WO2006094849A1

WO2006094849A1 - Aqueous coating substance compositions for decorative paint effects

Info

Publication number: WO2006094849A1
Application number: PCT/EP2006/050230
Authority: WO
Inventors: Patrick GLÖCKNER; Andreas Wenning
Original assignee: Degussa Gmbh
Priority date: 2005-03-10
Filing date: 2006-01-16
Publication date: 2006-09-14
Also published as: CN1942543A; DE102005010964A1

Abstract

The invention relates to aqueous coating substance compositions for decorative paint effects, consisting of at least one binding agent, one modified ketone/aldehyde resin, one pigment creating an effect and, optionally, auxiliary agents and additional substances.

Description

Aqueous coating materials composition for effect varnishes

The invention relates to aqueous coating material compositions for effect paints consisting of at least one binder, a modified ketone / aldehyde resin, an effect-imparting pigment and optionally auxiliaries and additives.

The coating compositions are used as effect coatings and dyes, such as As metallic, interference or pearlescent basecoats, for the coating of articles from z. As metals and plastics, wherein the coating is largely free of formaldehyde. The coating compositions are suitable for all customary application methods that are used in modern metal and plastic coating and the printing ink industry, such. As the spray application, the electrostatic spray application and printing by means of various printing processes. The coating compositions are characterized by a particularly high rate of drying and excellent optical properties.

Articles made of metals and plastics are usually provided with an organic coating (see "Römpp Lexikon, paints and printing inks, publisher Dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998"), so - depending on the application - on the one hand to protect the material On the other hand, the organic coatings assume decorative functions, and in modern consumer and consumer goods, decorative aspects are becoming increasingly important articles coated with effect varnishes such as metallic and / or pearlescent varnishes has been steadily increasing in recent years In addition to classical applications (eg automobiles), consumer goods and consumables are also becoming of lesser value with such coatings Examples are housings of mobile phones or notebooks. In printing inks are increasingly effect pigments z. B. used in advertising brochures.

Coating materials which contain metal, interference and / or pearlescent effect pigments are, according to "Römpp Lexikon, Paints and Printing Inks, publisher Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998. "They are used as single or double-coat paints in many other applications in automotive and industrial coating and are already characterized by a more or less strong metal or pearlescent effect due to the effect pigment content for the achievement of an optimal or desired hue or brightness flop, the orientation of the effect pigments is influenced by the application technique (eg dry / wet spraying) and by the fixation of the pigments after or during the evaporation of the volatile ingredients.

After the application of the coating materials, rapid drying is desirable in order to ensure rapid further processing and to avoid defects caused by, for example, As soiling such as dust and dirt, etc., to avoid. Especially with effect paints, it is necessary that during the evaporation of the volatile constituents a misorientation of the effect pigments is prevented. For this reason, rheology-influencing additives are often added to aqueous coatings.

Hard resins based on ketones and aldehydes are known to increase the hardness of coating materials.

Water-dispersible condensation products of ketones and aldehydes or their derivatives or reaction products which may contain such products are described in EP 0 617 103 A1, EP 0838485, EP 0838486 (DE 19643704), DE 25 42 090, DE-OS 31 44 673 and DE-OS 3406474 (EP 0154835).

In DE-OS 25 42 090 sulfonic acid carrying water-soluble compounds are described, which are available deviating from the erfindungsgenräßen method in a common condensation reaction of cycloalkanone, formaldehyde and alkali metal bisulfite.

In DE-OS 31 44 673 water-soluble condensation products are listed, which are also obtained by joint reaction of ketones, aldehydes and acid groups introducing compounds. Examples of the latter are sulfites, amidosulfonic acid, aminoacetic acid and phosphorous acid salts. According to DE-OS 25 42 090 and DE-OS 31 44 673, products containing electrolyte (eg Na ions) are obtained. However, such resins, among other things, deteriorate the water resistance of coating systems.

