color or effect imparting pigments and optionally at least one filler. Example of effect imparting pigments include pig entoe metallic, e.g., those comprising aluminum, copper or other metals; interference pigments, such as metallic pigments coated with metal oxides, eg, titanium dioxide-coated aluminum, coated mica, such as mica coated with titanium dioxide, for example, and graphite-effect imparting pigments. Examples of color imparting pigments and fillers include titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, silica, barium sulfate, micronized mica, tailor's soap, kaolin, clay, azo pigments, pigments of phthalocyanine, quinacridone pigment, pigments of pyrrolo pyrrole and perylene pigments. The effect imparting pigments are generally employed in the form of a commercially available aqueous or non-aqueous paste, optionally mixed with Organic solvents and additives, which preferably are water-thinnable, and are then mixed with the aqueous binder vehicle with high shear stress. The powder imparting pigments can be processed first to form a slurry with organic solvents that can be thinned with water and additives. In this regard, it should be ensured that the lamella effect imparting pigments are not mechanically damaged during mixing. The color pigments and / or fillers can be made into a paste in a portion of the aqueous binder vehicle, for example. The formation of the paste can also be effected preferably in a slurry resin which can be thinned with special water. An example of a polyurethane-based paste resin, which is preferably used in an aqueous phase lacquer according to the invention, is presented in R'OSi and / or HOSi. The formation of the paste can be carried out in customary processing units known to those skilled in the art. Next, the formation of the paste is carried out to be completed with the residual ratio of the aqueous binder vehicle to the aqueous paste resin to produce the terminal color pigment. If paste resins are present in the coating medium, they are added to the binder vehicle plus the interlacing agent, which optionally is present for the calculation of the resin solids. If the water-based lacquer is formulated based on a self-interlacing polyurethane tessera, the only preferred eßtabilized entity containing ROS groups and / or HOSi, lateral and / or terminal, this one contains bases as neutralizing agents. Examples include ammonia or organic amines such as triethylamine or N-methylmorpholine and amine alcahaleß taleß such as dimet ilisopropanolamine, dimethoethanolamine or 2-amino-2-meth i-1-propanol. Self-entangling water-based lacquers can have a solids content of 10-50 $ in weight, for example. For effective basecoats, this preferably is 15-30% by weight, for example, and for a single-color bakecoat, preferably, it is higher, for example, 20-45% by weight. The ratio of pigment to binder vehicle plus optional interlacing agents plus the optional rosin resin in the aqueous baεe lacquer may be between 0.03: 1 and 3: 1, for example. For effect base lacquers, this is preferable from 0.06: 1 to 0.6: 1 for example; and for a single-color base coat this is preferable higher, for example 0.06: 1 to 2.5: 1 based on the weight of the β-β-lidasin in each case. The solvent content of the water-based lacquers is preferably less than 20% by weight, preferably less than 15% by weight, most preferably less than 10% by weight. The aqueous lacquers of self-lacing can be applied by the usual methods. Freferible nte are applied by spraying to a thickness of 3A The dry coating thickness is preferably 10 to 25 μm for example, and for basecoats of only one color, it is preferably higher, for example. The application is preferably carried out by the wet-wet process, ie, after an air-ventilation phase, eg, at 20-A 0 ° C, water-based lacquer coatings. they are overpainted with a customary clear lacquer to a thick dry coating preferably of 30-60 m and are entangled together with the latter, with the condensation of the HOSi groups to form siloxane bridges, at temperatures of 20 to 140 ° C, For example, the drying conditions for the topcoat coating (clearcoat and clearcoat) depend on the clearcoat material used.They may involve temperatures from 20 to 150 ° C, for example. r The temperature is preferred from 20 to A0 ° C. Temperatures above 100 ° C, for example above 110 ° C, are preferred for the purpose of reverse milling. In principle, all transparent clearcoats or transparent pigmented coating means are suitable as the clearcoat. In this regard, they may use one or two component paints containing solvents, water-thinnable transparent lacquers, transparent coating powders, or hardenable transparent lacquers. _'on radiation. The multilayer coatings coated by the process according to the invention can be applied to different types of substrates. The latter are generally etá.licoß substrates or plastics. They are often pre-coated, that is, plastic substrates can be provided with a plastic sizing coating, for example. The metal substrates generally have an electrophoretically depointered size primer and optionally one or more additional lacquer coatings, such as a filler coating (surface primer, for example). These slumps are usually hardened. However, the aqueous bake lacquer may be applied wet to wet to interlaced filler coatings, as described in, for example EP-A-0 23A 037. In this case, the bake lacquer generally baked together with the filler liner before the application of a transparent lacquer coating. It is also possible to apply the water-based lacquer directly, without additional intermediate coatings, to a coating of the baked or baked baking dish, also as is possible for other known water-based or solvent-based lacquers. The multiple layer coatings obtained from the application of the procedure according to the invention, satisfy the requirements that are currently customary for painting work for vehicles with rotor. The procedure according to the invention of this form is suitable for vehicle painting work and vehicle repair painting work. It can also be used in other areas, eg, plastics coating, particularly for the coating of vehicle components. The multi-layer coating produced by the process according to the invention has a good surface area. The adhesion between the coatings and the basecoat coating is good and also does not exhibit any defects of separation, even when subjected to a cabinet environment with moisture. The invention is particularly suitable for use in automotive paint work (mass production and painting work for repair). The multiple layer coatings produced by the process according to the invention use the lacquer of aqueous self-linking baεe containing, as binders, polyurethane resins comprising groups R ROSi and / or HOSi side and / or terminals , and are characterized by their excellent resistance to condensation water.

