WO2007077058A1

WO2007077058A1 - Resins containing ionic liquids

Info

Publication number: WO2007077058A1
Application number: PCT/EP2006/068866
Authority: WO
Inventors: Patrick GLÖCKNER; Friedrich Georg Schmidt
Original assignee: Degussa Ag
Priority date: 2006-01-03
Filing date: 2006-11-24
Publication date: 2007-07-12
Also published as: DE102006000648A1; CN101003608A

Abstract

The invention relates to resins and to a method for their production, said resins being obtained by the reaction or proportional reaction of A) ketone resins, ketone/aldehyde resins and urea/aldehyde resins containing hydroxy groups and/or their hydrogenated resultant products with B) at least one aromatic, aliphatic and/or cycloaliphatic di- or polyisocyanate and C) at least one ionic liquid, which has at least one reactive function vis-à-vis isocyanate groups. The invention also relates to the use of said resins as the main constituent, base constituent or additional constituent in aqueous coating substances that contain and are devoid of solvents, ballpoint pen pastes, pigment pastes, printing inks and inks, polish, glazes, fillers, cosmetics and/or sealing and insulating materials, in addition to adhesives and synthetic materials.

Description

IONIC LIQUIDS CONTAINING RESINS

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, base component or additive component in aqueous, solvent-borne and solvent-free coating materials, Ballpoint pen pastes, pigment pastes, printing inks and inks, polishes, glazes, laminations, fillers, cosmetics and / or sealants and insulating materials, and adhesives and plastics.

Ketone-formaldehyde resins have been known for a long time. Process for the preparation are for. As described in DE 33 24 287, US-PS 2,540,885, US-PS 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 practiced for a long time (DE 826 974, DE 8 70 022, DE 32 41 735, JP 11012338, US 6,222,009). Urea aldehyde resins are e.g. in DE 27 57 220, DE-OS 27 57 176 and EP 0 271 776 described.

Due to their high melting points / ranges such resins are normally used in coating materials z. B. used as an additive hard resins to improve certain properties such as drying tendency, gloss, hardness or scratch resistance. Because of their relatively low molecular weight, in particular, customary ketone-aldehyde resins have a low melt viscosity and solution viscosity and therefore serve, for example, in coating materials. as film-forming functional fillers.

However, the brittleness of these products associated with the high melting points / ranges coupled with relatively low molecular weight prevents the use of the resins in e.g. Coating materials in larger quantities. In addition, adhesion properties of coating materials can be impaired by the addition of relatively large amounts of unmodified ketone, ketone / aldehyde or urea / aldehyde resins.

The object of the invention was to modify ketone, ketone / aldehyde or urea / aldehyde resins and / or their hydrogenated secondary products so that they stand out from the stand Differentiate the technology by using novel compounds and to develop a process for their preparation. The resins are said to be stable to saponification and in particular to have lower brittleness than the prior art resins without, however, degrading properties such as gloss, hardness or scratch resistance. In addition, adhesion properties of coating materials and adhesives should be supported by using these resins.

The problem 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 (hereinafter abbreviated to IL) implemented ,

The resins are stable to hydrolysis and have less brittleness than the starting resins. Adhesive properties of coating materials and adhesives are positively influenced by using the resins according to the invention, wherein gloss, hardness and scratch resistance are retained.

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.

Suitable 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 from 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 admixture. 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.

In general, however, all in the literature for ketone and ketone Aldehydharzsynthese called suitable ketones, usually all C-H-acidic ketones, can be 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 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:

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 the Ri and R _{2 are} hydrocarbon radicals (eg., Alkyl, aryl and / or alkylaryl radicals) each having up to 20 carbon atoms and / or formaldehyde 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 Hexamethylendiharnstoff 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 and polyisocyanates are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate,

Propylcyclohexandiisocyanat, Methyldiethylcyclohexandiisocyanat, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexanediisocyanate, such as hexamethylene diisocyanate (HDI) or l, 5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, as l, 6 Diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonantriisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate , Undecanediol and triisocyanate, dodecanedi 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 _O -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 the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such. For example, IPDI, TMDI, HDI and / or Hi ₂ MDI with polyhydric alcohols (eg., Glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines, or the triisocyanurates obtained 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 having at least one isocyanate-reactive function, for. B. OH, NH and carried out 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 be carried out in situ during the preparation of the pre-adduct.

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 such salts are used as the IL, which has a melting temperature below 75 ⁰ C, preferably below 5O ⁰ C, more preferably below 2O ⁰ C hold. Preferably, ionic liquids contain organic cations. Preference is given to ionic liquids which have one or more cations according to the following structures,

)

10

11 12

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 an interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ ) linear or branched aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon radical having 2 to 100 carbon atoms, preferably having 2 to 80 carbon atoms, particularly preferably having 2 to 40 carbon atoms, which is substituted, for example with amino, hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen atoms 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.

