WO2007062953A1

WO2007062953A1 - Aqueous resins

Info

Publication number: WO2007062953A1
Application number: PCT/EP2006/067967
Authority: WO
Inventors: Patrick GLÖCKNER; Lutz Mindach; Friedrich Georg Schmidt
Original assignee: Degussa Gmbh
Priority date: 2005-12-03
Filing date: 2006-10-31
Publication date: 2007-06-07
Also published as: CN1978482A; DE102005057853A1

Abstract

Aqueous resin dispersions obtainable by reacting or partially reacting A) hydroxy-containing ketone resins, ketone/aldehyde resins, urea/aldehyde resins or their hydrogenated conversion products and B) at least one aromatic, aliphatic and/or cycloaliphatic di- or polyisocyanate and at least one ionic liquid which has a function reactive toward isocyanate groups C) and additional functional groups and subsequent mixing of the resin with water, a process for their preparation and their use as a main component, base component or additive component in coating materials, ballpoint pen pastes, pigment pastes, printing inks and other inks, polishes, glazes, putties, cosmetic articles and/or sealants and insulating materials and also adhesives.

Description

Aqueous resins

The present invention relates to aqueous ketone, ketone / aldehyde or urea / aldehyde resin dispersions, to a process for their preparation and to the use as main component, base component or additional component in coating materials, ballpoint pen pastes, pigment pastes, printing inks and inks, polishes, glazes, laminations, Fillers, cosmetics and / or sealants and insulating materials and adhesives.

The condensation to ketone, ketone / aldehyde and urea / aldehyde resins is known (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH Weinheim 1993, Vol 23, pp. 99-105). Such resins are generally water-insoluble.

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. Such resins, however, deteriorate inter alia the corrosion protection of coating systems.

DE-OS 34 06 473 and DE-OS 34 06 474 and EP-AO 154 835 describe processes for the preparation of stable aqueous dispersions of urea / aldehyde resins or ketone / (aldehyde) resins, after which the resin melt or their highly concentrated solution in the presence of organic protective colloids optionally dispersed in water with the addition of emulsifiers. A disadvantage of this method is the fact that such organic protective colloids and emulsifiers, the application of the aqueous ketone / (aldehyde) - or Disturb urea / aldehyde resins in the coating sector. The hydrophilic protective colloids and optionally emulsifiers remain in the coating and make them sensitive to moisture. The coating swells when exposed to moisture, loses its hardness and loses its anti-corrosion effect.

Water-dispersible condensation products are described in EP 0 838 486 A1, EP 0 838 485 and EP 0 154 835. The targeted introduction of ionic liquids as further functionalization and for the conversion of organic resins into stable aqueous solutions, dilutions and dispersions is not the subject of these applications.

The object of the invention was to develop ketone, ketone / aldehyde or urea / aldehyde resin dispersions and a process for their preparation, which differs from the prior art by the use of novel emulsifiers. The aqueous resin dispersions should be stable to hydrolysis or storage and should not have the disadvantages described above. In particular, the moisture resistance of coating materials and adhesives containing the products of the invention should be high. In addition, the resins should be suitable for use in paints and adhesives.

The problem underlying the invention is surprisingly achieved according to the claims by hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives with (poly) isocyanates and so-called ionic liquids (hereinafter abbreviated to IL) implemented.

After addition of water, the ketone, ketone / aldehyde, urea / aldehyde resins of the invention thus modified and their hydrogenated secondary products give stable aqueous solutions, dilutions and dispersions, without requiring further neutralization.

The aqueous systems of the invention are compared to those of the prior Technology already known systems completely saponification-stable and contain no further interfering additives z. B. in the form of other emulsifiers, protective colloids or electrolytes.

Although the IL moieties remain in the coating, it was surprising that in contrast to known emulsifiers such as e.g. Polyethers no moisture-sensitive coatings were obtained, so that there is a good anti-corrosion effect.

The present invention relates to aqueous resin dispersions, and a process for their preparation obtainable by reaction or proportionate reaction of

A) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and

B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate and

C) at least one ionic liquid which has an isocyanate-reactive function and has additional functional groups,

and then mixing the resin with water.

It was particularly surprising that ILs, some of which alone had no water solubility, were rendered water-soluble, water-dilutable or water-dispersible by reaction according to the invention with components A) and B).

