WO2008028769A1 - Low-temperature-curable polyurethane compositions containing uretdione groups and with quaternary ammonium halides - Google Patents

Abstract

Low-temperature-curable polyurethane compositions containing uretdione groups. The invention relates to polyurethane compositions which contain uretdione groups and which cure at low baking temperatures, to processes for preparing such compositions, and to their use for producing polymers, more particularly film-forming coatings and adhesives.

Description

 Low temperature curable, uretdione group-containing

Polyurethane compositions with quaternary ammonium halides

The invention relates to uretdione-group-containing polyurethane compositions which cure at low stoving temperatures, processes for the preparation of such compositions and their use for the production of plastics, in particular lacquer coatings and adhesives.

Externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) paint and adhesive composition.

So describes z. For example, DE-OS 27 35 497 PUR coatings with excellent weathering and heat stability. The crosslinkers, the preparation of which is described in DE-OS 27 12 931, consist of ε-caprolactam blocked isocyanurate-containing isophorone diisocyanate. There are also known urethane, biuret or urea group-containing polyisocyanates whose isocyanate groups are also blocked.

The disadvantage of these externally blocked systems is the cleavage of the blocking agent during the thermal crosslinking reaction. Since the blocking agent can thus emit into the environment, special measures must be taken to clean the exhaust air and / or recovery of the blocking agent for environmental and occupational hygiene reasons. In addition, the crosslinkers have a low reactivity. Curing temperatures above 170 ^° C. are required.

DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione polyaddition compounds whose terminal isocyanate groups are blocked irreversibly with monoalcohols or monoamines.

Particularly disadvantageous are the chain terminating constituents of the crosslinkers, the insufficient network densities of the PUR paint coatings and thus moderate solvent resistance.

Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents. The compositions based on these uretdione group-containing polyisocyanates have in common that they do not emit volatile compounds in the curing reaction. However, the baking temperatures are at least 180 ⁰ C at a high level.

The use of amidines as catalysts in PU coating composition is described in EP 803 524. Although these catalysts lead to a lowering of the curing temperature, but show a considerable yellowing, which is generally undesirable in the coating area. The reason for this yellowing is probably the reactive nitrogen atoms in the amidines. These can react with atmospheric oxygen to N-oxides, which are responsible for the discoloration.

EP 803 524 also mentions other catalysts which have hitherto been used for this purpose, but without showing any particular effect on the curing temperature. These include known from polyurethane chemistry organometallic catalysts such. As dibutyltin dilaurate (DBTL), or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2] octane (DABCO).

In WO 00/34355 catalysts based on metal acetylacetonates, z. As zinc acetylacetonate claims. Such catalysts are actually capable of curing the uretdione group-containing

To reduce polyurethane powder coating compositions show as

Reaction products but mainly allophanates (M. Gedan-Smolka, F. Lehmann,

D. Lehmann "New catalysts for the low temperature curing of uretdione powder coatings" International Waterborne, High solids and Powder Coatings Symposium,

New Orleans, 21-23.2.2001). Allophanates are the reaction products one mole of alcohol and two moles of isocyanate, while in conventional urethane chemistry, one mole of alcohol reacts with one mole of isocyanate. Due to the unwanted allophanate formation so technically and economically valuable isocyanate groups are destroyed.

The object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which can be cured even at very low temperatures and are particularly suitable for the production of plastics and high-gloss or matt, light and weather-stable highly reactive coating and adhesive compositions.

Surprisingly, it has been found that certain catalysts accelerate the cleavage of uretdione groups to such an extent that, when using uretdione-containing curing agents, the curing temperature of polyurethane compositions can be considerably lowered.