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 - 0-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, alkyl borate, especially triethylhexylborate, arylborate, halogenophosphate, 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, 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, component B) is first reacted with C) in such a way that at least one free isocyanate group is retained, which is then reacted with component A). can be implemented further.

The reaction can be carried out in bulk or in the presence of a suitable solvent. Preferred solids contents when using a solvent 40 to 95% by mass, particularly preferably 50 to 80% by mass.

Suitable solvents are those which are inert to isocyanates. Preference is given, e.g. Acetates, ketones, ethers, glycol ethers, aliphatics, aromatics, ionic liquids without isocyanate-reactive groups alone or in mixture. However, it is also possible to use what are known as reactive diluents which are customarily used in UV-curable coating materials, such as e.g. Acrylate-functionalized mono-, di- or higher alcohols.

In a preferred embodiment 1), e.g. one mole of a hydroxy-functional ionic liquid (component C)) with one mole of diisocyanate (component B)), if appropriate using a suitable solvent and a suitable catalyst, so 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 or their hydrogenated derivatives (A) and reacted.

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. 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.

In a preferred embodiment, 2) a mole of (related to M _n) of a solution or melt of the hydroxy group-containing ketone, ketone aldehyde, urea-aldehyde resins or their hydrogenated derivatives (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).

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.

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-NCO 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, N-dimethylcyclohexylamine (DMCA) or l, 5-diazabicyclo [2.3.0] non-5-en (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 brighteners, photosensitizers and initiators, additives for Influencing theological properties such. B. thixotropic and / or thickening agents, leveling agents, Anti-skinning agents, plasticizers, defoamers, antistatic agents, lubricants, wetting and dispersing agents, other oligomers and / or polymers, such as 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 glass transition temperature (T _g ) of the reaction products of A) and B) and C) is between -30 and 12O ⁰ C, preferably between -10 and 100 ⁰ C, more preferably between 0 and 8O ⁰ C. The molecular weight M _{n of} the inventive Products 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 preferably between 0 and 5.

The resins according to the invention are stable to hydrolysis, 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,

Cosmetic articles and / or sealants and insulating materials and adhesives and plastics, in particular for improving adhesion properties with good gloss, good hardness and scratch resistance. Examples

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

Restrict scope:

Example 1.)

Reaction of a polyisocyanate B) with an IL C) and subsequent reaction with a

Ketone-aldehyde resin A)

To a solution of 212 g of Tego IL T16 ES (Degussa AG) and 0.2 g of dibutyltin dilaurate in 238 g of acetone are added in a nitrogen atmosphere with stirring 138 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 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 KOH / g, synthetic resin

SK, Degussa AG), which is dissolved in 259 g of acetone, and with 0.5 g of a 10% DBTL

Solution in acetone added. It is stirred under reflux temperature until an NCO

Content below 0.1% (determination according to DIN 53185) is reached. The reaction product is freed from the solvent. Glass transition temperature = 7 ⁰ 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, Kunstharz SK, Degussa AG), 78 g Tego IL K5 (Degussa AG) and 0.1 g of dibutyltin dilaurate are added with stirring in a nitrogen atmosphere at 14O ⁰ C 31.35 g of isophorone diisocyanate so quickly added that the exothermic reaction remains well manageable. Then the temperature is increased within one hour to 18O ⁰ 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 ⁰ 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, synthetic resin

SK, Degussa AG), 81 g of Tego IL P51P (Degussa AG) and 0.1 g of dibutyltin dilaurate are added with stirring in a nitrogen atmosphere at 14O ⁰ C 32.35 g of isophorone diisocyanate so quickly added that the exothermic reaction remains well manageable. Then the temperature is increased within one hour to 18O ⁰ C and held until the NCO number is less than 0.05% (determined according to DIN 53185). Melting point = 99 ⁰ 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 composition:

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 ⁰ C, 50% relative humidity). Then, gloss and adhesion of the films were determined. Film own shanks:

Knife 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 adding the components essential to the invention, elasticity, adhesion, scratch resistance of the coatings are improved, without adversely affecting gloss and hardness.

Claims

claims:

1. Resins obtainable by implementation or pro-rata implementation of

C) at least one ionic liquid having at least one isocyanate-reactive function.

2. Resins according to claim 1, characterized in that in the ketone-aldehyde of component A) C-H-acidic ketones are used.

3. Resins according to at least one of the preceding claims, 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 are used as starting bonds alone or in mixtures.

4. Resins according to at least one of the preceding claims, characterized in that in the ketone-aldehyde resins of component A) alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms, individually or in mixture.