Suitable ketones for preparing the ketone-aldehyde resins and ketone resins (component A) all ketones, especially acetone, acetophenone are, Melhylelhylketonj _^ j ^^ j ^ ui ^ iK ^ U ^ ^ lKcix 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 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones there may be mentioned 4-tert.-amylcyclohexanone, 2-sec.-butylcyclohexanone, 2-tert.-butylcyclohexanone, 4-tert.-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

1 Deleted: general

In the omiteomeinoii, however, all the literature for ketone and ketone- ^v

Aldehyde resin syntheses as suitable called ketones, usually all C-H-acidic ketones are used. Preference is given to ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture and ketone resins based on cyclohexanone.

As aldehyde component of the ketone-aldehyde resins (component A) 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 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.

Particularly preferred starting compounds for component A) acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone are used alone or in mixture and formaldehyde.

Hydrogenated secondary products of the resins of ketone and aldehyde are also used as component A). The ketone-aldehyde resins described above are in the presence of a

Hydrogenated catalyst with hydrogen at pressures up to 300 bar. Here is the Carbonyl group of the ketone-aldehyde resin converted into a secondary hydroxy group. Depending on the reaction conditions, a part of the hydroxy groups can be split off, so that methylene groups result. To illustrate, the following scheme is used:

n = k + m

As component A), furthermore, urea-aldehyde resins are used using a urea of the general formula (i)

in which X is oxygen or sulfur, A is an alkylene radical and n is 0 to 3, with 1.9 (n + 1) to 2.2 (n + 1) mol of an aldehyde of the general formula (ii)

in which R 1 and R 2 are hydrocarbon radicals (for example alkyl, aryl and / or alkylaryl radicals) in each case having up to 20 carbon atoms and / or formaldehyde is used.

Suitable ureas of the general formula (i) with n = 0 are z. As urea and thiourea, with n = 1 methylene diurea, ethylene diurea, tetramethylene diurea and / or Hexamethylendiharnsto ff and mixtures thereof. Preference is given to urea.

Suitable aldehydes of the general formula (ii) are, for example, isobutyraldehyde, 2-methylpentanal, 2-ethylhexanal and 2-phenylpropanal and mixtures thereof. Isobutyraldehyde is preferred.

Formaldehyde may be in aqueous form, some or all of alcohols such. As methanol or ethanol may be used as paraformaldehyde and / or trioxane.

In general, all monomers described in the literature for the preparation of aldehyde-urea resins are suitable.

Typical methods of preparation and compositions are e.g. B. in DE 27 57 220, DE-OS 27 57 176 and EP 0 271 776 described.

Suitable as component B) are aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanates.

Examples of diisocyanates are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate,

Methyldiethylcyclohexandiisocyanat, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or l, 5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as l, 6-diisocyanato 2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate, such as 4-isocyanatomethyl-l, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediol and - triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (Hi ₂ MDI), isocyanatomethylmethylcyclohexyl isocyanate, 2,5 (2,6) -bis (isocyanato-methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-

Bis (isocyanatomethyl) cyclohexane (1,3-Hg -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in admixture.

Another preferred class of polyisocyanates as component B) are those by dimerization, trimerization, allophanatization, biuretization and / or urethanization the simple diisocyanates prepared compounds having more than two isocyanate groups per molecule, for example, the reaction products of these simple diisocyanates, such as. B. IPDI, TMDI, HDI and / or Hi ₂ MDI with polyhydric alcohols (eg., Glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines, or the triisocyanurates, 5 by trimerization of simple diisocyanates, such as IPDI, HDI and Hi ₂ MDI, are available.

The introduction of the ionic liquid (IL, component C)) can be carried out by reacting a (poly) isocyanate and / or mixtures of different (poly) isocyanates with ILs with at least

10 a isocyanate-reactive function, eg. B. OH, NH and with at least one further functional group in the way that at least one NCO function is maintained and subsequent reaction with A).

However, the introduction of component C) can also take place in-situ during the preparation of the pre-adduct.