EXAMPLE OF PREPARATION 1 339 g of a polyether of adipic acid, hexanediol and iophthalic acid (OH #: 104) and 19 g of dimethylolpropionic acid were dissolved in 160 g of N-methynorhydrolidone and heated to 40 ° C. Then, 5 g of isophorone diisocyanate were added in such a way that the reaction temperature of A 0 ° C was not exceeded. The mixture was kept at this temperature until an NCO content of 2% was obtained (based on the solid resin), determined in accordance with DIN 53 1A5. Then, they successively added 14.6 g of 3-amino-propyltriethoxysilane and 16.2 g of diethanolamine. The reaction mixture was maintained at A 0 ° C haßta which did not detect NCO groups (titration). 12.6 g of triethylamine were homogenously incorporated for neutralization. After adding the neutralized resin solution to 596 g of deionized water with vigorous stirring, a dispersion of finally divided aqueous polyurethane was obtained.

EXAMPLE OF PREPARATION 2 339 g of a polyester of adipic acid, hexanediol and isophthalic acid (OH No.: 104) and 19 g of di-1-propionic acid were dissolved in 160 g of N-methylaralkidone and heated to 40 ° C. Then, they added J25 g of Iodohorone diisocyanate in such a way that the reaction temperature of 60 ° C was exceeded. The mixture was kept at this temperature until an NCO content of 2% (based on the solid resin) was obtained, determined in accordance with DIN 53 1A5. Then, 43.Ag of 3-amine-propyltriatetiginate and 2.3g of diethanolamine were successively added. The reaction mixture was kept at A0 ° C haßta that detected NCO group libree (titration). J2.6 g of triethylamine was homogenously incorporated for neutralization. After adding 596 g of deionized water for 5 minutes, a finely divided aqueous polyurethane dispersion was obtained.

EXAMPLE OF PREPARATION 3 339 g of a polyester of adipic acid, hexanediol and iophthalic acid (OH #: 104) and 19 g of dimethylolide ionic acid were dissolved in 160 g of N-methyl and Ipirrolidane and heated to 40 ° C. Then, J 5 g of isophorone diisocyanate was added in such a way that the reaction temperature of A 0 ° C was not exceeded. The mixture was kept at this temperature until an NCO content of 2% was obtained (based on the reeine eolide), determined in accordance with DIN 53 165. Then, 42 g of 3-amine-propyltriethoxysilane and 2.3 g were successively added. of diethanolamine. The reaction mixture was maintained at A 0 ° C until no groups were detected.

NCO free (titulación). J2.6 g of triethyl film were homogenously incorporated for neutralization. After adding 596 g of deionized water for 5 minutes, a dispersion of finely divided aqueous polyurethane was obtained.