Conventional uretdione-containing polyurethane compositions can be cured under normal conditions (DBTL catalysis) only from 180 ⁰ C. With the help of the low-temperature curing polyurethane compositions according to the invention not only energy and (curing) time can be saved at from 100 to 160 ⁰ C curing, but it can also be coated or bonded many temperature-sensitive substrates that at 180 ⁰ C undesirable yellowing , Decomposition and / or embrittlement phenomena. In addition to metal, glass, wood, leather, plastics and MDF boards, certain aluminum substrates are also suitable. In the latter case, an excessively high temperature load sometimes leads to an undesired change in the crystal structure.

The present invention relates to highly reactive uretdione-containing polyurethane compositions containing essentially A) at least one uretdione-containing hardener based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight, B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH / gram C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , wherein R ¹ - R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl, each linear or branched , unbridged or bridged with other radicals R ¹ - R ⁴ , with the formation of cycles, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more Alcohols, amino, ester, keto, thio, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms may have, and R ^{5 is} either Cl, Br, or I, so that the proportion of the catalyst under C) 0.001 - 5 Ge wt .-% of the total amount of components A) and B), and wherein the catalysts C) may be surrounded with an inert shell and encapsulated with it, and

D) if appropriate at least one acid group-reactive compound having a weight fraction, based on the total formulation, of 0.1 to 10%,

E) optionally at least one acid in monomeric or polymeric form in a weight proportion, based on the total formulation, of 0.1 to 10%,

F) optionally solvents,

G) optionally auxiliaries and additives.

Another object of the invention is also a process for the preparation of the polyurethane compositions.

The invention also provides the use of the polyurethane compositions according to the invention for the production of liquid and powdery

Lacquer coatings on metal, plastic, glass, wood or leather substrates or other heat-resistant substrates.

The invention also provides the use of the polyurethane compositions according to the invention as adhesive compositions for bonding metal, plastic, glass, wood or leather substrates or other heat-resistant substrates.

The invention likewise relates to metal coating compositions, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, wood coating compositions, glass coating compositions, leather coating compositions and plastic coating compositions.

Uretdione group-containing polyisocyanates are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 417,603. A comprehensive review of industrially relevant processes for the dimerization of isocyanates to uretdiones is provided by J. Prakt. Chem. 336 (1994) 185-200. In general, the reaction of isocyanates to uretdiones in the presence of soluble dimerization catalysts such. As dialkylaminopyridines, trialkylphosphines, phosphorous acid triamides or imidazoles. The reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case. In principle, a wide range of isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. According to the invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethylene diisocyanate (hydrogenated MDI) H ₁₂ MDI, 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethyl-hexamethylene diisocyanate / 2,4,4 - Trimethyl hexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI) are preferably used. Very particular preference is given to IPDI and HDI.

The implementation of these uretdione group-bearing polyisocyanates to uretdione groups having curing agents A) includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as. As polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been described frequently (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524). Preferred uretdione curing agents A) have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 35% by weight (calculated as C ₂ N ₂ O ₂ , molecular weight 84). Preference is given to polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol and monomeric dialcohols, such as. As ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropane (1, 3), butanediol (1, 4), hexanediol (1, 6), 2-methylpentanediol -1, 5, 2,2,4-thmethylhexanediol (1,6), 2,4,4-thymethylhexanediol (1,6), heptanediol (1,7), dodecanediol (1,12), octa -decene-9,10-diol- (1,12), thiodiglycol, octadecanediol (1,18), 2,4-dimethyl-2-propylheptanediol (1,3), diethylene glycol, triethylene glycol, tetraethylene glycol , trans and cis-1,4-cyclohexanedimethanol used.

In addition to the uretdione groups, the hardeners may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.

As hydroxyl-containing polymers B) it is preferred to use polyesters, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates having an OH number of 20-500 (in mg KOH / gram). Particularly preferred Polyester with an OH number of 30 - 150, an average molecular weight of 500

- 6000 g / mol. Such binders have been described, for example, in EP 669 354 and EP 254 152. Of course, mixtures of the above-mentioned polymers can be used.

