DE102006000648A1 - Ionic liquids contained resins - Google Patents

Abstract

Resins and a process for their preparation, obtainable by reacting or partially reacting DOLLAR AA) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins and / or their hydrogenated secondary products and DOLLAR AB) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate and DOLLAR AC) at least one ionic liquid which has at least one function that is reactive towards isocyanate groups, DOLLAR A and its use as a main component, base component or additional component in aqueous, solvent-containing and solvent-free coating materials, ballpoint pen pastes, pigment pastes, printing inks and Inks, polishes, glazes, fillers, cosmetic articles and / or sealants and insulation materials as well as adhesives and plastics.

Description

The The present invention relates to resins based on ionic liquids and ketone, ketone / aldehyde, urea / aldehyde resins and their hydrogenated derivatives, a process for their preparation and the Use as main component, basic component or additional component in aqueous, solvent-based and solvent-free Coating materials, ballpoint pen pastes, pigment pastes, printing inks and inks, polishes, glazes, laminations, fillers, cosmetics and / or sealing and insulating materials as well as adhesives and plastics.

Ketone-formaldehyde resins have been known for a long time. Methods for the preparation are described, for example in DE 33 24 287 , US Pat. No. 2,540,885, US Pat. No. 2,540,886, DE-PS 11 55 909, DL-PS 12 433, DE-PS-13 00 256 and DE-PS 12 56 898. The hydrogenation of these resins has been going on for a long time practiced ( DE 826 974 . DE 8 70 022 . DE 32 41 735 . JP 11012338 . US 6,222,009 ). Urea aldehyde resins are used, for example, in DE 27 57 220 , DE-OS 27 57 176 and EP 0 271 776 described.

by virtue of Their high melting points / ranges normally make such resins in coating materials e.g. used as an additive hard resin, to certain properties such as drying speed, shine, Hardness or To improve scratch resistance. Because of their relatively low molecular weight own in particular usual Ketone-aldehyde resins have a low melt and solution viscosity and are used therefore in coating materials u.a. as film-forming functional fillers.

The with the high melting points / ranges at the same time relative low molecular weight associated brittleness of these products however, the use of the resins in e.g. Coating materials in larger quantities. In addition, you can Adhesive properties of coating materials by adding larger amounts unmodified ketone, ketone / aldehyde or urea / aldehyde resins be worsened.

The The object of the invention was ketone, ketone / aldehyde or Urea / aldehyde resins and / or to modify their hydrogenated secondary products so that they are differ from the prior art by using novel compounds and to develop a process for their production. The resins should be stable to hydrolysis and in particular a lower brittleness as the resins of the prior art, but without properties such as. Shine, hardness or scratch resistance to deteriorate. In addition, adhesion properties should be of coating materials and adhesives by using these Resins supported become.

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

The Resins are stable to hydrolysis and have less brittleness as the starting resins. Adhesive properties of coating materials and adhesives are made by using the resins of the present invention positively, giving gloss, hardness and scratch resistance stay.

• A) Hydroxygruppen-haltigen Keton-, Keton/Aldehyd-, Harnstoff/Aldehyd-Harzen und/oder deren hydrierten Folgeprodukten und
• B) mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- oder Polyisocyanat und
• C) mindestens einer Ionischen Flüssigkeit, die mindestens eine gegenüber Isocyanatgruppen reaktionsfähige Funktion aufweist.

The present invention provides resins and a process for their preparation obtainable by reaction or proportionate reaction of

• A) hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins and / 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 at least one isocyanate-reactive function.

When Ketones for the preparation of the ketone and ketone aldehyde resins (component A) are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, tert-butyl methyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, Cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cyclohepanone and cyclooctanone, cyclohexanone and all alkyl-substituted Cyclohexanones having one or more alkyl radicals, in total Have 1 to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

in the Generally can but all in the literature for Ketone and ketone-aldehyde resin syntheses as suitable called ketones, usually all C-H-acidic ketones are used. Prefers are ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in admixture and ketone resins based on cyclohexanone.

When Aldehyde component of the ketone-aldehyde resins (component A) are suitable principally unsubstituted or branched aldehydes, e.g. Formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde as well as dodecanal. In general, all in the literature for ketone resin syntheses be used as suitable called aldehydes. It is preferred however, formaldehyde is used alone or in mixtures.