EXAMPLE OF PREPARATION 4 339 g of a polyether of adipic acid, hexanediol and isophthalic acid (OH No.: 104) and 19 g of dimethyl and propionic acid were dissolved in 160 g of N-methylpyrrolidone and heated to 40 ° C. Then,. 116 g of 1-hexamethylene trimeti diisocyanate was added. so that the reaction temperature of A0 ° C was not exceeded. The mixture was maintained at this temperature until η obtained an NCO content of 2 $ (based on the solid resin), determined in accordance with DIN 53 1A5. Then, 33.6 g of 3-a-ino-propyltriethoxy-ylene and 4.6 g of diethanolamine were successively added. The reaction mixture was maintained at A 0 ° C until no free NCO groups were detected (titration). After adding the resin to a mixture of 10.9 g of N, N-dimethyiiopropanolamine and 596 g of deionized water with vigorous stirring, a finely divided aqueous polyurethane dispersion was obtained.

EXAMPLE OF PREPARATION 5 339 g of a polyester of adipic acid, hexanediol and iophthalic acid (OH No.: 104) and 19 g of dimethylolpropionic acid were dissolved in 160 g of N-methyl Ipyrrolidone and heated to 40 ° C. Then, 1 5 g of isophorone di-biacyanate was added in such a way that the reaction temperature of A 0 ° C was not exceeded. The mixture was maintained at this temperature until an NCO content of 2 $ was obtained (based on the ßolid resin), determined in accordance with DIN 53 1A5. Afterwards, 35.4 g of 3-amino-propyltriethoxy-silane were successively added. The reaction mixture was kept at A 0 ° C until free NCO groups were detected (titration). 14.5 g of triethylamine were homogenously incorporated for neutralization. After adding 596 g of deionized water for 5 minutes, a finely divided aqueous polyurethane dispersion was obtained.

EXAMPLE OF PREPARATION 6 346 g of a polycapralactone diol (Na of OH: 102) and 19 g of dimethylopropionic acid were dissolved in 160 g of N-methylpyrrolidone and heated to 40 ° C. Then, 136 g di, 3-bis (1-isocyanato-l-methilet i 1) -bepcene (TMXDI) was added in such a way that the reaction temperature of 100 ° C was not exceeded. The mixture was maintained at this temperature until A NCO content of 2 $ was obtained (based on solid resin), determined in accordance with DIN 53 1A5. Afterwards, 43.6 g of 3-amino-propyl-methoxysilane and 2.3 g diethanolamine were successively added. The reaction mixture maintained at A0 ° C haßta that no free NCO groups were detected (titration). 12.6 g of triethylamine were homogenously incorporated for neutralization. After adding 622 g of deionized water for 5 minutes, ε obtained a diεperesion of finely divided polyurethane aquauane.

EXAMPLE OF PREPARATION 7 A) Preparation of a carboxy-functional polymer containing epoxide groups: 100 g of an anhydrous mixture (Acid No./Na0-466), prepared by the reaction of trimethyl anhydride with i, 2-propanediol, and in this way tiring Trimethyl anhydride and anhydride of the following formulas: -? n where x = 1 to 6, which was homogenized in 106 g of xylene at 50 ° C, were added dropwise for 1 hour to a solution in 70 g of methyl ethyl ketone of 141 g of a polyester OH No. = AA) which was prepared based on phthalic anhydride, isophthalic acid, malic anhydride, pratanol and glycerin as described in (OH No. = AA) the reaction mixture was stirred at 90 ° C haeta which reached an acid number in water of 165 (100 $ of reein). Then, 32 g of water were mixed, and an acid number in butanol of 166 (100% resin) was obtained after stirring for 6 hours of AO at 90 ° C. The temperature of the mixture was reduced to 60 ° C, and after adding 0.3 g of lithium benzoate, 132 g of an epoxidized linase oil (epoxide No. = 0.7) were added dropwise over 2 hours. The mixture was stirred until the acid number in butanal was reduced to 66.5. Then, a mixture of 42 g of dimethylamine (60% in water) was stirred in 660 g of water. An opalescent, light yellow solution was obtained, from which the organic solvent was removed by distillation at 0.1 bar and 40 ° C. After filtration, an aqueous resin solution, practically transparent, yellow was obtained. Solid content: $ 32 (one hour at J25 ° C. b) preparation of the polymer dispersion. 705 g of the above aqueous dispersion (32%) and 196 g of water were introduced into a reactor equipped with a stirrer, reflux condenser, internal thermometer and a measuring device for the monomers and for the initiator.