EP 0 617 103 A1 describes the reaction of polyisocyanates (a) and dihydroxyl compounds (b) having a molecular weight of 500 to 5,000 which do not convert groups which can be converted into ionic groups (for example carboxylic acid groups), but other functional groups such as or ether groups (see page 3, lines 17-21). The polyurethane thus obtained is still with a compound (c) which contains in addition to NCO-reactive groups nor a überfuhrbare group in an ionic group, and optionally with diols or polyols (d) having a molecular weight of 60 to 500, which no further functional Wear groups (see page 4, lines 5 to 15), implemented. Subsequently, this reaction product is reacted with a condensation resin and transferred to the aqueous phase.

DE 3406474 (EP 0154835) describes aqueous dispersions of ketone resins or ketone / aldehyde resins using organic protective colloids. The disadvantage that protective colloids remain in the subsequent coating and can adversely affect properties such as resistance to water and moisture, prevents their use in high-quality coating compositions.

EP 0838485 describes esterified products. It is known that ester groups hydrolyze, whereby polymer degradation takes place and the storage stability is adversely affected. In addition, a reaction or incompatibility with pigments can be caused by freely accessible acid groups.

EP 0838486 describes aqueous resin dispersions obtainable by reaction or proportionate reaction of

I. hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and

II. At least one hydrophilic modified isocyanate and / or polyisocyanate with at least one free NCO group obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds which have at least one isocyanate-reactive function in addition to the hydrophilic or potentially hydrophilic group and which have a hydrogen active according to the Zerewitinoff test, and at least one hydrophilic group and / or a potentially hydrophilic group, and then mixing the neutralized resin with water.

The object of the present invention was to find aqueous coating compositions for effect paints and printing inks, wherein the coating should be largely free of formaldehyde. The coating compositions should have a high drying rate and have a particularly positive influence on the effect formation.

The object underlying the invention has surprisingly been achieved by the use of special coating compositions, which are described in more detail below.

The invention relates to aqueous coating compositions for the effect coating of articles, substantially containing A) 20 to 94.5 wt .-% of at least one aqueous binder, and B) 5 to 79.5 wt .-% of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / aldehyde resin, and C) 0.5 to 25 wt .-% of at least one effect pigment, and D) 0 to 74.5 wt .-% of at least one additive, wherein the sum of the weights of Component A) to D) is 100 wt .-%.

It has been found that the combination of the below-described coating composition compositions of components A) to D) all required Fulfill criteria.

Component A)

The aqueous binders A) essential to the invention are used in amounts of from 20 to 94.5% by weight, preferably from 30 to 79.5% by weight.

Preference is given to aqueous binders from the group of polyurethanes, polyacrylates, polyethers, polyesters, alkyd resins, cellulose ethers, derivatives of cellulose, polyvinyl alcohols and derivatives, rubbers, maleate resins, phenol / urea-aldehyde resins, aminoplasts (for example melamine, benzoguanamine resins ), Epoxy acrylates, epoxy resins, silicic acid esters and alkali metal silicates (eg waterglass) and / or silicone resins. The aqueous binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

Component B) The essential component B) is used in amounts of from 5 to 79.5% by weight, preferably from 10 to 60% by weight.

As component B) are aqueous resin dispersions obtainable by reaction or proportionate reaction of

I. hydroxy-containing ketone / aldehyde resins or their hydrogenated derivatives and

II. At least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one

Isocyanate and / or polyisocyanate with compounds which in addition to the hydrophilic or potentially hydrophilic group have at least one isocyanate-reactive function, and subsequent mixing of the optionally neutralized resin with water.

Suitable ketones for the preparation of the ketone / aldehyde resins (component I) are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2, 4,4-

Trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, mention may be made of 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

It is in principle also possible, although less preferred, to use ketones which have other functional groups, such as. B. amino and / or acid groups grout.

In general, however, all in the literature for ketone and ketone / aldehyde resin syntheses called suitable ketones, usually all C-H-acidic ketones, can be used. Preferred are ketone / aldehyde resins based on acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture.