15

For the purposes of the present invention, ionic liquids are understood as meaning salts which have a melting point of not more than 100 ^° C. For an overview of ILs, see See Welton (Chem. Rev. 99 (1999), 2071) and Wasserscheid et al. (Angew Chem 112 (2000), 3926). Preferably used as IL are salts which have a melting temperature below

20 75 ⁰ C, preferably below 5O ⁰ C, more preferably below 2O ⁰ C own. Preferably, ionic liquids contain organic cations. Preference is given to ionic liquids which have one or more cations according to the following structures,

8th

10

13 14

Wherein R 1, R ₂ , R 3, R 4, R 5 and R 6 are the same or different and are hydrogen, hydroxy, alkoxy, sulfanyl (RS), NH ₂ , NHR, NRR ', wherein R and R 'may be the same or different, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, or halogen, in particular F, Cl, Br or I, where for cations of structure 10 and 11 one of Rl to R4, preferably all Rl to R4 preferably are not hydrogen; and / or a saturated or unsaturated, linear or branched aliphatic hydrocarbon radical having 1 to 40, preferably 1 to 30, preferably 1 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and or halogen group, or may be unsubstituted; and / or a cycloaliphatic hydrocarbon radical having 5 to 30, preferably 5 to 10, preferably 5 to 8 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or can be unsubstituted; and / or an aromatic hydrocarbon radical having 6 to 30, preferably 6 to 12, preferably 6 to 10 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or can be unsubstituted; and / or an alkylaryl radical having 7 to 40, preferably 7 to 14, preferably 7 to 12 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or unsubstituted can be; and / or a linear or branched aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon radical having from 2 to 100 carbon atoms, preferably from 2 to 80 carbon atoms, particularly preferably from 2 to 40, interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ ) Carbon atoms substituted with, for example, amino, hydroxy, alkyl of 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen groups, or may be unsubstituted; and / or a one or more functionalities selected from the group -O-C (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃ ) -, -S (O) ₂ -O-, -O-S (O) ₂ -, -S (O) ₂ -NH-, - NH-S (O) ₂ -, -S (O) ₂ -N (CH ₃ ) -, -N (CH ₃ ) -S (O) ₂ -, interrupted linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, the substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or a terminal -OH, -NH ₂ , -N (H) CH ₃ -functionalized linear or branched aliphatic hydrocarbon radical having 1 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen group, or may be unsubstituted, may be.

Preferred are ionic liquids which have a cation based on ammonium, pyridinium, pyrrolidinium, pyrrolinium, oxazolium, oxazolinium, imidazolium, thiazolium or phosphonium ions.

The ionic liquids preferably have one or more anions selected from phosphate, halogen phosphates, in particular hexafluorophosphate, halides, especially chloride, alkyl phosphates, aryl phosphates, nitrate, sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, perfluorinated alkyl and aryl sulfates, sulfonate, alkyl sulfonates, aryl sulfonates, perfluorinated alkyl and aryl sulfonates, in particular trifluoromethylsulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, arylborates, amides, in particular perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, in particular acetates, preferably acetate and / or trifluoroacetate, and / or Bis (perfluoroalkylsulfonyl) amide anions, on.

In a particularly preferred embodiment of the IL, at least one salt is used which contains as cation an imidazolium, a pyridinium, an ammonium or phosphonium ion of the following structures:

Imidazolium Ion Pyridinium Ion Ammonium Ion Phosphonium Ion

wherein R 1, R 2, R 3 and R 4 may be the same or different and a saturated or unsaturated, linear or branched aliphatic hydrocarbon radical having 1 to 40, preferably 1 to 30, preferably 1 to 20 carbon atoms substituted, for example, with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or a linear or branched aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon radical having from 2 to 100 carbon atoms, preferably from 2 to 80 carbon atoms, particularly preferably from 2 to 40, interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ ) Carbon atoms which may be substituted, for example, with amino, hydroxy, alkyl of 1 to 8, preferably 1 to 4 carbon atoms and / or halogen groups, or may be unsubstituted; and / or a one or more functionalities selected from the group -O-C (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃ ) -, -S (O) ₂ -O-, -O-S (O) ₂ -, -S (O) ₂ -NH-, - NH-S (O) ₂ -, -S (O) ₂ -N (CH ₃ ) -, -N (CH ₃ ) -S (O) ₂ -, interrupted linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, the substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or a terminal -OH, -NH ₂ , -N (H) CH ₃ -functionalized linear or branched aliphatic hydrocarbon radical having 1 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen group, or may be unsubstituted, and an anion selected from tetrafluoroborate, alkylborate, in particular triethylhexylborate, arylborate, halogenphosphate, in particular hexafluorophosphate, nitrate, sulfonates, in particular perfluorinated alkyl and aryl sulfonates, hydrogen sulfate, alkyl sulfates, halides, in particular chlorides, acetates, thiocyanates, perfluorinated amides, dicyanamide and / or bis (perfluoroalkylsulfonyl) amide, in particular bis (trifluoromethanesulfonyl) amide (CF ₃ Sθ ₂ ) ₂ N).