This mixture was heated to 60 ° C with stirring, and a solution of 0.5 g of ammonium peroxydieulfate in 35 g of water was added. 5 minutes after the addition of the initiator, 35 g of a monomer mixture comprising 125 g of methyl methacrylate, 94 g of n-methyl acrylate and 17 g of glycidyl mefcacrilate were added, and after an additional 15 minutes of prepolyme The remaining amount of the monomer was added over 2 hours. After 10 minutes from the end of the addition, 0.2 g of additional ammonium peroxide, dissolved in 10 g of water, was added over 10 minutes, and the batch was stirred for 2 hours at 0 ° C in order to carry out the reaction. I complete the reaction. A stable aqueous dispersion was obtained, which had a wind content of approximately 40 $.

PREPARATION EXAMPLE & a) Preparation of a functional polymer with carboxy containing epoxide groups 100 g of an anhydride mixture (Acid Na./Hß0, = 560) prepared by the reaction of trimethylic anhydride with 1,2-pranediol, which was homogenized in 30 g of acetone at 50 ° C, was added dropwise over 1 hour to a solution of 125 g of a palisater. (OH No. = 107) in 70 g of methyl ethyl ketone. The reaction mixture was stirred at 90 ° C haßta which reached an acid number in water of 197 (with respect to 4A LOO $ of resin). Then, 15 g of water were also mixed. After stirring for 6 hours at 60 ° C to 90 ° C, the acid number in butanol was 160 (100% resin). The temperature of the mixture was reduced to 60 ° C, and for 133 hours 133 g of a layered epoxy linseed oil (epoxide number = 6.9) were added dropwise over 2 hours. The mixture was stirred until the number of acid in butanol was reduced to 90. Then, a mixture of 56 g of dimethylamino ethanol in 540 g of water was stirred. An opalescent, light yellow solution was obtained, from which the organic solvent was removed by distillation at 0.1 bar at 40 ° C. After the filtration, ß obtained a solution of aqueous resin, practically transparent, yellowish. Solids content: approximately $ 39 (one hour at 125 ° C). b) preparation of the polymer dispersion. 355 g of the aqueous dispersion (39%) of 6a to 452 g of water were mixed in a reactor equipped with a stirrer, reflux condenser, electric thermometer and measuring device for the manufactures and for the initiator. The mixture was heated to 60 ° C with stirring and an O.Sg solution of ammonium peroxydisulfate in 35 g of water was added. 5 minutes after the addition of the initiator, 35 g of a monomer mixture comprising 165 g of methyl methacrylate, 142 g of N-butyl acrylate and 24 g of hydroxyethyl acrylate were added, and after 15 additional minutes of prepolymerization, the remaining monomer amount was added for 2 hours. 10 minutes after the addition was complete, an additional 0.2 g of ammonium peroxydisulfate, dissolved in 10 g of water, was added for 10 minutes, and the batch was stirred for an additional 2 hours at A 0 ° C in order to effect completely the reaction. A stable aqueous dispersion was obtained, which had a solids content of about 40 $.

EXAMPLE OF PREPARATION 9 Preparation of a paste resin 1395 g of a linear, saturated polyester (synthesized from adipic acid and neapetol ester and glycolic acid hydroxypivalic ester) with a number of OH 312 and a viscosity (at 25 ° C) of A.7 Pas were heated at 90 ° C, with vigorous stirring, with 161 g of dimethylolpropionic acid and 163 g of triamethylpropane to effect the dissolution in a reaction basin equipped with an internal thermometer and a reflux condenser. After adding 665 g of tetramethylxylene diisocyanate, the mixture was slowly heated to 120 ° C until the NCO content was less than 0.2 $. Then, the mixture was diluted with 661 g of ethoxypropanol. Solids (30 min 150 ° C) 75 $ by weight Number of acid (with respect to solids 27 Viscosity at 25 $, diluted at 40 $ with methoxypropanol 210 mPas.