As aldehyde component of the ketone / aldehyde resins (component I.) are in principle unsubstituted or branched aldehydes, such as. As formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone / aldehyde resin syntheses can be used. Preferably, however, formaldehyde is used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.

As starting compounds for the ketone / aldehyde resins of component I, particular preference is given to using acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and also heptanone alone or in a mixture and formaldehyde.

The resins of ketone and aldehyde can also be hydrogenated in the presence of a suitable catalyst with hydrogen at pressures of up to 300 bar. This is part of the Carbonyl groups of the ketone / aldehyde resin converted into secondary hydroxyl groups. For resins of aldehydes and ketones, in addition to the Carbonylgruppierung on other hydrogenatable functions such. B. grout aromatic structures, these other structures can be converted by suitable hydrogenation. In the case of z. B. aromatic structures are obtained cycloaliphatic structures.

The possibly necessary hydrophilic modification takes place for. Example by reacting the resin I with a component IL, consisting of at least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds in addition to the hydrophilic or potentially hydrophilic group - ie those groups which become hydrophilic only after neutralization - have at least one isocyanate-reactive function such as. B. hydroxy or amino groups.

Examples of such compounds for the hydrophilic modification of (poly) isocyanates are amino acids, hydroxysulfonic acids, aminosulfonic acids and hydroxycarboxylic acids. Preference is given to using dimethylolpropionic acid or derivatives thereof. The hydrophilic modification can also be carried out with non-ionic groups (eg with polyethers) or already neutralized compounds.

Hydroxycarboxylic acids, in particular dimethylolpropionic acid, are therefore particularly preferred because they are neutralized with volatile bases, such as. As amines, show strong hydrophilic effect, after evaporation of the volatile base, however, this effect decreases greatly. Coatings therefore do not lose by z. B. Moisture their protective function, as a swelling does not take place.

The dimethylolpropionic acid is also particularly preferred since it is capable of hydrophilically modifying (potentially) two hydrophobic polyisocyanates via its two hydroxyl groups.

Suitable polyisocyanates for the preparation of II. Are preferably di- to tetrafunctional Polyisocyanates. Examples of these are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexanediisocyanate, phenylene diisocyanate, toluene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane isocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonane triisocyanate, such as 4-isocyanatomethyl 1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi and triisocyanates, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI), isocyanatomethylmethylcyclohexyl isocyanate, 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4- Bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI) all in or in mixture.

Another preferred class of polyisocyanates are the compounds prepared by di- or trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates with more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or H. ₁₂ MDI with polyhydric alcohols (eg glycerol, trimethylolpropane,

Pentaerythritol) or polyvalent polyamines or the triisocyanurates obtainable by trimerization of the simple diisocyanates such as IPDI, HDI and H ₁₂ MDI.

Particular preference is given to a hydrophilically modified polyisocyanate (II) of dimethylolpropionic acid or derivatives thereof and IPDI and / or TMDI and / or H ₁₂ MDI and / or HDI in a molar ratio of 1: 2.

The preparation of component B) is carried out in the melt or in solution of a suitable organic solvent, which - if desired - can be separated by distillation after preparation.

Preferred solids contents in the case of a reaction in solution are 30 to 95 wt .-%, particularly preferably 60 to 80 wt .-%. Suitable auxiliary solvents are low-boiling inert solvents which do not form a miscibility gap with water over wide ranges, have a boiling point at atmospheric pressure below 100 ° C. and, if desired, can be easily distilled to a residual content of less than 2% by weight and in particular of less than 0.5% by weight, based on the final dispersion or aqueous solution, and that it can be reused. Suitable solvents of this type are for. As acetone, methyl ethyl ketone or tetrahydro-uranium. Basically suitable are also higher-boiling solvents such. As n-butyl glycol, di-n-butyl glycol and N-methylpyrrolidone, which then remain in the dispersion.