According to the invention, a mixture of at least two different ionic liquids can also be used as component C). In this case, the IL can have at least two different anions and / or two different cations.

The reaction of A) with B) and C) can be carried out in one or two stages, wherein in a two-stage procedure, first component B) is reacted with C) in such a way that at least one free isocyanate group is retained, which is then mixed with component A ) can be implemented further. The reaction can be carried out in bulk or preferably in the presence of a suitable auxiliary solvent. Preferred solids contents when using an auxiliary solvent are 50 to 95% by mass, more preferably 55 to 80% by mass.

Suitable auxiliary solvents are either preferably those which have a boiling point below 100 ⁰ C at 1013 hPa and can be removed by distillation from the final aqueous system again completely to a residual content of 0.5 Massββ and re-use, such as acetone, methyl ethyl ketone or tetrahydrofuran , or possibly higher boiling, which remain in the aqueous system, such as butyl glycol, butyl diglycol or N-methylpyrrolidone. The below 100 ⁰ C boiling auxiliary solvents are therefore preferred because they allow the production of purely aqueous, solvent-free and therefore environmentally friendly dispersions. The use of higher-boiling solvents - possibly also proportionally - or solvent mixtures having a boiling point above 100 ⁰ C is technically possible, but not preferred and not desirable. An advantage of the method according to the invention 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. In a preferred embodiment 1), for example, one mole of a hydroxy-functional ionic liquid (component C)) with one mole of diisocyanate (component B)) is optionally reacted using a suitable solvent and a suitable catalyst such that an isocyanate group remains unreacted.

The product produced is added to a solution or melt of the hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde resins or their hydrogenated secondary products (A) and reacted.

It has proved to be advantageous, 1 mol of component A - based on M _n - with 0.25 to 10 mol, especially 0.5 to 5 mol of the reaction product of the components B) and C) to bring to reaction.

Depending on the reactivity of the components to each other, the temperature of the reaction is selected. There have in all reaction steps, temperatures from 30 to 125 ⁰ C, preferably between 50 and 100 ⁰ C proven.

The reaction product can be dispersed in water without further neutralization.

If desired, the solvent optionally present can be separated off after the end of the reaction, in which case a solution until dispersion of the product according to the invention is then generally obtained.

In a preferred embodiment 2), e.g. one mole of a di- or polyhydroxy-functional ionic liquid (component C)) with one mole of diisocyanate (component B)) per hydroxyl group, if appropriate using a suitable solvent and a suitable catalyst so that an isocyanate group based on the OH functionality remains unreacted. For example, when using a dihydroxy-functional ionic liquid, two isocyanate groups remain unreacted.

The product produced becomes a solution or melt of the hydroxy group-containing Ketone, ketone-aldehyde, urea-aldehyde or their hydrogenated secondary products (A) and reacted.

It has proved to be advantageous to react 1 mol of the component A - based on M _n - with 0.1 to 10 mol, especially 0.25 to 5 mol of the reaction product from the components B) and C).

The reaction product can be dispersed in water without further neutralization.

Optionally, a suitable catalyst for the preparation of the resins of the invention can be used. Suitable are all known in the literature compounds that accelerate an NH or OH-NC O-reaction, such as. As catalysts, based on the metals tin, bismuth, zirconium, titanium, zinc, iron and / or aluminum, such as. As carboxylates, chelates and complexes and / or purely organic catalysts such. B. tert. Amines, for example 1,4-diazabicyclo [2.2.2] octane (DABCO), l, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), N ₅ N- dimethylcyclohexylamine (DMCA) or l, 5-diazabicyclo [2.3.0] non-5-en (DBN).