A mixture of 5A.3 g of dimethylethanolamine and 56.3 g of water was rapidly added to 1963 g of this reein solution and heated to 60 ° C. The mixture was then slowly diluted with water to form a highly viscous, turbid paste, which could be easily processed with heat and which had the following properties and characteristics: Solids (30 min, 150 ° C) 32.3% by weight viscosity a 25 ° C 1.3 Pas * MEQ value 42 pH 7.6 * Measured on a rotary viscosity meter with a coaxial cylinder arrangement in accordance with DIN 53 016 and DIN 53 019 after applying shear for 5 minutes at a shear rate of 231 sec-A.

PREPARATION OF THE COMPONENTS FOR THE FOLLOWING EXAMPLES OF LACQUER EXAMPLE OF PREPARATION 10 Preparation of a binder vehicle solution 50.00 g of the water-thinnable binder vehicle described above in Preparation Example 7 were mixed with: 43.94 g of deionized water and 6. 00 g of butoxyethanol, and the pH was adjusted to 6.2 - 6.4 with 6.06 g of N-dimethylamino ethanol.

EXAMPLE OF PREPARATION 11 Preparation of an aluminum slurry 20.50 g of a commercially available aluminum slurry with a metal content of 65 was shaken well with a mixture comprising: 7.00 g of butoxyethanal and 15.50 g of deionized water, and then mixed with a mixture comprising: 4.00 g of a binder vehicle described above in the preparation axis 7, and with 4.50 g of the binder vehicle described above in Preparation Example 2, 10,006 butoxyethanol, 34.70 g. of deionized water, and 3.00 g of a commercially available acid acrylate thickener. The pH was adjusted to 6.2-6.4 with a mixture of 0.06 g of N-dimethylaminoethanol and 0.72 g of deionized water.

EXAMPLE OF PREPARATION 12 Preparation of a blue pigment paste. Using a solvent, 10.00 g of Cu-phthalocyanine pigment were pre-dispersed in 17.00 g of a resin of commercially available lexameth and elastin and 10.00 g of butoxyethanol, and then added an additional 5.00 g of the melamine resin and 10.00 g of ethoxyethanol, the mixture was completely dried in a ribbon mill, followed by mixing with a mixture of 0.90 g. g of a commercially available acid acrylate ester, and 16.91 g of deionized water. The pH was adjusted to 7.1-7.3 with 2.00 g of N-aminoethanol and 16.19 g of deionized water.

EXAMPLE OF PREPARATION 13 Preparation of a green pigment paste 20.00 g of a chlorinated phthalocyanine pigment, in a solvent, in a mixture comprising 20.00 g of a binder vehicle described above in Preparation Example 9, 35.00 g of butoxy ethanol and 0.50 were predicted. g of N-dimethylaminoethanol, and subsequently completely dispersed in a ribbon mill. Then, the mixture was diluted with 24.50 g of deionized water.

EXAMPLE OF PREPARATION 14 The procedure was as described in Preparation Example 10, except that the binder vehicle described in Preparation Example 6 (50.00 g) was used.

EXAMPLE OF PREPARATION 15 The procedure was as described in Preparation Example 11, except that the binder vehicle described in Preparation Example 6 (4.00 g) was used together with the binder vehicle described in Preparation Example 2 (4.50 g).

Example of lacquer formulations EXAMPLE 1 1. 1 Production of a blue metallic base lacquer, thinner with water. 30.00 g of the binder vehicle solution described in Preparation Example 10 were stirred for 30 minutes with 19.00 g of the aluminum paste described in Preparation Example 11, 1.90 g of Acrylate Acid Thickener (camo previously used) 17.44 g of deionized water and 0.25 g of N-dimethylaminoethanol; 25.50 g of the polyurethane dispersion described in the preparation example 6 were stirred in this mixture and the pigment paste described in the preparation example J.2 was added in an amount of 0.94 g. Then, 4.00 g of N-butanal was added with stirring, and the viscosity was adjusted to 90-95 mPa.s at a shear rate of 100 sec-A with 0.96 g of water.