The needed Formaldehyde is usually as about 20 to 40 wt .-% aqueous or alcoholic (e.g., methanol or butanol) solution. Other uses formaldehyde, e.g. also the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, e.g. Benzaldehyde, may be mixed with formaldehyde Also included.

Especially preferred starting compounds for component A) are acetophenone, Cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone 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 hydrogenated in the presence of a catalyst with hydrogen at pressures of up to 300 bar. The carbonyl group of the ketone-aldehyde resin is 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:

in der X Sauerstoff oder Schwefel, A einen Alkylenrest bedeuten und n für 0 bis 3 steht, mit 1,9 (n + 1) bis 2,2 (n + 1) mol eines Aldehyds der allgemeinen Formel (ii)

in der R₁ und R₂ für Kohlenwasserstoffreste (z.B. Alkyl-, Aryl- und/oder Alkylarylreste) mit jeweils bis zu 20 Kohlenstoffatomen stehen und/oder Formaldehyd verwendet.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 the R ₁ and R _{2 are} hydrocarbon radicals (eg, alkyl, aryl and / or alkylaryl) each having up to 20 carbon atoms and / or formaldehyde used.

suitable Urea of general formula (i) with n = 0 are e.g. urea and thiourea with n = 1 methylene diurea ethylene diurea Tetramethylenediurea and / or hexamethylenediurea and their Mixtures. Preference is given to urea.

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

formaldehyde can in aqueous Form, some or all of alcohols such. Methanol or ethanol may be used as paraformaldehyde and / or trioxane.

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

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

When Component B) are suitable aromatic, aliphatic and / or cycloaliphatic Di- and / or polyisocyanates.

Examples of di- and polyisocyanates are 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 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 diisocyanate and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexylisocyanate, 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), alone or in mixture.

Another preferred class of polyisocyanates as component B) are the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of the simple diisocyanates with more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, TMDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (for example glycerol, trimethylolpropane, pentaerythritol) or polyvalent polyamines, or the triisocyanurates obtainable by trimerization of the simple diisocyanates, such as, for example, IPDI, HDI and H ₁₂ MDI.

The introduction the ionic liquid (IL, component C)) can be prepared by reacting a (poly) isocyanate and / or mixtures of different (poly) isocyanates with ILs with at least one opposite Isocyanate reactive groups Function, e.g. OH, NH and at least one other functional Group done in the way that at least one NCO function obtained stays and then Implementation with A).

The introduction the component C) can also in situ during Präaddukt production respectively.

wobei R1, R2, R3, R4, R5 und R6, gleich oder unterschiedlich sind und Wasserstoff, Hydroxy-, Alkoxy-, Sulfanyl- (R-S-), NH₂-, NHR-, NRR'-Gruppe, wobei R und R' gleiche oder unterschiedliche, substituierte oder unsubstituierte Alkylgruppen mit 1 bis 8 Kohlenstoffatomen sein können, oder Halogen, insbesondere F, Cl, Br oder I, wobei für Kationen der Struktur 10 und 11 einer der Reste R1 bis R4, bevorzugt alle Reste R1 bis R4 vorzugsweise ungleich Wasserstoff sind; und/oder ein gesättigter oder ungesättigter, linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 1 bis 40, vorzugsweise 1 bis 30, bevorzugt 1 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 30, vorzugsweise 5 bis 10, bevorzugt 5 bis 8 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein aromatischer Kohlenwasserstoffrest mit 6 bis 30, vorzugsweise 6 bis 12, bevorzugt 6 bis 10 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein Alkylarylrest mit 7 bis 40, vorzugsweise 7 bis 14, bevorzugt 7 bis 12 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein durch ein oder mehrere Heteroatome (Sauerstoff, NH, NCH₃) unterbrochener linearer oder verzweigter aliphatischer und/oder cycloaliphatischer und/oder aromatischer Kohlenwasserstoffrest mit 2 bis 100 Kohlenstoffatomen, bevorzugt mit 2 bis 80 Kohlenstoffatomen, besonders bevorzugt mit 2 bis 40 Kohlenstoffatomen, der substituiert, beispielsweise mit Amino-, Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppen, oder unsubstituiert sein kann; und/oder ein durch ein oder mehrere Funktionalitäten, ausgewählt aus der Gruppe -O-C(O)-, -(O)C-O-, -NH-C(O)-, -(O)C-NH, -(CH₃)N-C(O)-, -(O)C-N(CH₃)-, -S(O)₂-O-, -O-S(O)₂-, -S(O)₂-NH-, -NH-S(O)₂-, -S(O)₂-N(CH₃)-, -N(CH₃)-S(O)₂-, unterbrochener linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein endständig -OH, -NH₂, -N(H)CH₃ funktionalisierter linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann.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 a review of ILs, see, for example, Welton (Chem. Rev. 99 (1999), 2071) and Wasserscheid et al. (Angew Chem 112 (2000), 3926). Preferably used as IL are those salts which have a melting temperature below 75 ° C, preferably below 50 ° C, particularly preferably below 20 ° C. Preferably, ionic liquids contain organic cations. Preference is given to ionic liquids which have one or more cations according to the following structures,