However, one advantage of component B) lies precisely in the fact that it is possible completely to dispense with organic solvents in the finished aqueous resin dispersion and still obtain solids-rich, stable dispersions.

The reaction of I and II is preferably allowed to proceed so far that a residual NCO content of 1% NCO (determined according to DIN 53185) is exceeded, and particularly preferably progresses so far that the residual NCO content of the product of I and II ranges from 0.1 to 0.5% NCO. In the reaction of I and II unreacted remaining NCO functions can be, according to the prior art, either chain extension reactions, eg. For example, by adding polyamines or water use, or if necessary, a chain termination by addition to NCO groups monofunctional compounds (eg., Monoalcohols, monoamines) initiate.

In the case of potentially hydrophilic groups, the products according to the invention can be mixed with a suitable neutralizing agent, which then gives water-dilutable, water-dispersible or water-soluble products.

The neutralization of the potentially hydrophilic groups of the resins according to the invention can be carried out with inorganic and / or organic bases, such as. As ammonia or organic amines. Preferably used are primary, secondary and / or tertiary amines, such as. For example, ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexalamine, benzylamine, morpholine, piperidine and triethanolamine. Particular preference is given to volatile, tertiary amines, in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, triethylamine, tripropylamine and tributylamine in the case of anionic potential groups. So-called cationic potential ionic groups can be neutralized with inorganic and / or organic acids, such as. As acetic acid, formic acid, phosphoric acid, hydrochloric acid, etc.

The degree of neutralization is preferably 50 to 130% of the neutralization amount necessary for stoichiometric neutralization.

The neutralized hydrophilic resin or the resin solution is either passed into water or it is preferably mixed with water while stirring. Before adding water can

Reaction product of I and II optionally with other non-hydrophilic set

Resins or other components combined and then dispersed together.

By this measure, a technically advantageous high solids content of

Achieve dispersions of more than 45% by weight. Basically, the solids content ranges between 20 and 70 wt .-%, preferably between 25 and 60 wt .-%.

After dispersing, the organic auxiliary solvent can preferably be removed in vacuo and, if appropriate, worked up again.

The component B) can be used as a binder component but also as Anreibeharz for the component C).

Component C)

The invention essential component C) is used in amounts of 0.5 to 25 wt .-%, preferably from 2 to 20 wt .-%.

Suitable as component C) are, for. B. metallic effect pigments such. As aluminum, copper, copper / zinc and zinc pigments, fire-colored bronzes, iron oxide-aluminum pigments, interference or pearlescent effect pigments such. Example, metal oxide mica pigments, bismuth oxychloride, basic lead carbonate, fish silver or micronized titanium dioxide, platelet-shaped graphite, platelet iron oxide, multi-layer effect pigments from PVD films or by the CVD method produced (Chemical Vapor Deposition) and Liquid crystal (polymer) pigments.

A comprehensive list can be found in "Römpp Lexikon, paints and inks, publisher dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 "and in" BASF Manual Lackiertechnik, Artur Goldschmidt, Hans -Joachim Streitberger, Vincentz Verlag, Hannover, 2002 ".

Component D)

Component D) is used in amounts of from 0 to 74.5% by weight, preferably from 5 to 60% by weight.

As component D) are suitable auxiliaries and additives such as inhibitors, organic solvents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers, plasticizers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, colorants such as dyes and pigments, matting agents, fire protection equipment, internal release agents, fillers; Isocyanate hardener and / or propellant.

Preparation of the Compound Compositions from Components A) to D):

The preparation of the coating compositions is carried out by intensive mixing of the components at temperatures of 20 to 80 ° C ("Textbook of Lacktechnologie", Th.

Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, page

229 ff.).

Non-liquid components may be first dissolved in suitable solvents or water prior to mixing, then the remaining components are added with stirring. In the case of z. As pigments and / or fillers is a

Dispersing. However, the effect pigments are not dispersed, but only stirred. The formaldehyde content of the coating compositions is below 100 ppm, preferably below 50 ppm and more preferably below 10 ppm.