Solid content: 16.0 $ in weight (120 minutes in a circulating air drying oven at J20 ° C). 1.2 application of the basecoat and a clearcoat. The base lacquer described in 1.1 was applied using a spray gun of compressed air atomizer to a steel sheet, which was pre-coated in a normal manner with a coating of Zn phosphate, electrodepoissic lacquer by inmeretion and sizing by spray, so that a total dry coating thickness of 15 m was obtained by applying the two coatings. The conditions for the application of the base lacquer were an ambient temperature of 23 ° C and? 60 ° of relative atmospheric humidity. After application, the coated steel sheet was forced air for 5 minutes at 50 ° C in a drying oven with circulating air, and after cooling to 23 ° C it was overpainted in a usual manner with a commercially available acrylate-elastin resin transparent lacquer and baked for 30 minutes at 130 ° C. In this way, a uniform defect-free coating was obtained, which exhibited an excellent metallic effect, a very high gloss and an excellent resistance to condensation water.

EXAMPLE 2 2. 1 production of a silver metal base lacquer, thinner with water. A metal-based silver lacquer was produced, analogously to Example 1.1, from 40.00 g of the binder vehicle solution described in Preparation Example 14, 19.00 g of the de-chalk aluminum paste in Preparation Example 15, 1.90 g of acid acrylate thickener, 0.26 g of N-dimethylamine ethanol, 22.00 g of a polyurethane dispersion (as in preparation example 2), 4.00 g of n-butanol and 12.62 g of deionized water. The content of aeolides was 16.0 $ by weight (120 minutes in a drying oven with air in irculation at 120 ° C).

The viscosity was 90-95 mPa.s at a cutting force velocity of 100 sec- *. 2.2 Application of the bake lacquer and a clear lacquer. A sheet of prerevented steel, as described in Example 1.2, was coated with the basecoat and dried with forced air for 5 minutes at 50 ° C in a drying oven with circulating air. After cooling, the basecoat was overcoated with a clearcoat of two commercially available acrylate-isocyanate components and baked for 30 minutes at 130 ° C. The reverse obtained in this way was characterized by a high gloss, an absolutely uniform defect-free formation, a pronounced metallic effect and excellent resistance to dampening water.

EXAMPLE 3 3. 1 production of a green metal bake lacquer, thinner with water. The base lacquer was produced, analogously to Example 1.1, from 59.00 g of the binder vehicle solution as in Preparation Example 10, 16.50 g of an aluminum paste as in Preparation Example 11, 1.90 g of acid acrylate thickener, 0.26 g of N-dimethylaminoethanol, 4.60 g of camo polyurethane dispersion in Preparation Example 4, 0.60 g of the green pigment paste described in Preparation Example 13, 4.00 g of n-butapol, and 10.94 g of deionized water.

Solids content: 17.1 $ by weight (120 minutes in a drying oven with air in circulation at 120 ° C). Viscosity: 90 - 95 mPa.s at a shear rate of 100 sec_A. 3.2 application of the lacquer and a transverse lacquer. As described in Example 1.2, the bae lacquer of 3.1 ee was applied to a pre-coated sheet of steel and, after drying with forced air, on top with a commercially available clear lacquer of melamine-rilate-meiamine and baked for 30 minutes. minutes at 130 ° C. A green metallic coating was obtained, the spectrum of property of which It was as good as that of examples 1.2 and 2.2.

EXAMPLE 4 4. 1 production of a cracked base lacquer, of a single color. 300 g of a custom paste paste (as in DE-OS 4 000 669) were mixed with 350 g of a pigment in Latin, red color index 166). The pH was adjusted to 6.5 with dimetiranala ina, and the solids content was adjusted to 50% by weight by adding deionized water. The mixture was then completely dispersed in a lißtón mill to make it transparent. 4.2 1.4 g of a commercially available thickener based on polyacrylic acid (solids content: 10% by weight, pH 7.5) were mixed with 129 g of the diesperion of Example 1 and 40 g of the paste resin of example 4. 1 Then 24 g of a commercially available ipsalutable melamine resin in water (Setamine US 136 / BB 70 manufactured by AK70) were added with stirring, then 10 g of the red paste of Example 4.1 was added and stirred homogeneously. The viscosity was adjusted to an application viscosity of 100-130 mPa.s using deionized water; this was measured on a rotational viscometer at 25 ° C and at a shear rate of 231 sec-1. 56 4. 3 Application of the basecoat and a clearcoat. The water-based lacquer obtained was applied by spraying a custom body work panel, which was sprayed and pre-rendered with cathodic inversion coating and a filler. This was done to give a dry coating thickness of 30 u. After application, the coating was ventilated with air for 10 minutes at room temperature and then pre-dried for 10 minutes at 60 ° C. Then, a commercially available self-hardening melamine resin clear lacquer was commercially available based on acrylate resin to give a dry coating thickness of 35 μm and was dried for 16 minutes at 120 ° C (temperature of the Workpiece). A multi-capable coating was obtained which exhibited excellent resistance to condensation water (DIN 50 017, 420 hours, 40 ° C).