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 ', where R and R' identical or different, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, or halogen, in particular F, Cl, Br or I, wherein for cations of structure 10 and 11 one of the radicals R1 to R4, preferably all radicals R1 to R4 are 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 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 one or more functionalities selected from the group -OC (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃₎ -, -S (O) ₂ -O-, -OS (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, 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 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.

Prefers become ionic liquids, which is 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, alkyl borates, aryl borates, amides, in particular perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, in particular acetates, preferably acetate and / or trifluoroacetate, and / or bis (perfluoroalkylsulfonyl) amide anions.

wobei R1, R2, R3 und R4 gleich oder unterschiedlich sein können und ein gesättigter oder ungesättigter, linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 1 bis 40, vorzugsweise 1 bis 30, bevorzugt 1 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein durch ein oder mehrere Heteroatome (Sauerstoff, NH, NCH₃) unterbrochener linearer oder verzweigter aliphatischer und/oder cycloaliphatischer und/oder aromatischer Kohlenwasserstoffrest mit 2 bis 100 Kohlenstoffatomen, bevorzugt mit 2 bis 80 Kohlenstoffatomen, besonders bevorzugt mit 2 bis 40 Kohlenstoffatomen, der substituiert, beispielsweise mit Amino-, Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppen, oder unsubstituiert sein kann; und/oder ein durch ein oder mehrere Funktionalitäten, ausgewählt aus der Gruppe -O-C(O)-, -(O)C-O-, -NH-C(O)-, -(O)C-NH, -(CH₃)N-C(O)-, -(O)C-N(CH₃)-, -S(O)₂-O-, -O-S(O)₂-, -S(O)₂-NH-, -NH-S(O)₂-, -S(O)₂-N(CH3)-, -N(CH₃)-S(O)₂-, unterbrochener linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann; und/oder ein endständig -OH, -NH₂, -N(H)CH₃ funktionalisierter linearer oder verzweigter aliphatischer Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, der substituiert, beispielsweise mit einer Hydroxy-, Alkyl mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatomen und/oder Halogen-Gruppe, oder unsubstituiert sein kann, sowie ein Anion ausgewählt aus Tetrafluorborat, Alkylborat, insbesondere Triethylhexylborat, Arylborat, Halogenphosphat, insbesondere Hexafluorphosphat, Nitrat, Sulfonate, insbesondere perfluorierte Alkyl- und Arylsulfonate, Hydrogensulfat, Alkylsulfate, Halogenide, insbesondere Chloride, Acetate, Thiocyanate, perfluorierte Amide, Dicyanamid und/oder Bis(perfluoralkylsulfonyl)amid-, insbesondere Bis(trifluormethansulfonyl)amid ((CF₃SO₂)₂N).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:

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 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 / 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 one or more functionalities selected from the group -OC (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃₎ -, -S (O) ₂ -O-, -OS (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 of 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, alkyl borate, especially triethylhexyl, arylborate, halogen phosphate, especially hexafluorophosphate, nitrate, sulfonates, especially perfluorinated alkyl and aryl sulfonates, hydrogen sulfate, alkyl sulfates, halides, in particular Chlorides, acetates, thiocyanates, perfluorinated amides, dicyanamide and / or bis (perfluoroalkylsulfonyl) amide, especially bis (trifluoromethanesulfonyl) amide ((CF ₃ SO ₂ ) ₂ N).