The claimed, aqueous coating compositions are for painting and / or printing of objects made of different materials, such as. As metals, plastics, wood, paper, inorganic materials such. As concrete, stone or ceramic, etc. suitable. They have a high drying speed and excellent effect formation. The dried, cured or crosslinked films have good adhesion properties on underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.

The claimed aqueous coating compositions have a satisfactory flow on the substrates used and are free from surface defects, such as craters and wetting disorders.

The claimed aqueous coating compositions have a solids content of from 10% to 80%, preferably from 20% to 60%.

The coating compositions according to the invention are used as single-coat paints or as basecoats for multicoat paint systems and as printing inks.

The following examples are intended to further illustrate the invention but not to limit its scope:

Examples

Preparation of component B)

1. Preparation of the adduct 444 g are added with stirring to a mixture of 134 g of dimethylolpropionic acid, 380 g of acetone and 6 g of a 10% strength by weight solution of dibutyltin dilaurate in acetone Isophorone diisocyanate added so that the exothermic reaction remains well manageable. It is heated to 60 ° C and held this temperature up to an NCO number of 9.2%.

To the cooled to room temperature solution is added with stirring 2300 g of a 55% by weight acetone solution of hydrogenated acetophenone / formaldehyde resin (synthetic resin SK Degussa AG) and 12 g of a 10 wt .-% acetone DBTL solution and heated to the reflux temperature of about 60 ° C. The mixture is allowed to stir at this temperature until the NCO number of the solution has fallen below 0.1% NCO.

Transfer to the aqueous phase

Alternative A:

The solution of the hydrophilically modified resin prepared under 1) is neutralized at room temperature with stirring by adding 89 g of dimethylaminoethanol and the solution is dispersed by adding 4200 g of demineralized water with stirring. The auxiliary solvent acetone and water proportionally are removed in vacuo to give a storage-stable, finely divided, slightly opalescent resin dispersion having a solids content of about 33% by weight.

Alternative B: The solution prepared under 1) is added with stirring 3300 g of a 55 wt .-% strength acetone solution of a hydrogenated acetophenone / formaldehyde resin (synthetic resin SK Degussa AG), neutralized at room temperature with stirring with 89 g of dimethylaminoethanol and dispersed Solution by adding 4400 g of demineralized water with stirring. The auxiliary solvent acetone and water as a proportion are removed in vacuo and obtain a storage-stable whitish dispersion having a solids content of about 50 wt .-%.

Properties of the dispersions Storage stability

The dispersions A and B according to point 2) were examined for storage stability with regard to changes in the pH, the viscosity and the visual appearance.

* Rotational viscometer; D: 100 to 900 s ^" Example of a coating material composition:

Demineralised water = fully desalinated water

Pos. 2 was added to Pos. 3 slowly and with constant stirring. The viscosity increased slightly. After combining, stirring was continued for a further 15 minutes. The viscosity was adjusted with deionized water to 30 to 40 s (Ford Cup 4, 23 ° C). The formaldehyde content of the coating materials is less than 1 ppm.

The paint was applied to aluminum bonding panels by means of spraying in a dry layer thickness of about 14 to 17 microns and flashed for 8 min at room temperature. So then a commercial lK-PUR clearcoat was applied and cured for 25 min at 140 ° C.

Compared to the comparison, the coating of the example is characterized by a significantly better orientation of the effect pigments and an excellent flop effect.

Claims

claims:

1. Aqueous coating composition for the effect coating of

Essentially containing A) 20 to 94.5% by weight of at least one aqueous binder, and B) 5 to 79.5% by weight of a hydrophilized ketone / aldehyde resin and / or a hydrophilized hydrogenated ketone / aldehyde resin , and C) 0.5 to 25 wt .-% of at least one effect pigment, and

D) O to 74.5 wt .-% of at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%.