If necessary, so-called chain terminators can be used to terminate the reaction. Suitable for this purpose are mono-functional compounds such as amines or alcohols. Examples include alkyl, dialkylamines, arylamines such as butylamine, benzylamine, dibutylamine, diethylamine, aliphatic and / or aromatic alcohols such as ethanol, butanol. Before addition of water, the reaction product of A), B) and C) may optionally be combined with other non-hydrophilic resins or other water-soluble or water-dilutable components and then dispersed together. This measure makes it technically advantageous to achieve a high solids content of the dispersions of more than 35% by mass, preferably from 35 to 40% by mass, to about 50% by mass.

The resin dispersions of the invention are at least 6 weeks at 50 ⁰ C sedimentation stable.

The reaction product of A), B) and C) may other excipients and additives selected from inhibitors, surfactants, oxygen and / or radical scavengers, catalysts, sunscreens, Färb brighteners, photosensitizers and initiators, additives to influence theological Properties such. Thixotropic and / or thickening agents, leveling agents, anti-skinning agents, plasticizers, defoamers, antistatic agents, lubricants, wetting and dispersing agents, other oligomers and / or polymers, e.g. Polyesters, polyacrylates, polyethers, epoxy resins, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire retardants, fillers and / or propellants.

The novel resin dispersions are suitable as the main component, base component or additional component in coating materials, ballpoint pen pastes, pigment pastes, printing inks and inks, polishes, glazes, laminations, fillers, cosmetics and / or sealants and insulating materials and adhesives.

By using the products according to the invention, moisture-insensitive coatings with good adhesion properties and good corrosion protection effect are obtained. In addition, a very good pigment wetting ability is observed.

Examples

The invention will be illustrated by the following examples.

Example 1.) a) reaction of a polyisocvanate B) with an IL C) and subsequent reaction with a ketone-aldehyde resin A)

138 g of isophorone diisocyanate 5 are added rapidly to a solution of 212 g of Tego® II Tl 6 ES (Degussa AG) and 0.2 g of dibutyltin dilaurate in 238 g of acetone in a nitrogen atmosphere with stirring, so that the exothermic reaction remains readily controllable. The mixture is then stirred at 60 ⁰ C until the NCO number of the solution has fallen below 6.5% NCO (determined according to DIN 53185).

After cooling to room temperature, the reaction product thus prepared in a nitrogen atmosphere with 388 g of a ketone / aldehyde resin (OHZ 310 mg KO H / g, resin 10 SK, Degussa AG), which is dissolved in 259 g of acetone, and 0.5 g of a 10% DBTL solution in acetone. The mixture is stirred at reflux temperature until an NCO content of less than 0.1% is reached.

b) dispersing the modified resin 1-a)

15 250 g of the solution prepared under 1) are dispersed at room temperature by addition of 350 g of demineralized water with vigorous stirring. The auxiliary solvent acetone and water are removed in vacuo, and there is a storage-stable, white resin dispersion having a solids content of about 48% by mass, a pH of 5.2 and a viscosity below 30 mPas.

20

Example 2) a) Reaction of a polyisocyanate B) with an IL C) and subsequent reaction with a ketone-aldehyde resin A)

To a solution of 371 g of Tego IL T16 ES (Degussa AG) and 0.25 g of dibutyltin dilaurate in 25 336 g of acetone are added in a nitrogen atmosphere with stirring 121 g of isophorone diisocyanate so quickly added that the exothermic reaction remains well manageable. The mixture is then stirred at 60 ⁰ C until the NCO number of the solution has fallen below 2.8% NCO (determined according to DIN 53185).

After cooling to room temperature, the reaction product thus prepared in 30 nitrogen atmosphere with 243 g of a ketone / aldehyde resin (OHZ 310 mg KO H / g, synthetic resin

SK, Degussa AG), which is dissolved in 162 g of acetone, and with 0.25 g of a 10% DBTL

Solution in acetone added. It is stirred under reflux temperature until an NCO Content below 0.1% is reached.

b) dispersing the modified resin 2-a)

250 g of the solution prepared under 1) are dispersed at room temperature by addition of 350 g of demineralized water with vigorous stirring. The auxiliary solvent acetone and water are removed in vacuo, and there is a storage-stable, white resin dispersion having a solids content of about 34% by mass, a pH of 5.6 and a viscosity below 50 mPas.