According to the invention can as Component C) also a mixture of at least two different ionic species liquids be used. Here, the IL can be at least two different Have anions and / or two different cations.

The Reaction of A) with B) and C) can take place in one or two stages, wherein in two-stage driving first component B) with C) is reacted in the way that at least one free isocyanate group is maintained, which then reacted with the component A) on can be.

The Reaction may be in bulk or in the presence of a suitable solvent respectively. Preferred solids contents are when using a solvent 40 to 95% by mass, particularly preferably 50 to 80% by mass.

When solvent suitable are those that are opposite Isocyanates are inert. Preference is given, e.g. Acetates, ketones, ethers, Glycol ethers, aliphatics, aromatics, ionic liquids without isocyanate-reactive groups alone or in mixture. It can but also so-called reactive diluents can be used in UV-curing Coating materials usually Find application such. Acrylate-functionalized mono-, di- or higher Alcohols.

In a preferred embodiment 1) are used e.g. one mole of a hydroxy-functional ionic liquid (Component C)) with one mole of diisocyanate (component B)) optionally under Use of a suitable solvent and a suitable catalyst so reacted that an isocyanate group remains unreacted.

The product prepared is added to a solution or melt of the hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde or their hydrogenated derivatives (A) and ge to the reaction ge introduced.

It has proved to be advantageous, 1 mol of component A) - based on M _n - with 0.2 to 15 mol, especially 0.25 to 10 mol of the reaction product of the components B) and C) to bring to reaction.

ever after reactivity the components of each other, the temperature of the reaction is selected. It have temperatures between 30 and 125 ° C, preferably between 50 and 100 ° C proven.

In a preferred embodiment 2), one mole (relative to M _n ) of a solution or melt of the hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde resins or their hydrogenated secondary products (A) with, for example, one mole of a hydroxy-functional ionic liquid (component C )) and one mole of diisocyanate (component B)), if appropriate, using a suitable solvent and a suitable catalyst until the NCO number is less than 0.2%.

It has proved to be advantageous to react 1 mol of component A), based on M _n , with in each case from 0.2 to 15 mol, in particular from 0.25 to 10 mol, of components B) and C).

ever after reactivity the components of each other, the temperature of the reaction is selected. It have temperatures between 30 and 125 ° C, preferably between 50 and 100 ° C proven.

Possibly may be a suitable catalyst for the preparation of the resins of the invention be used. All known in the literature are suitable Compounds which have a NH or Accelerate OH-NCO reaction, e.g. Catalysts, based on the metals tin, bismuth, zirconium, titanium, zinc, iron and / or Aluminum, e.g. Carboxylates, chelates and complexes and / or pure organic catalysts such as e.g. tert. Amines, for example, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), N, N-dimethylcyclohexylamine (DMCA) or 1,5-diazabicyclo [2.3.0] non-5-ene (DBN).

The Reaction product from A), B) and C) can be further auxiliaries and additives, selected from organic solvents, Water, inhibitors, surface-active Substances, oxygen and / or Radical scavengers, Catalysts, light stabilizers, color whiteners, photosensitizers and initiators, additives for influencing rheological properties such as. Thixotropic agents and / or thickening agents, leveling agents, anti-skinning agents, Plasticisers, defoamers, Antistatic agents, lubricants, wetting and dispersing agents, others Oligomers and / or polymers, e.g. Polyesters, polyacrylates, Polyethers, epoxy resins, preservatives such as e.g. also fungicides and / or biocides, thermoplastic additives, dyes, pigments, Matting agents, fire retardants, fillers and / or blowing agents, contain.

The glass transition temperature (T _g ) of the reaction products of A) and B) and C) is between -30 and 120 ° C, preferably between -10 and 100 ° C, more preferably between 0 and 80 ° C.

The molecular weight M _{n of} the products according to the invention is between 500 and 30,000 g / mol. preferably between 750 and 10,000 g / mol, more preferably between 800 and 5,000 g / mol.

The molecular weight M _{w of} the products according to the invention is between 1,000 and 80,000 g / mol. preferably between 1,500 and 20,000 g / mol, more preferably between 1,500 and 10,000 g / mol.