2. Aqueous coating composition according to claim 1, characterized in that the solids content of the coating compositions is between 10 wt .-% to 80 wt .-%, preferably between 20 wt .-% and 60 wt .-%, the formaldehyde content of the coating compositions below 100 ppm, preferably below 50 ppm and more preferably below 10 ppm and the content of organic

Solvent is below 20 wt .-%, preferably below 10 wt .-%, more preferably below 2 wt .-%.

3. Aqueous coating composition according to claims 1 and 2, characterized in that as component A) aqueous binders from the group polyurethanes, polyacrylates, polyethers, polyesters, alkyd resins, cellulose ethers, derivatives of cellulose, polyvinyl alcohols and derivatives, rubbers, maleate resins, phenolic Urea / aldehyde resins, aminoplasts (eg, melamine, benzoguanamine resins), epoxyacrylates, epoxy resins, silicic acid esters, and alkali silicates (eg, water glass) and / or silicone resins may be used alone or in admixture.

4. Aqueous coating composition according to claim 3, characterized in that the component A) preferred, aqueous binder foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

5. Aqueous coating material composition according to one of the preceding claims, characterized in that as component B) aqueous resin dispersions are used, obtainable by reaction or proportionate reaction of I. hydroxy-containing ketone / aldehyde or their hydrogenated derivatives and II. At least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group obtainable by reacting at least one

6. Aqueous coating composition according to claim 5, characterized in that as component I for the preparation of component B) resins are used which contain C-H-acidic ketones.

7. Aqueous coating composition according to claim 6, characterized in that CH-acidic ketones selected from acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4 , 4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in each case

Mixture be used.

8. Aqueous coating composition according to claim 7, characterized in that as alkyl-substituted cyclohexanones 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3.3 , 5-trimethylcyclohexanone alone or in mixture.

9. Aqueous coating material composition according to claim 5, characterized in that are used as component I for the preparation of component B) resins which

Containing aldehydes.

10. Aqueous coating material composition according to one of the preceding claims, characterized in that as the aldehyde component for the preparation of component I of component B)

Formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde, dodecanal are used alone or in mixtures.

11. Aqueous coating material composition according to any one of the preceding claims, characterized in that hydrogenation products of the resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone alone or in mixture and formaldehyde are used as component I. ,

12. Aqueous coating composition according to any one of the preceding claims, characterized in that the component II. Of component B) is prepared using tert.

Amino alcohols, aminocarboxylic acids, hydroxysulfonic acids, aminosulfonic acids or / and hydroxycarboxylic acids.

13. An aqueous coating material composition according to one of the preceding claims, characterized in that component II. of component B) is prepared using

Dimethylolpropionic.

14. Aqueous coating material composition according to one of the preceding claims, characterized in that component II. Of component B) is already neutralized before reaction with component I.

15. Aqueous coating composition according to one of the preceding claims, characterized in that for the preparation of II. Of component B) di- to tetrafunctional polyisocyanates are used.

16. Aqueous coating material composition according to any one of the preceding claims, characterized in that for the preparation of II. Of component B) polyisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups or mixtures of these are used.

17. Aqueous coating composition according to any one of the preceding claims, characterized in that 1-isocyanato-3.3.S-trimethyl-S-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,6-diisocyanatohexane (HDI), bis (4- Isocyanatohexyl) -methane (H ₁₂ MDI) can be used alone or in a mixture.

18. Aqueous coating material composition according to any one of the preceding claims, characterized in that for the preparation of II. The component B) polyisocyanates with biuret, uretdione or isocyanurate structure are used.

19. Aqueous coating material composition according to any one of the preceding claims, characterized in that for the preparation of II. Component B) polyisocyanates from the reaction of polyhydric alcohols and / or amines are used with monomeric isocyanates.

20. Aqueous coating material composition according to one of the preceding claims, characterized in that for the preparation of II. The component B) dimethylolpropionic acid and isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6-diisocyanatohexane and / or bis (4-isocyanatohexyl) methane in a molar ratio of 1: 2 become.