The invention also provides the use of at least one catalyst C) of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , where R ¹ -R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, Heteroaryl, alkoxyalkyl, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1-18 carbon atoms and each radical R ¹ - R ^{4 may} additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, and R ^{5 is} either Cl, Br, or I. means, wherein these catalysts can be surrounded with an inert shell and thus encapsulated, in polyurethane compositions and the catalysts themselves.

The catalysts C) essential to the invention satisfy the formula [NR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where R ¹ -R ⁴ simultaneously or independently of one another are alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R ¹ -R ⁴ , with the formation of cycles, bicyclic or tricyclic radicals and the bridging atoms in addition to carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹

- R ⁴ additionally one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate, double bonds, triple bonds or

Halogen atoms may have, and R ^{5 is} either Cl, Br, or I, said catalysts may be surrounded with an inert shell and encapsulated therewith.

Examples of such catalysts under C) are tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride,

Tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium ammonium chloride chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium, benzyltriethylammonium, Benzyltripropylammoniumchlorid, benzyltributylammonium chloride, methyltributylammonium chloride, Methyltripropyl- ammoniunnchlond, ammoniunnbronnid methyltriethylammonium, Methyltriphenylammoniumchlorid, phenyltrimethylammonium, Benzyltrimethylammoniunnbronnid, Benzyltriethyl-, Benzyltripropylammoniumbronnid, bromide Benzyltributylammoniunn-, Methyltributylammoniumbromid, Methyltripropylammoniunnbronnid, methyl triethylannnnoniunnbronnid, Methyltriphenylammoniunnbronnid, Phenyltrimethylammonium chloride, benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium diiodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide and phenyltrimethylammonium iodide.

Of course, mixtures of such catalysts can be used. Particular preference is given to using tetrabutylammonium chloride. They are in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, particularly preferably from 0.5 to 1, 5 wt .-%, based on the components A) and B) in of the

Paint or adhesive composition included. The catalysts can

Contain crystal water, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted. A variant of the invention includes the polymeric attachment of such catalysts C) to the curing agent A) or to the hydroxyl-containing

Polymer B) with a. So z. B. free alcohol, thio or amino groups of

Ammonium salts with acid, isocyanate, or glycidyl groups of the hardener A) or hydroxyl-containing polymers B) are reacted to integrate the catalysts C) in the polymeric composite.

In this context, it must be noted that the activity of this

Catalysts in the presence of acids decreases significantly. The conventional reactants of the uretdione-containing hardener include hydroxyl-containing

Polyester. Due to the method of preparation of polyesters, these sometimes wear in small extent nor acid groups. In the presence of such acid-group-bearing polyesters, it makes sense to use the catalysts mentioned either in excess relative to the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.

Reactive acid-scavenging compounds D) are well known in paint chemistry. Thus, for example, epoxy compounds, carbodiimides, hydroxyalkylamides or 2-oxazolines, but also inorganic salts such as hydroxides, bicarbonates or carbonates with acid groups at elevated temperatures. In question come here z. B. Triglycidyl ether isocyanurate (TGIC), Araldit PT 910, Araldit PT912 (mixtures of di- and triglycidyl esters, Hunstman), EPIKOTE 828 (diglycidyl ether based on bisphenol A, Schell), Versaticsäureglycidylester, Ethylhexylglycidylether, Butylglycidylether, POLYPOX R 16 (pentaerythritol tetra- glycidyl ether, UPPC AG) as well as other types of polypoets with free epoxy groups, VESTAGON EP HA 320, (hydroxyalkylamide, Degussa AG), but also phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline, 2-hydroxypropyl-2- oxazoline, 5-hydroxypentyl-2-oxazoline, sodium carbonate, potassium carbonate and calcium carbonate. Of course, mixtures of such substances come into question. These reactive compounds can be used in proportions by weight of from 0.1 to 10%, preferably from 0.5 to 3%, based on the total formulation.

