WO2006094850A1

WO2006094850A1 - Aqueous coating substance compositions having an improved resistance to stoning

Info

Publication number: WO2006094850A1
Application number: PCT/EP2006/050231
Authority: WO
Inventors: Patrick GLÖCKNER; Andreas Wenning; Werner Andrejewski
Original assignee: Degussa Gmbh
Priority date: 2005-03-10
Filing date: 2006-01-16
Publication date: 2006-09-14
Also published as: WO2006094850A8; CN1942544A; DE102005010947A1

Abstract

The invention relates to aqueous substance coating compositions having an improved resistance to stoning, made of at least one binding agent, one modified ketone/aldehyde resin and, optionally, auxiliary agents and additional substances for coating metals and plastics.

Description

Aqueous coating compositions with improved stone chip protection

The invention relates to aqueous coating compositions with improved stone chip protection effect consisting of at least one binder, a modified ketone / aldehyde resin and optionally auxiliaries and additives for the coating of metals and plastics.

The coating compositions are used in particular for the

Improvement of the stone impact protection effect on plastics and metals, wherein the coating is largely free from formaldehyde. Suitable are the

Coating composition for all common application methods that are used in modern metal and plastic coating, such. B. the spray application and the electrostatic spray application.

The coating compositions are characterized by a particularly high rate of drying and by a particularly high hardness with very good elasticity and adhesion properties. Particularly noteworthy is the excellent protective effect against mechanical damage due to intensive and short-term stress as it is mainly due to z. B. Rockfall can be caused.

Articles made of metal or plastic for high-quality applications are now usually provided with an organic coating (see "Römpp Lexikon, paints and printing inks, publisher Dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998"), depending on the field of application - on the one hand protect the substrate (eg protection of the object against aging, corrosion, weathering, mechanical destruction, contamination, etc.) On the other hand, the organic coatings take on decorative functions.

For economic reasons, a rapid drying of the coating material is desirable in order to ensure rapid further processing and defects caused by z. B. soiling such as dust, dirt, etc., to avoid.

To a sufficiently high level of protection against z. B. to ensure mechanical stress, As high a hardness of the coating is desired. However, elasticity decreases in conventional coatings with increasing hardness. However, good elastic properties are also required.

Very good adhesion properties are indispensable for the permanent protection of the substrate. Especially with metal substrates, a very good adhesion is required, so that a high corrosion protection effect is achieved. For use in multicoat paint systems, excellent intercoat adhesion is of great importance. In addition, many durable goods are subject to constant mechanical stress, so that high demands are placed on a coating with regard to abrasion resistance and resistance to external influences.

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 sulfo groups carrying water-soluble compounds are described, which are available deviating from the process of the invention 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 deteriorate, inter alia, 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 and containing no groups which can be converted into ionic groups (for example carboxylic acid groups), but other functional groups such as ester or ether groups (see page 3, lines 17 to 21), contain. 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. Then this will be

Reaction product 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-grade 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 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 at least one isocyanate-reactive Have function and have one according to the Zerewitinoff test active hydrogen, as well as 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 which give coatings which are characterized by very good adhesion properties and stone impact resistance. The coatings should be largely free of formaldehyde. Also, the coating materials should have a high drying speed.

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, in particular for improving the stone impact resistance on different substrate substrates, substantially containing

A) 20 to 98 wt .-% of at least one aqueous binder, and

B) 2 to 80 wt .-% of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / aldehyde resin, and

C) 0 to 75 wt .-% of at least one additive, wherein the sum of the weights of component A) to C) is 100 wt .-%.

It has been found that the combination of the coating material compositions described below from components A) to C) fulfill all the required criteria.

Component A) The aqueous binders A) essential to the invention are used in amounts of from 20 to 98% by weight, preferably from 30 to 80% 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 (eg.

Melamine, benzoguanamine resins), epoxy acrylates, epoxy resins, silicic acid esters and

Alkali silicates (eg waterglass) and / or silicone resins used. The aqueous binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

Component B)

The component B) essential to the invention is used in amounts of from 2 to 80% by weight, preferably from 4 to 60% by weight.