5. Resins according to at least one of the preceding claims, 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.

6. Resins according to at least one of the preceding claims, characterized in that acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone are used alone or mixed in component A).

7. Resins according to at least 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 iso-butyraldehyde, valeric aldehyde, dodecanal are used alone or in mixtures.

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

9. Resins according to at least 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. Resins according to at least 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. Resins 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 alone or in mixture and formaldehyde are used ,

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

Formaldehyde be used.

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

14. Resins according to at least 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. Resins according to at least one of the preceding claims, characterized in that as component A) urea-aldehyde resins are prepared using urea, isobutyraldehyde and formaldehyde are used.

16. Resins according to at least one of the preceding claims, characterized in that di- and triisocyanates as component B) 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,

Hexanediocanate, such as hexamethylene diisocyanate (HDI) or l, 5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, Nonandiis ocyanat, such as 1,6-diisocyanato-2,4,4-trimethylhexane or l, 6-diisocyanato -2,2,4-trimethylhexane (TMDI),

Nonantriis ocyanat, such as 4-isocyanatomethyl-1,8-octanediisocyanate (TIN), decane and triisocyanate, undecanediol and triisocyanate, dodecanedi and triisocyanates,

Isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (Hi ₂ 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.

17. Resins according to at least 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. Resins according to at least one of the preceding claims, characterized in that as component B) isocyanates based on IPDI, TMDI, Hi ₂ MDI and / or HDI are used.

19. Resins according to at least one of the preceding claims, characterized in that are used as component C) ionic liquids of organic cations.

20. 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

8th

10

11 12

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 from 1 to 40, preferably 1 to 30, preferably 1 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 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 may 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 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 2 to 100 carbon atoms, preferably 2 to 80, interrupted by one or more heteroatoms (oxygen, NH, NCH ₃ )

Carbon atoms, particularly preferably having 2 to 40 carbon atoms, which may be substituted, for example with amino, hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen groups, or unsubstituted and / or a by one or several 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 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 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.

21. Resins according to at least 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. 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, 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.

23. 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 containing as cation an imidazolium, a pyridinium, an ammonium or phosphonium ion of contains the following structures:

Imidazolium Ion Pyridinium Ion Ammonium Ion Phosphonium Ion

where R 1, R 2, R 3 and R 4 may be identical 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 having 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 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 one by 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 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, in particular

Bis (trifluoromethanesulfonyl) amide ((CF ₃ SO ₂ ) ₂ N).

24. Resins according to at least one of the preceding claims, characterized in that as component C) is also a mixture of at least two different ionic

Liquids is used and in this case the IL can have at least two different anions and / or two different cations.

25. 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).

26. Resins according to at least one of the preceding claims, characterized in that further auxiliaries and additives are contained.

27. 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 influencing 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 blowing agents are included.

28. 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 12O ⁰ C, preferably between -10 and 100 ⁰ C, more preferably between 0 and 8O ⁰ 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 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.

29. Resins according to at least one of the preceding claims, characterized in that the reaction of A) with B) and C) takes place in substance.

30. Resins according to at least one of the preceding claims, characterized in that the reaction of A) with B) and C) takes place in the presence of a solvent.

31. Resins according to at least one of the preceding claims, characterized in that the solvents used are inert to isocyanates.

32. Resins according to at least one of the preceding claims, characterized in that the solvents used are selected from acetates, ketones, ethers, glycol ethers, aliphatic, aromatic, reactive diluents for UV-curable coating materials, ionic liquids without isocyanate-reactive groups alone or in admixture.

33. Process for the preparation of resins by reaction or proportionate reaction of

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

by one-stage or two-stage reaction of A) with B) and C), 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 then reacted further with component A) can be at temperatures between 30 and 125 ⁰ C, preferably between 50 and 100 ⁰ C.

34. Process for the preparation of resins according to the preceding claim, characterized in that that a suitable catalyst can be used.

35. A process for the preparation of resins according to claims 33 to 34, characterized in that 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, N-dimethylcyclohexylamine (DMCA) or l, 5-diazabicyclo [2.3.0] non-5-en (DBN).

36. Use of the resins according to at least one of the preceding claims as the main component, base component or additive component in solvent-borne, solvent-free and aqueous coating materials, ballpoint pastes adhesives, inks and inks, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials and plastics ,

37. Use of the resins according to at least one of the preceding claims as main component, base component or additional component in solvent-borne, solvent-free and aqueous coating materials, ballpoint pen adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers,

Cosmetic articles and / or sealing and insulating materials for improving elasticity, scratch resistance and adhesion properties with good gloss and good hardness.

38. Articles, manufactured and / or coated with a coating composition comprising a resin according to at least one of the preceding

Contains claims.