Acids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, phthalic acid, succinic acid, but also copolyesters or copolyamides having an acid number of at least 20. Suitable solvents under F) are all liquid substances which do not react with other ingredients, eg. Acetone, ethyl acetate, butyl acetate, xylene, Solvesso 100, Solvesso 150, methoxypropyl acetate and dibasic ester.

For the polyurethane compositions customary in the paint or adhesive technology additives G) as leveling agents, for. As polysilicone or acrylates, light stabilizers z. B. hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. Fillers and pigments such. Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.

Optionally, additional catalysts, such as are already known in polyurethane chemistry may be included. These are mainly organometallic catalysts, such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 -1 wt .-%.

The homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. As heated stirred tanks, kneaders, or extruders, carried out, with upper temperature limits of 120 to 130 ⁰ C should not be exceeded. The homogeneous mixture of all constituents, depending on the starting substances or after the use of solvents, either solid or liquid. The well-mixed mass is applied to the substrate by suitable application (eg rolling, spraying). For solid formulations, the application of ready to spray powders on suitable substrates by the known methods, such. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering. After application, the coated workpieces are heated to a temperature of 60 to 220 ⁰ C, preferably 6 to 30 minutes at 80 to 160 ⁰ C for curing for 4 to 60 minutes. The subject matter of the invention will be explained in more detail below with reference to examples.

Examples:

M.p .: melting point; T _G : glass transition point; OH number: hydroxyl number

General Preparation of Polyurethane Compositions

The crushed feedstocks are intimately mixed in a muller and then homogenized in the extruder to a maximum of 130 ⁰ C. After cooling, the extrudate is crushed and ground with a pin mill to a particle size <100 microns.

Lacquer compositions (in% by weight):

nicht erfindungsgemäßes Vergleichsbeispiel

non-inventive comparative example

Examples 2 and 3 each still contained 1, 6% Araldit PT 912, 0.5% benzoin, 1, 0% Resiflow PV 88 and 30.0% Kronos 2160

Examples 1 and V1 were sprayed onto steel sheets and cured at 30 '160 ⁰ C.

Examples 2 and 3 were sprayed on steel sheets and cured at 15 '150 ⁰ C.

results

The MEK test (double strokes) reflects the solvent resistance (methyl ethyl ketone) of the coating, while the pendulum hardness allows a statement about the hardness of the coating. Both are dependent on networking the coating. Obviously, sufficient crosslinking has taken place in Inventive Example 1, but not in Comparative Example 1.

Both examples 2 and 3 are fully cured and have good paint mechanics.