Suitable as component B) are aqueous resin dispersions obtainable by reaction or proportionate reaction of I. hydroxyl-containing ketone / 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 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 which contain a total of 1 to Have 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones there can be mentioned 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.

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, methyldiethylcyclohexane diisocyanate, 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 diisocyanate, 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 (isocyanato-methyl) bicyclo [2.2.1] heptane

(NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanato-methyl) cyclohexane (1,4-H ₆ -XDI) alone or in a 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 (for example glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines or the triisocyanurates obtainable by trimerization of the simple diisocyanates, such as, for example, 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 are therefore easily distilled to a residual content of less than 2% by weight and, if desired, by distillation less than 0.5% by weight, based on the finished 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. In principle, 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 progress so far that the residual NCO content of the product I and II im

Range 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 too

Chain extension reactions, e.g. B. by adding polyamines or water, or possibly a chain termination by addition to NCO groups monofunctional

Initiate compounds (eg monoalcohols, monoamines).

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, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine. Particularly preferred are volatile, tertiary Amines, in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-l-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 addition of water, the reaction product of I and II may optionally be combined with other non-hydrophilic resins or other components and then dispersed together. By this measure, a technically advantageous high solids content of the dispersions of over 45 wt .-% can be achieved. 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.

Component C)

Component C) is used in amounts of from 0 to 75% by weight, preferably from 5 to 60% by weight.

As component C) 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, antistatic agents, plasticizers, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, Matting agents, fire retardants, internal release agents, fillers, isocyanate hardeners and / or blowing agents.

Preparation of the Coating Compositions from Components A) to C): The coating compositions are prepared by intensive mixing of the components at temperatures of from 20 to 80 ° C. ("Lehrbuch der Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed V. Zorll, Vincentz Verlag, Hannover, 1998, page 229 ff.) If necessary, non-liquid components are first dissolved in suitable solvents or water before mixing, then the remaining components are added with stirring. As pigments and / or fillers is carried out a dispersion.

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 have a solids content of from 15% to 80%, preferably from 20% to 60%.

The claimed, aqueous coating compositions are particularly suitable for the coating of objects made of metals and plastics. They have a high rate of drying and thus very high blocking resistance.

The dried, cured or crosslinked films have a high hardness with good elasticity and adhesion properties, which is expressed in good to very good values in the scratch adhesion, cross-cut test, pendulum or Buchholzhärte and the Erichsentiefung.

Particularly noteworthy is the excellent protective effect of the claimed, aqueous coating compositions against mechanical damage due to intensive and short-term stress, as described above all by z. B. Rockfall can be caused.

The claimed, aqueous coating compositions have a perfect course on the substrates used and are free from Surface disorders, such as craters and wetting disorders.

The coating compositions of the invention are used as fillers, paints such. As primers, primers, fillers, basecovers, topcoats and clearcoats used for metals and / or plastic substrates. They are particularly suitable for the (electrostatic) spray application.

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

Restrict 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.

2. Transfer to the aqueous phase

Alternative A:

The prepared under 1) solution of the hydrophilic modified resin is neutralized at room temperature with stirring by the addition of 89 g of dimethylaminoethanol. Then is dispersed by adding 4200 g of deionized 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 by adding the solution of 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.

Property A B pH Initial value 8.9 8.8 at 6 months 8.9 8.8

Viscosity 23 ° C * Initial value 375 - 714 mPa s 69 - 138 mPa s after 6 months 335 - 563 mPa s 67 - 135 mPa s

Appearance slightly opalescent white after 6 months slightly opalescent white

* Rotational viscometer; D: 100 to 900 s ^"1

Example of a coating composition (primcr):

VE-H ₂ O = fully demineralized water

Adjusting the pH with DMEA / deionised water to a pH of about 8.2 to 8.8; Adjust the viscosity with demineralised water (Ford Cup 4, 23 ° C) to 40 - 45 s. The formaldehyde content of both coating materials is less than 1 ppm.