The Gardner color number (50% in ethyl acetate) of the products according to the invention is between 0 and 10, preferably between 0 and 7, particularly preferred between 0 and 5.

The resins of the invention are saponification-stable, have a low brittleness and are suitable as the main component, base component or additional component in aqueous, solvent-based and solvent-free Coating materials, ballpoint pen pastes, pigment pastes, printing inks and inks, polishes, glazes, fillers, cosmetics and / or sealing and insulating materials as well as adhesives and plastics, in particular for improvement of adhesion properties with good gloss, good hardness and scratch resistance.

Examples

The The following examples are intended to illustrate the invention made but further do not restrict their scope:

Example 1.)

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

To a solution from 212 g of Tego IL T16 ES (Degussa AG) and 0.2 g of dibutyltin dilaurate in 238 g of acetone under stirring in a nitrogen atmosphere, 138 g of isophorone diisocyanate added so quickly that the exothermic reaction well manageable remains. Subsequently one stirs at 60 ° C continue until the NCO number of the solution is 6.5% NCO (determination after DIN 53185) has fallen below.

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 KOH / g, resin SK, Degussa AG), which is dissolved in 259 g of acetone, and 0.5 g of a 10% added DBTL solution in acetone. It is stirred at reflux temperature until an NCO content of less than 0.1% (determined according to DIN 53185) is reached. The reaction product is freed from the solvent.
Glass transition temperature = 7 ° C; Mn = 2,100 g / mol; M _w 4,600; Gardner color number (50% in ethyl acetate) = 3.8.

Example 2.)

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

To a mixture of 235 g of a ketone / aldehyde resin (OHZ 310 mg KOH / g, resin SK, Degussa AG), 78 g Tego IL K5 (Degussa AG) and 0.1 g dibutyltin dilaurate with stirring in a nitrogen atmosphere at 140 ° C 31 , Added 35 g of isophorone diisocyanate so quickly that the exothermic reaction remains well manageable. The temperature is then increased within one hour to 180 ° C and held until the NCO number is less than 0.05% (determined according to DIN 53185).
Melting point = 91 ° C; Glass transition temperature = 43 ° C; Mn = 1,000 g / mol; M _w 2,100; Gardner color number (50% in ethyl acetate) = 2.8.

Example 3.)

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

To a mixture of 243 g of a ketone / aldehyde resin (OHZ 310 mg KOH / g, Kunstharz SK, Degussa AG), 81 g of Tego IL P51P (Degussa AG) and 0.1 g of dibutyltin dilaurate with stirring in a nitrogen atmosphere at 140 ° C 32 , Added 35 g of isophorone diisocyanate so quickly that the exothermic reaction remains well manageable. The temperature is then increased within one hour to 180 ° C and held until the NCO number is less than 0.05% (determined according to DIN 53185).
Melting point = 99 ° C; Glass transition temperature = 46 ° C; Mn = 1,300 g / mol; M _w 3,200; Gardner color number (50% in ethyl acetate) = 3.8. Example of a coating material composition

Messerkratzhaftung auf unterschiedlichen Substraten:

• 0 = sehr gute Haftung; 10 = keine Haftung

The resin solutions A (comparison) and I-III were applied with a doctor blade to a glass plate and on different plastic plates. The wet layer thickness was 100 μm. The coated test plates were stored after evaporation of the volatiles for 14 days under standard conditions (23 ° C, 50% relative humidity). Then, gloss and adhesion of the films were determined. Film properties:

Knife scratch adhesion on different substrates:

• 0 = very good adhesion; 10 = no liability

Abbreviations

• ABS: acrylonitrile-butadiene-styrene copolymer
• PC: polycarbonate
• PE: polyethylene
• PVC: polyvinyl chloride

By Addition of the invention essential components are elasticity, adhesion, Scratch resistance of the coatings improved without gloss and Hardness negative to be influenced.