EXAMPLE 5 Production of a double metallic silver coating. 20 g of a commercially available aluminum paste suitable for the aqueous baεe lacquer were mixed together, containing 65% by weight of aluminum, 20 g of butyl glycol, 6 g of N-me and Ipyrrolidone and 1 g of a commercially available surfactant. available, to form a bronze dispersion. Then, 1.4 g of a commercially available ester was mixed to baεe to polyacrylic acid (content of εolids: 10% in peeo, pH 7.5). Then, 129 g of the dispersion of Example 1 and 40 g of the paste resin of Example 4.1 were shaken in the bronze dispersion. Then 24 g of a commercially available water-insoluble melamine resin (Setamine US 136 / BB 70 manufactured by Akzo) were added with stirring. The viscosity was adjusted to an application viscosity of 100-130 mPa.s using deionized water; eßto was measured on a rotary viscosity meter at 25 ° C and at a shear rate of 231 sec-A. The water-based lacquer obtained was applied by spraying a custom body work panel, which was phosphatized and precoated by cathodic inversion coating and with filler. This was done to give dry coating thickness of 15 pm. After application, the coating was ventilated with air for 10 minutes at room temperature and then pre-dried for 10 minutes at 60 ° C. Then, a commercially available self-hardening melamine resin clear lacquer was commercially available based on acrylate resin to give a dry coating thickness of 35 p and eec for 16 minutes at 120 ° C (part temperature of work). A multi-layer coating was obtained which exhibited excellent resistance to condensation water.