Example of a coating composition:

DI water = fully demineralized water

Adjust the viscosity with deionized water (Ford Cup 4, 23 ⁰ C) to 40 - 45 s.

Test panels: Coating structure (spray application) on phosphated steel sheet: cathodic dip coating, coating materials according to the examples, metallic basecoat, clearcoat Drying conditions: flash-off time approx. 10 min, then 20 min 16O ⁰ C

By adding the components essential to the invention 1) or 2) adhesion, intercoat adhesion and gloss of the coatings are improved.

To assess water resistance, the coatings were exposed to 100 ^° C hot steam for 30 minutes. While the coating of the comparative example already swells after 20 minutes, the coating materials according to Examples A and B were unchanged after 30 minutes. This results in an improved corrosion protection effect.

The dispersions are present in the coating composition in ranges of 1 and 90, preferably between 2 and 50, more preferably between 3 and 30 wt .-%.

Claims

claims:

1. Aqueous resin dispersions obtainable by reaction or proportionate reaction of

and then mixing the resin with water.

2. Aqueous resin dispersions according to claim 1, characterized in that C-H-acidic ketones are used in component A).

3. Aqueous resin dispersions according to one of the preceding claims, characterized in that in the ketone-aldehyde of component A), 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, cyclooctanone, cyclohexanone

Starting bonds are used alone or in mixtures.

4. Aqueous resin dispersions according to one of the preceding claims, characterized in that alkylsubstituierte in the ketone-aldehyde of component A)

Cyclohexanone having one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms, used individually or in mixture.

5. Aqueous resin dispersions according to one of the preceding claims, characterized in that in the ketone-aldehyde of component A) 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone , 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

6. Aqueous resin dispersions according to any one of the preceding claims, characterized in that acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone are used alone or in a mixture in the component A).

7. Aqueous resin dispersions according to one of the preceding claims, characterized in that as aldehyde component of the ketone-aldehyde resins in component A)

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

8. Aqueous resin dispersions according to one of the preceding claims, characterized in that are used as aldehyde component of the ketone-aldehyde resins in component A) formaldehyde and / or para-formaldehyde and / or trioxane.

9. Aqueous resin dispersions according to one of the preceding claims, characterized in that resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone alone or in mixture and formaldehyde (component A) are used.

10. Aqueous resin dispersions according to one of the preceding claims, characterized in that that as component A) resins according to claims 2 to 9, which were hydrogenated after preparation, are used.

11. Aqueous resin dispersions according to the preceding claim, characterized in that as component A) hydrogenated derivatives of the resins consisting of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone used alone or in mixture and formaldehyde become.

12. Aqueous resin dispersions according to any one of the preceding claims, characterized in that as component A) urea-aldehyde resins, prepared using a urea of the general formula (i)

R ₁ O

\

CH- / (ü)

R ₂ in the Ri and R _{2 are} hydrocarbon radicals each having up to 20 carbon atoms and / or

Formaldehyde be used.

13. Aqueous resin dispersions according to one of the preceding claims, characterized that urea-aldehyde resins prepared using urea and thiourea, methylene diurea, ethylene diurea, tetramethylene dihydrogen and / or hexamethylene diurea or mixtures thereof are used as component A).

14. Aqueous resin dispersions according to any one of the preceding claims, characterized in that as component A) urea-aldehyde resins prepared using isobutyraldehyde, formaldehyde, 2-methylpentanal, 2-ethylhexanal and 2-phenylpropanal or mixtures thereof are used.

15. Aqueous resin dispersions according to one of the preceding claims, characterized in that urea-aldehyde resins prepared using urea, isobutyraldehyde and formaldehyde are used as component A).

16. Aqueous resin dispersions according to one of the preceding claims, characterized in that diisocyanates as component B) are selected from cyclohexane diisocyanate,

Methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene 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 like 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), bis (isocyanatomethylcyclohexyl) methane (Hi ₂ 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 (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), used alone or in mixtures.

17. Aqueous resin dispersions according to one of the preceding claims, characterized in that polyisocyanates prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization simple diisocyanates, are used as component B).

18. Aqueous resin dispersions according to any one of the preceding claims, characterized in that are used as component B) isocyanates based on IPDI, TMDI, H12MDI and / or HDI.