Claims (38)

Resins available through implementation or pro-rata implementation of A) hydroxy-containing Ketone, ketone / aldehyde, urea / aldehyde resins and / or their hydrogenated derivatives and B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate and C) at least one ionic liquid containing at least one across from Isocyanate group reactive function having. Resins according to claim 1, characterized in that used in the ketone-aldehyde resins of component A) C-H-acidic ketones become. Resins according to at least one of the preceding claims, characterized characterized in that in the ketone-aldehyde resins 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 as starting bonds used alone or in mixtures. Resins according to at least one of the preceding claims, characterized characterized in that in the ketone-aldehyde resins of component A) alkyl-substituted cyclohexanones having one or more alkyl radicals, which have a total of 1 to 8 hydrocarbon atoms, individually or in mixture. Resins according to at least one of the preceding claims, characterized characterized in that in the ketone-aldehyde resins of component A) 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone. Resins according to at least one of the preceding claims, characterized characterized in that acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or mixed in component A) become. Resins according to at least one of the preceding claims, characterized characterized in that as aldehyde component of the ketone-aldehyde resins in component A) formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde, dodecanal alone or in mixtures be used. Resins according to at least one of the preceding claims, characterized characterized in that as aldehyde component of the ketone-aldehyde resins in component A) formaldehyde and / or para-formaldehyde and / or Trioxane can be used. Resins according to at least one of the preceding claims, characterized characterized in that resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, Heptanone alone or in mixture and formaldehyde (component A) be used. Resins according to at least one of the preceding claims, characterized characterized in that as component A) resins according to claims 2 to 9, which after preparation were hydrogenated, are used. Resins according to the preceding claim, characterized that as component A) hydrogenated derivatives of the resins consisting from acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, Heptanone alone or in mixture and formaldehyde. Resins according to at least one of the preceding claims, characterized in that as component A) urea-aldehyde resins, prepared 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 each having up to 20 carbon atoms and / or formaldehyde used. Resins according to at least one of the preceding claims, characterized characterized in that prepared as component A) urea-aldehyde resins using urea and thiourea methylene diurea Ethylene diurea tetramethylene diurea and / or hexamethylene diurea or mixtures thereof are used. Resins according to at least one of the preceding claims, characterized characterized in that prepared as component A) urea-aldehyde resins using isobutyraldehyde, formaldehyde, 2-methylpentanal, 2-ethylhexanal and 2-phenylpropanal or mixtures thereof used become. Resins according to at least one of the preceding claims, characterized characterized in that produced as component A) urea-aldehyde resins using urea isobutyraldehyde and formaldehyde become. Resins according to at least one of the preceding claims, characterized in that di- and triisocyanates are selected as component B) 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, 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, dodecanedi and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexylisocyanate, 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. Resins according to at least one of the preceding claims, characterized characterized in that polyisocyanates prepared by dimerization, Trimerization, allophanatization, biuretization and / or urethanization simple diisocyanates, are used as component B). Resins according to at least one of the preceding claims, characterized in that as component B) isocyanates based on IPDI, TMDI, H ₁₂ MDI and / or HDI are used. Resins according to at least one of the preceding claims, characterized characterized in that as component C) ionic liquids organic cations are used. Resins according to the preceding claim, characterized in that as component C) ionic liquids are used which contain one or more cations according to the following structures

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 ', where R and R' identical or different, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, or halogen, in particular F, Cl, Br or I, wherein for cations of structure 10 and 11 one of the radicals R1 to R4, preferably all radicals R1 to R4 are 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 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 one or more functionalities selected from the group consisting of OC (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃ ) -, -S (O) ₂ -O-, -OS (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, substituted, for example, with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or unsubsti can be tuiert; 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. Resins according to at least one of the preceding claims, characterized characterized in that as component C) ionic liquids containing a cation based on ammonium, pyridinium, Pyrrolidinium, pyrrolinium, oxazolium, oxazolinium, imidazolium, Thiazolium or phosphonium ions have. Resins according to at least 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, especially trifluoromethylsulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, arylborates, amides, especially perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, especially acetates Acetate and / or trifluoroacetate, and / or bis (perfluoroalkylsulfonyl) amide anions. Resins according to at least one of the preceding claims, characterized in that as component C) ionic liquids are particularly preferably used which contain at least one salt, which as cation an imidazolium, a pyridinium, an ammonium or phosphonium ion of the following structures includes:

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 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 / 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 one or more functionalities selected from the group -OC (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O) CN (CH ₃₎ -, -S (O) ₂ -O-, -OS (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, 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 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; and an anion selected from tetrafluoroborate, alkyl borate, in particular triethylhexyl borate, aryl borate, halogenophosphate, 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, especially bis (trifluoromethanesulfonyl) amide ((CF ₃ SO ₂ ) ₂ N). Resins according to at least one of the preceding claims, characterized characterized in that as component C) also a mixture of at least two different ionic liquids is used and in this case the IL at least two different anions and / or may have two different cations. Resins according to at least one of the preceding claims, characterized in that the reaction product of A), B) and C) 1 mol of component A) - based on M _n - and 0.2 to 15 mol, especially 0.25 to 10 mol of components B) and C). Resins according to at least one of the preceding claims, characterized characterized in that other auxiliaries and additives are included. Resins according to at least one of the preceding claims, characterized in that further auxiliaries and additives selected from inhibitors, surface-active substances, organic solvents, water, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for Influence rheological properties such as thixotropic with fillers and / or thickeners, leveling agents, skin preventatives, plasticizers, defoamers, antistatic agents, lubricants, wetting and dispersing agents, further oligomers and / or polymers, such as polyesters, polyacrylates, polyethers, epoxy resins, preservatives, such as, for example, fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire retardants, fillers and / or blowing agents. Resins according to at least one of the preceding claims, characterized in that • the glass transition temperature (T _g ) of the reaction products of A) and B) and C) is between -30 and 120 ° C, preferably between -10 and 100 ° C, more preferably between 0 and 80 ° C is; The molecular weight M _{n of} the products according to the invention is between 500 and 30,000 g / mol. preferably between 750 and 10,000 g / mol, more preferably between 800 and 5,000 g / mol; The molecular weight M _{w of} the products according to the invention is between 1,000 and 80,000 g / mol. preferably between 1,500 and 20,000 g / mol, more preferably between 1,500 and 10,000 g / mol; The color number according to Gardner (50% in ethyl acetate) of the products according to the invention is between 0 and 10, preferably between 0 and 7, particularly preferably between 0 and 5. Resins according to at least one of the preceding claims, characterized characterized in that the reaction of A) with B) and C) in substance he follows. Resins according to at least one of the preceding claims, characterized characterized in that the reaction of A) with B) and C) in the presence of a solvent he follows. Resins according to at least one of the preceding claims, characterized characterized in that the solvents used are isocyanates are inert. Resins according to at least one of the preceding claims, characterized characterized in that the solvents used are selected from acetates, ketones, ethers, glycol ethers, aliphatics, aromatics, reactive for UV-curing coating materials, Ionic liquids without isocyanate-reactive groups alone or in a mixture. Process for the preparation of resins by reaction or proportionate implementation of A) hydroxyl-containing ketone, Ketone / aldehyde, urea / aldehyde resins and / or their hydrogenated derivatives and B) at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate and C) at least an ionic liquid, the at least one opposite Isocyanate group reactive function has and additional has functional groups, by single-stage or two-stage Implementation of A) with B) and C), with two-stage driving first the Component B) is reacted with C) in such a way that at least a free isocyanate group is maintained, which then with the component A) can be reacted further, at temperatures between 30 and 125 ° C, preferably between 50 and 100 ° C. Process for the preparation of resins after the previous one Claim, characterized in that a suitable catalyst can be used. Process for the preparation of resins according to claims 33. to 34., characterized in that catalysts based on Metals tin, bismuth, zirconium, titanium, zinc, iron and / or aluminum, such as. Carboxylates, chelates and complexes and / or purely organic Catalysts such as e.g. tert. Amines, for example, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), N, N-dimethylcyclohexylamine (DMCA) or 1,5-diazabicyclo [2.3.0] non-5-ene (DBN). Use of the resins after at least one of the previous ones claims as main component, basic component or additional component in solvent-containing, solvent-free and aqueous Coating materials, ballpoint pastes, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials as well as plastics. Use of the resins after at least one of the previous ones claims as main component, basic component or additional component in solvent-containing, solvent-free and aqueous Coating materials, ballpoint pastes, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials for improving elasticity, scratch resistance and adhesion properties with good gloss and good hardness. objects manufactured and / or coated with a coating composition, which contains a resin according to at least one of the preceding claims.