Claims (6)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A process for producing a multi-layered decorative coating by applying a color bake lacquer and / or imparting effect of an aqueous bake lacquer containing polyurethane to an optionally revetted substrate and applying a coating of transparent lacquer, characterized in that it uses a self-entangling, aqueous coating medium or the base lacquer, which contains, as a binder vehicle, a dispersion of aqueous polyurethane resin based on a linear structure polyurethane resin. or branched having a number average molecular weight (Mn) of 2500 to 120,000, a content of 10 to 400 mmoles of hydroxyl groups and / or R'O side and / or terminals bonded to silicon, wherein R '= alkyl of C to Ca or C (0) R "'and R'" = Cx alkyl to CAO, per 100 g of solid resin, a number of hy droxyl from 0 to 150 mg KOH / g with respect to the solid resin, wherein the hydroxyl groups bound s to silicon are not included in the calculation of the OH number, and a content of ionic groups, groups convertible to ionic group and / to group β hydrophilic from 5 to 200 Fc per 100 g of solid resin. 2. - An aqueous self-interlacing base lacquer coating medium containing color pigments and / or effect imparters suitable for producing the base lacquer coating of a multi-layer decorative coating in accordance with claim 1 , and containing, as binder vehicle, a polyurethane resin dispersion based on a polyurethane resin of linear or branched structure having a number average molecular weight (Mn) of 2500 to 120,000, a content of 10 to 400 mols of hydroxyl groups and / or R'O side and / or terminal, linked to silicon, where R '= C to C alkyl? or C (0) R '' ', and R' "= C to C10 alkyl, per 100 g of solid reein,? n hydroxyl number from 0 to 150 mg KOH / g with respect to the solid resin, in dande The hydroxyl groups linked to silicon are not included in the calculation of the OH number, and a content of ionic groups, groups convertible to ionic groups and / or hydrofilic groups of 5 to 200 mEqu per 100 g of solid retin. - A coating method or means according to claim 1 or 2, further characterized in that the polyurethane resin has a content of 20 to 300 mmoles of gr? Poe hryroxyl and / or R'O side and / or terminals ligated to the silica 4.- A method or means of disclosure in accordance with any of the preceding claims, further characterized in that the dispersion of aqueous polyurethane resin contained as a binder vehicle can be obtained by the reaction of a prepolymer of gelled, linear or branched polyurethane, containing ionic, glycid groups capable of forming hydrophilic ions and / or groups. and which is functional isocyanate, with one or more compounds of the general formula ((HX ~) rR) Si (OR ') to (R ") c (I) wherein X = 0, S, NH or NR1' - ', R = a bifunctional, trifunctional or tetrafunctional organic radical, with a molecular weight of 13 to 500, R' = an alkyl of C to Ca or C (0) R '' ', R "= R"' = C to Cto alkyl, RIV = C to C alkyl, a = 1, 2 or 3, b = 1, 2 or 3, c = 0, 1 or 2, n = 1 to 3, wherein a plurality of radicals R ', R' 'and R' '' may be the same or different and wherein the sum of a + b + c is 4, optionally in admixture with one or more alkanolamines containing NHa and / or NH groups with a functionality OH at least 1, and convert the product of optionally neutralized reaction to an aqueous dispersion by mixing with water using more than 10 times the stoichiometric excess of the amount of water necessary for the hydrolysis of the R'OSi groups. 5. A method or a coating means according to claim 4, further characterized in that the polyurethane prepolymer functional with isacyanate can be obtained by reacting, in an anhydrous medium, of: a) at least one linear compound or branched containing At least two groups that react with isocyanate and have an average molecular weight of 60 to 10,000, b) at least one organic polyisocyanate, c) at least one compound that contains a group that reacts with isocyanate and therefore is an ionic group, a group capable of forming ions and / or a hydrophilic group, with a number-average molecular weight (N) of up to 10,000, and a ratio of NC0 / 0H greater than 1 to 4: 1. 6. A coating method or means according to claim 5, further characterized in that the linear or branched compound of component a) is at least one polyol based on one or more polyethers, polyesters, polyurethane and / or polycarbonate, which contain at least OH groups in the molecule and which have a number-average molecular weight (Mn) of 600-10,000, optionally with the joint use of one or more of the lower alcohols and / or difunctional low molecular weight amines and / or amino alcohols, which are different from each other and which have a molecular weight of less than 600, preferably less than 400. 7. A process or coating medium according to any of the preceding claims , further characterized in that the aqueous coating medium for coating the basecoat contains one or more self-interlacing binder or externally interlacing binder in a different manner. amount from 0 to 75 $ in weight with respect to the total resin solids. 6. - A coating method or means according to any of the preceding claims, further characterized in that the aqueous coating medium for the basecoat coating has a β-solid content of 10 to 50% in peb to a ratio of pigment to vehicle binder most of the entanglement agent and paste paste, which are optionally present from 0.03: 1 to 3: 1, with respect to the weight of the solids in each case. 9. A process according to any of claims 1 and 3 to 6, further characterized in that the water-based lacquer coating is applied to a dry coating thickness from 6 to 50 pm, and after a vent phase. The air is wet-wetted with a customary clear topcoat to a dry coating thickness of 30-60 p.m. and a dry side together with the latter from 20 to 150 ° C. 10. A method of compliance with any of claims 1 and 3 to 9, further characterized in that it is carried out for the reverse of multiple layers of motor vehicle. PROCEDURE TO PRODUCE DECORATIVE COATINGS OF MULTIPLE LAYERS SUMMARY OF THE INVENTION A method and a coating means for producing multi-layered decorative coating on a substrate is described, wherein a coating of bake lacquer is applied and is overcoated with a clear lacquer coating, wherein a lacquer coating is used. Self-inclosing, aqueous bake lacquer, which contains, as a binder vehicle, a dispersion of aqueous polyurethane resin based on a polyurethane resin having a number average molecular weight (Mn) of 2500 to 120,000, a content from 10 to 400 mmoles of hydroxyl groups and / or R'O side and / or terminals bonded to silicon, where R '= C to C * alkyl or C (0) R "', and R '" = alkyl of C to CÍO, per 100 g of solid resin, a hydroxyl number from 0 to 150, where the hydroxyl groups bound to silicon are not included in the calculation of OH number, and a content of ionic groups, groups convertible to group β Ionic and / or hydrophilic groups of 5 to 200 mFqu per 100 g of solid resin. GD / mvs * crm *