19. Aqueous resin dispersions according to one of the preceding claims, characterized in that are used as component C) ionic liquids of organic cations.

20. Aqueous resin dispersions according to the preceding claim, characterized in that as component C) ionic liquids are used which contain one or more cations cation according to the following structures

13 14

Wherein R 1, R ₂ , R 3, R 4, R 5 and R 6 are the same or different and are hydrogen, hydroxy, alkoxy, sulfanyl (RS), NH ₂ , NHR, NRR ', wherein R and R 'same or different, substituted or unsubstituted alkyl groups with

1 to 8 carbon atoms, or halogen, in particular F, Cl, Br or I, wherein for cations of the structure 10 and 11 one of the radicals Rl to R4, preferably all radicals Rl to R4 are preferably not hydrogen; and / or a saturated or unsaturated, linear or branched aliphatic hydrocarbon radical having 1 to 40, preferably 1 to 30, preferably 1 to 20

Carbon atoms which may be substituted, for example with a hydroxy, alkyl of 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or a cycloaliphatic hydrocarbon radical having 5 to 30, preferably 5 to 10, preferably 5 to 8 carbon atoms, which is substituted, for example with a hydroxy,

Alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or an aromatic hydrocarbon radical having 6 to 30, preferably 6 to 12, preferably 6 to 10 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or can be unsubstituted; and / or an alkylaryl radical having 7 to 40, preferably 7 to 14, preferably 7 to 12 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or unsubstituted can be; and / or a linear or branched aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon radical having from 2 to 100 carbon atoms, preferably from 2 to 80 carbon atoms, particularly preferably from 2 to 40, interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ ) Carbon atoms, the substituted, for example, with amino, hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen groups, or may be unsubstituted and / or one or more functionalities selected from the group -O-C (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃ ) - , -S (O) ₂ -O-, -O-S (O) ₂ -, -S (O) ₂ -NH-, -NH-S (O) ₂ -, -S (O) ₂ -N ( CH ₃ ) -, -N (CH ₃ ) -S (O) ₂ -, interrupted linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen group, or may be unsubstituted; and / or a terminal -OH, -NH ₂ , -N (H) CH ₃ -functionalized linear or branched aliphatic hydrocarbon radical having 1 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen group, or may be unsubstituted, may be.

21. Aqueous resin dispersions according to any one of the preceding claims, characterized in that as component C) ionic liquids are used which are a cation based on ammonium, pyridinium, pyrrolidinium, pyrrolinium, oxazolium, oxazolinium, imidazolium, thiazolium or phosphonium ions.

22. Aqueous resin dispersions according to any one of the preceding claims, characterized in that as component C) ionic liquids are used, preferably one or more anions selected from phosphate, halogen phosphates, in particular

Hexafluorophosphate, halides, especially chloride, alkyl phosphates, aryl phosphates,

Nitrate, sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, perfluorinated alkyl and

Aryl sulfates, sulfonate, alkyl sulfonates, aryl sulfonates, perfluorinated alkyl and

Aryl sulfonates, in particular trifluoromethyl sulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkyl borates, arylborates,

Amides, in particular perfluorinated amides, dicyanamide, saccharinate, thiocyanate, Carboxylates, especially acetates, preferably acetate and / or trifluoroacetate, and / or bis (perfluoroalkylsulfonyl) amide anions, have.

23. Aqueous resin dispersions according to any one of the preceding claims, characterized in that as component C) ionic liquids are particularly preferably used which contain at least one salt which has as cation an imidazolium, a pyridinium, an ammonium or phosphonium ion of contains the following structures:

Imidazolium Ion Pyridinium Ion Ammonium Ion Phosphonium Ion

wherein R 1, R 2, R 3 and R 4 may be the same or different and a saturated or unsaturated, linear or branched aliphatic hydrocarbon radical having 1 to 40, preferably 1 to 30, preferably 1 to 20 carbon atoms substituted, for example, with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or may be unsubstituted; and / or a linear or branched aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon radical having from 2 to 100 carbon atoms, preferably from 2 to 80 carbon atoms, particularly preferably from 2 to 40, interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ ) Carbon atoms which may be substituted, for example, with amino, hydroxy, alkyl of 1 to 8, preferably 1 to 4 carbon atoms and / or halogen groups, or may be unsubstituted; and / or a one or more functionalities selected from the group -O-C (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃ ) -, -S (O) ₂ -O-,