Claims

claims: 1. Highly reactive uretdione group-containing polyurethane compositions in Essentially containing A) at least one uretdione-containing hardener based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight . B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH / gram, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , wherein R ¹ - R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , with the formation of cycles, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally being one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I, such that the proportion of the catalyst under C) is 0.001-5% by weight of the total amount of components A) and B). 2. A polyurethane composition according to claim 1, characterized D) that at least one acid group-reactive compound having a weight fraction, based on the total formulation, from 0.1 to 10 wt .-% is contained and / or E) that at least one acid in monomeric or polymeric form in a Weight content, based on the total formulation of 0.1 to 10%, is included. 3. A polyurethane composition according to claim 1 or 2, characterized in that solvent F) and / or auxiliaries and additives are contained. 4. Polyurethane compositions according to at least one of claims 1 to 3, characterized in that uretdione-containing hardener A) based on isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethylene diisocyanate (H ₁₂ MDI), 2-methylpentadiisocyanate (MPDI), 2.2 , 4-trimethyl-hexamethylene diisocyanate / 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and Tetramethylxylylene diisocyanate (TMXDI), alone or in mixtures. 5. Polyurethane compositions according to claim 4, characterized in that uretdione-containing hardener based on IPDI and / or HDI are included. 6. A polyurethane composition according to at least one of claims 1 to 5, characterized in that uretdione-containing hardener A) based on hydroxyl-containing polyester, polythioether, polyether, polycaprolactams, polyepoxides, polyester amides, polyurethanes, low molecular weight di-, tri- and / or tetra alcohols, monoamines and or monoalcohols, alone or in mixtures. 7. Polyurethane compositions according to claim 6, characterized in that polyester and / or monomeric dialcohols are included. 8. Polyurethane compositions according to at least one of claims 1 to 7, characterized in that as hydroxyl-containing polymers B) polyester, polyethers, polyacrylates, Polyurethanes and polycarbonates, alone or in mixtures, are included. 9. Polyurethane compositions according to claim 8, characterized in that polyesters are contained with an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol. 10. A polyurethane composition according to any one of claims 1 to 9, characterized in that catalysts C) are selected from tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium, tetramethylammonium, tetramethylammonium, tetramethylammonium, benzyltrimethylammonium, benzyltriethylammonium chloride, benzyl tripropylammonium chloride , Benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, phenyltrimethylammonium chloride, Benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenylthymethylammoniumbromide, benzyltrimethylammoniumiodide, benzyltriethylammoniumiodide, benzyltripropylammoniumiodide, benzyltributylammoniumiodide, methyltributylammoniumiodide, Methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, phenyltrimethylammonium iodide. 11. A polyurethane composition according to at least one of claims 1 to 10, characterized in that as catalyst C) tetrabutylammonium chloride is contained. 12. A polyurethane composition according to any one of claims 1 to 1 1, characterized in that as component D) epoxy compounds, carbodiimides, hydroxyalkylamides, basic salts and / or 2-oxazolines are included. 13. A polyurethane composition according to claim 12, characterized in that triglycidyl ether isocyanurate, Araldit PT 910, Araldit PT912, EPIKOTE ^® 828, versatic, Vestagon EP HA 320, phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline, 2 -Hydroxypropyl-2-oxazoline and / or 5-hydroxypentyl-2-oxazoline, sodium carbonate, potassium carbonate or Calcium carbonate, alone or in mixtures, are included. 14. Polyurethane compositions according to at least one of claims 1 to 13, characterized in that as acid E) sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, phthalic acid, succinic acid but also copolyesters or copolyamides having an acid number of at least 20 are included. 15. A process for the preparation of highly reactive uretdione group-containing polyurethane compositions, essentially containing A) at least one uretdione-containing hardener, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5 wt .-% and a uretdione content of 1 - 35 wt .-%, B ) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH / gram, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , wherein R ¹ - R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , with the formation of cycles, bicycles or Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more alcohol, amino, ester, keto, thio, urethane, urea , Allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ either Cl, Br or I means such that the proportion of the catalyst under C) is 0.001-5% by weight of the total amount of components A) and B), by homogenization. 16. Use of at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where R ¹ -R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , to form cyclics, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally may still contain one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I in polyurethane compositions. 