Test panels: Coating structure (spray application) on phosphated steel sheet: cathodic dip coating, primer according to Example, metallic basecoat, clearcoat Drying conditions: Flash off time approx. 10 min, then 20 min 160 ° C

By adding the invention essential component B) adhesion, intercoat adhesion, gloss and stone chip resistance of the coatings are improved.

Claims

claims:

1. Aqueous coating compositions having an improved anticaking effect substantially comprising A) from 20 to 95% by weight of at least one aqueous binder, and B) from 5 to 80% by weight of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / Aldehyde resin, and C) 0 to 75 wt .-% of at least one additive, wherein the sum of the weights of component A) to C) is 100 wt .-%.

2. Aqueous coating composition according to claim 1, characterized in that the solids content of the coating compositions is between 15 wt .-% to 80 wt .-%, preferably between 20 wt .-% and 60 wt .-%, the formaldehyde content of the coating compositions below 100th ppm, preferably below 50 ppm and more preferably below 10 ppm and the content of organic solvents is below 20% by weight, preferably below 10% by weight, particularly preferably below 2% by weight.

3. Aqueous coating material compositions according to claims 1 and 2, characterized in that as component A) 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 (e.g., melamine, benzoguanamine resins), epoxy resins, silicic acid esters and alkali silicates (e.g., water glass), silicone resins, fluorine-containing polymers may be used alone or in admixture ,

4. Aqueous coating material compositions according to claim 3, characterized the aqueous binders which are preferred as component A) are foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

5. Aqueous coating material compositions according to any one of the preceding claims, characterized in that as component B) aqueous resin dispersions are used, obtainable by

Implementation or proportionate implementation of

I. hydroxyl-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 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.

6. Aqueous coating compositions 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 material compositions according to claim 6, characterized in that C-H-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, used singly or in admixture.

8. Aqueous coating material compositions 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 a mixture be used.

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

10. Aqueous coating compositions according to any one of the preceding claims, characterized in that as aldehyde component for the preparation of component I of component B) formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde,

Dodecanal be used alone or in mixtures.

11. Aqueous coating compositions 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 compositions 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. Aqueous coating material compositions according to one of the preceding claims, characterized in that Component II. of component B) is prepared using dimethylolpropionic acid.

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

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

16. Aqueous coating compositions 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 thereof are used.

17. Aqueous coating compositions 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 compositions 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 compositions according to 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 compositions according to any one of the preceding claims, characterized in that for the preparation of II. Of 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 material compositions according to any one of the preceding claims, characterized in that the reaction of I. and II. The component B) and the subsequent dispersion carried out in bulk or in the presence of an auxiliary solvent.

22. Aqueous coating compositions 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 compositions according to the preceding claim, characterized in that the auxiliary solvent used is acetone or / and methyl ethyl ketone or / and tetrahydro-uranium.

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

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

26. Aqueous coating compositions according to any one of the preceding claims, characterized in that for neutralization 50 to 130% of the neutralization amount, which is necessary for a stoichiometric neutralization, is used.

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

28. Aqueous BescWeitungsstoffzusammensetzungen according to any one of the preceding claims, characterized in that as component C) auxiliaries and additives are used.

29. Aqueous coating compositions according to any one of the preceding claims, characterized in that as component C) 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 , Sunscreens, color-whiteners, photosensitizers and initiators, additives for influencing

Theological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers, antistatic agents, plasticizers, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers, Isocyanathärter and / or

Propellant.

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

A) from 23 to 95% by weight of at least one aqueous binder, and B) from 2 to 80% by weight of a hydrophilized ketone / aldehyde resin and / or a hydrophilized hydrogenated ketone / aldehyde resin, and

C) 0 to 75 wt .-% of at least one additive, wherein the sum of the weights of component A) to C) is 100 wt .-%, by intensive mixing by stirring and / or dispersing the components

Temperatures from +20 to +80 ° C.

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

32. Use of the aqueous coating compositions according to at least one of the preceding claims for the coating of objects made of metals and / or plastics.

33. Use of the aqueous coating compositions according to at least one of the preceding claims as primers for automotive coatings.

34. Coated articles of metal or plastic, manufactured and / or finished with a coating material composition according to at least one of the preceding claims.