-0-S (O) ₂ -, -S (O) ₂ -NH-, -NH-S (O) ₂ -, -S (O) ₂ -N (CH ₃₎ -, -N (CH ₃₎ -S (O) ₂ -, interrupted linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, which may be substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or unsubstituted; and / or a terminal -OH, -NH ₂ , -N (H) CH ₃ -functionalized linear or branched aliphatic hydrocarbon radical having 1 to 20 carbon atoms which is substituted, for example with a hydroxy, alkyl with 1 to 8, preferably 1 to 4 Carbon atoms and / or halogen group, or unsubstituted; may be, as well as an anion selected from tetrafluoroborate, alkyl borate, in particular

Triethylhexylborate, arylborate, halogenophosphate, in particular hexafluorophosphate, nitrate, sulphonates, in particular perfluorinated alkyl and arylsulphonates, hydrogensulphate, alkyl sulphates, halides, in particular chlorides, acetates, thiocyanates, perfluorinated amides, dicyanamide and / or bis (perfluoroalkylsulphonyl) amide, in particular bis ( trifluoromethanesulfonyl) amide ((CF ₃ SO ₂ ) ₂ N).

24. Aqueous resin dispersions according to one of the preceding claims, characterized in that as component C), a mixture of at least two different ionic liquids is used and in this case the IL at least two different

Anions and / or two different cations may have.

25. Resin dispersions according to one of the preceding claims, characterized in that the reaction of A) with B) and C) and the subsequent dispersion in

Water is taken in substance.

26. Resin dispersions according to one of the preceding claims, characterized in that the reaction of A) with B) and C) and the subsequent dispersion in

Water in the presence of an auxiliary solvent.

27. Resin dispersions according to one of the preceding claims, characterized in that the auxiliary solvent used has a boiling point below 100 ⁰ C at 1013 hPa.

28. Resin dispersions according to one of the preceding claims, characterized in that the auxiliary solvent used is N-methylpyrrolidone, acetone and / or methyl ethyl ketone and / or tetrahydrofuran.

29. Resin dispersions according to one of the preceding claims, characterized in that one or more non-water-soluble or water-dilutable components are added prior to addition of water.

30. A process for the preparation of aqueous resin dispersions by reaction or proportionate reaction of

A) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and B) at least one aromatic, aliphatic and / or cycloaliphatic di- or

Polyisocyanate and

C) at least one ionic liquid having an isocyanate-reactive function and having additional functional groups, and then mixing the resin with water.

31. A process for the preparation of aqueous resin dispersions according to the preceding claim, characterized in that the reaction of components A) with B) and C) is carried out in one stage or preferably two stages, wherein in two-stage operation, first component B) reacted with C) in the manner is that at least one free isocyanate group is maintained, which can then be further reacted with the component A)

32. A process for preparing aqueous resin dispersions according to the two previous claims, characterized in that a suitable catalyst can be used.

5 33. A process for the preparation of aqueous resin dispersions according to claims 30 to 32, characterized in that as a catalyst diazabicyclooctane (DABCO) or dibutyltin dilaurate (DBTL), titanic acid esters, zinc, zirconium, iron, bismuth salts are used.

34. Process for the preparation of aqueous resin dispersions according to claims 30 to 33, characterized in that chain terminators are used to terminate the reaction.

35. Process for the preparation of aqueous resin dispersions according to claims 30 to 34, 15, characterized in that chain terminators selected from monofunctional amines and / or alcohols are used to terminate the reaction.

36. Process for the preparation of aqueous resin dispersions according to claims 30 to 35, characterized in that chain terminators selected from alkyl, dialkylamines, arylamines and / or aliphatic and / or aromatic alcohols are used to terminate the reaction.

25 37. Use of the aqueous resin dispersions according to at least one of the preceding claims as main component, base component or additive component in coating materials, ballpoint pastes adhesives, printing inks and inks, polishes, glazes, laminations, pigment pastes, fillers, cosmetics and / or sealing and insulating materials.

30

38. Articles manufactured and / or coated with a coating material additive composition containing an aqueous resin dispersion according to at least one of the preceding claims.