17. Use according to claim 16, characterized in that compounds selected from tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride , Methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, phenyltrimethylammonium chloride, Benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyl tripropylammoniumbromid, benzyltributylammonium bromide, ammonium bromide Methyltributyl-, Methyltripropylammoniumbromid, methyltriethylammonium bromide, Methyltriphenylammoniumbromid, Phenylthmethylammoniumbromid, benzyltrimethylammonium, benzyltriethylammonium, Benzyltripropyl- ammonium iodide, Benzyltributylammoniumiodid, Methyltributylammoniumiodid, Methyltripropylammoniumiodid, Methyltriethylammoniumiodid, Methyltriphenyl- ammonium iodide, Phenylthmethylammoniumiodid be used. 18. catalyst for accelerating the curing of uretdione-containing polyurethane compositions according to at least one of claims 1 to 14, essentially comprising a uretdione-containing curing agent and optionally a hydroxyl-containing polymer of the formula [NR ¹ R ² R ³ R ^{4] +} [R ^{5] ",} wherein R ¹ - R ⁴ simultaneously or independently alkyl-, aryl-, aralkyl-, heteroaryl, alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate , Double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I means 19. The catalyst of claim 18 selected from tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyl tripropylammoniumchlorid, benzyltributylammonium chloride, Methyltributyl- ammonium chloride, Methyltripropylammoniumchlorid, methyltriethylammonium chloride , Methyltriphenylammonium chloride, phenyltrimethylammonium chloride, Benzyltrimethylammonium, benzyltriethylammonium, benzyl tripropylammoniumbromid, benzyltributylammonium, Methyltributyl- bromide, Methyltripropylammoniumbromid, methyltriethylammonium bromide, Methyltriphenylammoniumbromid, Phenylthmethylammoniumbromid, benzyltrimethylammonium, benzyltriethylammonium, Benzyltripropyl- ammonium iodide, Benzyltributylammoniumiodid, Methyltributylammoniumiodid, Methyltripropylammoniumiodid, Methyltriethylammoniumiodid, Methyltriphenyl- ammonium iodide, Phenylthmethylammoniumiodid. 20. A catalyst according to claim 19, consisting of tetrabutylammonium chloride. 21. Use of polyurethane compositions substantially containing A) at least one uretdione-containing hardener based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight, B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , where R ¹ -R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, unbridged or with others R ¹ - R ⁴ bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more alcohol, amino, , Ester, keto, thio, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I, so that the proportion of the catalyst under C) is 0.001-5 wt .-% of the total amount of components A) and B), for the production of liquid and powdery Paint and adhesive compositions. 22. Use according to claim 21, characterized in that starting compounds are contained according to at least one of claims 2 to 14. 23. Use according to claim 21 or 22 for the preparation of liquid or powdered paint and adhesive compositions for metal, plastic, wood, glass, leather or other heat-resistant substrates. 24. Metal coating compositions consisting essentially of a polyurethane composition A) at least one uretdione-containing curing agent based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight, B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where R ¹ -R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, unbridged or with others R ¹ - R ⁴ bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more alcohol, amino, , Ester, keto, thio, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I, such that the proportion of the catalyst under C) is 0.001-5% by weight of the total amount of components A) and B). 25. A wood coating composition essentially comprising a polyurethane paint composition A) at least one uretdione-containing curing agent based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight, B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , wherein R ¹ - R ^{4 are} simultaneously or independently of one another alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R ¹ -R ⁴ , with formation of cycles, bicyclic or tricyclic radicals and the bridging atoms besides carbon can also be heteroatoms , with 1-18 carbon atoms and each radical R ¹ -R ⁴ additionally additionally one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br or I, so that the proportion of the catalyst under C) 0.001 to 5 wt .-% of the Total amount of components A) and B) is. 26. Leather coating compositions, essentially containing one Polyurethanrlackzusammensetzung of A) at least one uretdione-containing curing agent based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5 wt .-% and a uretdione content of 1 - 35 wt .-% . B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , wherein R ¹ - R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl, each linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , with the formation of cycles, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally being one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms, and R ^{5 is} either Cl, Br, I, such that the proportion of the catalyst under C) is 0.001-5% by weight of the total amount of components A) and B). 27. Plastic coating compositions, essentially comprising a polyurethane composition A) at least one uretdione-containing curing agent based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 35% by weight, B) optionally a hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH, C) at least one catalyst of the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ^" , where R ¹ - R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkylreste, in each case linear or branched, unbridged or bridged with other radicals R ¹ - R ⁴ , with formation of cycles, bicycles or Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1-18 carbon atoms and each radical R ¹ - R ⁴ additionally one or more alcohol, amino, ester, keto, thio, Urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ either Cl, Br or I means such that the proportion of the catalyst under C) is 0.001-5% by weight of the total amount of components A) and B). 28. Metal coating according to claim 24 for automobile bodies, motor and bicycles, building parts and household appliances. 29. Coating compositions according to one of claims 24 to 28, characterized in that at least one of the components D) to G) is contained. 30. Coating compositions according to one of claims 24 to 29, characterized in that these compounds according to at least one of claims 2 to 14 contain.