21. Aqueous coating composition according to any one of the preceding claims, characterized in that the reaction of I. and II. Of component B) and the subsequent

Dispersion in bulk or in the presence of a co-solvent.

22. Aqueous coating composition according to the preceding claim, characterized in that the auxiliary solvent used has a boiling point below 100 ° C at 1013 hPa.

23. Aqueous coating composition according to the preceding claim, characterized in that the auxiliary solvent used acetone and / or methyl ethyl ketone and / or

Tetrahydroiuran is.

24. Aqueous coating material composition according to one of the preceding claims, characterized in that the neutralization of component B) takes place with inorganic or organic bases.

25. Aqueous coating composition according to the preceding claim, characterized in that are used for neutralization dimethylethanolamine and / or diethylethanolamine or / and 2-dimethylamino-2-methyl-l-propanol.

Aqueous composition of matter according to any one of the preceding claims, characterized in that for neutralization 50 to 130% of the amount of neutralization necessary for stoichiometric neutralization is used.

27. An aqueous coating material composition according to any one of the preceding claims, characterized in that one or more non-water-soluble or water-dilutable components are added before addition of water.

28. Aqueous coating composition according to any one of the preceding claims, characterized in that are used as component C) effect pigments.

29. Aqueous coating material composition according to one of the preceding claims, characterized in that as component C) effect pigments selected from the group of metal, pearlescent and / or interference effect pigments are used.

30. Aqueous coating composition according to any one of the preceding claims, characterized in that as component C) aluminum, copper, copper / zinc and zinc pigments, fire-colored bronzes, iron oxide-aluminum pigments, metal oxide mica, metal oxide-alumina , Metal oxide-silica, metal oxide-iron oxide pigments, bismuth oxychloride, basic lead carbonate, fish silver or micronized titanium dioxide, platelet-shaped graphite, bubble iron oxide, multilayer effect pigments PVD films or produced by the CVD method (Chemical Vapor Deposition) and liquid crystal (polymer) pigments can be used.

31. Aqueous coating composition according to any one of the preceding claims, characterized in that are used as component D) auxiliaries and additives.

32. Aqueous coating material composition according to one of the preceding claims, characterized in that as component D) auxiliaries and additives are used alone or in mixture, selected from the group of inhibitors, organic solvents, surface-active substances, oxygen and / or radical scavengers, catalysts , Light stabilizers, color whiteners, photosensitizers and initiators, additives for influencing theological properties such. Thixotropic and / or thickening agents, leveling agents, skin preventatives, defoamers, antistatic agents,

Plasticizers, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, colorants such as dyes and pigments, matting agents, fire protection equipment, internal release agents, fillers, Isocyanathärter and / or blowing agents.

33. A process for the preparation of aqueous coating compositions comprising substantially

A) 20 to 94.5% by weight of at least one aqueous binder, and B) 5 to 79.5% by weight of a hydrophilized ketone / aldehyde resin and / or a hydrophilized hydrogenated ketone / aldehyde resin, and

C) from 0.5 to 25% by weight of at least one effect pigment, and D) from 0 to 74.5% by weight of at least one additive, where the sum of the weights of components A) to D) is 100% by weight. is, by intensive mixing by stirring and / or dispersing the components at temperatures of +20 to +80 ° C.

34. Use of the aqueous coating compositions according to at least one of the preceding claims for the coating or printing of articles.

35. Use of the aqueous coating compositions according to at least one of the preceding claims as single-coat paints or as basecoats for multicoat paint systems and as printing inks.

36. Use of the aqueous coating compositions according to at least one of the preceding claims for the coating or printing of objects made of metals, plastics, wood, paper, glass and / or mineral substrates.

37. Coated articles of metals, plastics, wood, paper, glass and / or mineral substrates, produced and / or finished with a coating material composition according to at least one of the preceding claims.